PROCEDE DE PURIFICATION D?UNE HUILE DE PYROLYSE

PROCESS FOR PURIFYING A PYROLYSIS OIL

Abrégé français

La présente invention concerne un procédé de purification d?une huile de pyrolyse, consistant à fournir un courant S0 comprenant une huile de pyrolyse, l?huile de pyrolyse comprenant un ou plusieurs composés organiques halogénés et un ou plusieurs composés organiques comprenant des doubles liaisons conjuguées ; à soumettre le courant S0 à une hydrogénation dans au moins une zone de réaction Z1 contenant un catalyseur d?hydrogénation hétérogène, pour obtenir un courant S1 qui, par rapport à S0, est appauvri en le ou les composés organiques comprenant des doubles liaisons conjuguées ; à soumettre le courant S1 à une déshalogénation dans au moins une zone de déshalogénation Z2 en aval de Z1, pour obtenir un courant S2 qui, par rapport à S1, est appauvri en le ou les composés organiques halogénés.

Abrégé anglais

The present invention relates to a process for purifying a pyrolysis oil comprising providing a stream S0 comprising a pyrolysis oil, the pyrolysis oil comprising one or more halogenated organic compounds and one or more organic compounds comprising conjugated double bonds; subjecting the stream S0 to hydrogenation in at least one reaction zone Z1 containing a heterogeneous hydrogenation catalyst, obtaining a stream S1 being depleted, compared to S0, in the one or more organic compounds comprising conjugated double bonds; subjecting the stream S1 to dehalogenation in at least one dehalogenation zone Z2 downstream of Z1, obtaining a stream S2 being depleted, compared to S1, in the one or more halogenated organic compounds.

Revendications

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PCT/EP2022/080004
Claims
1. A process for purifying a pyrolysis oil, the process comprising:
(i) providing a stream SO comprising a pyrolysis oil, the pyrolysis oil
comprising one or
more halogenated organic compounds and one or more organic compounds com-
prising conjugated double bonds;
(ii) subjecting the stream SO provided in (i) to hydrogenation in at least
one reaction
zone Z1 containing a heterogeneous hydrogenation catalyst, obtaining a stream
S1
being depleted, compared to SO, in the one or more organic compounds
comprising
conjugated double bonds;
(iii) subjecting the stream S1 obtained from (ii) to dehalogenation in at
least one dehalo-
genation zone Z2 downstream of Z1, obtaining a stream S2 being depleted, com-
pared to S1, in the one or more halogenated organic compounds.
2. The process of claim 1, wherein the pyrolysis oil according to (i)
comprises the one or
more organic compounds comprising conjugated double bonds in a total amount in
the
range of from 0.1 to 75 g(I2)/100 g, preferably from 0.4 to 60 g(I2)/100 g,
more preferably
from 1 to 30 g(I2)/100 g of the pyrolysis oil.
3. The process of claim 1 or 2, wherein the one or more organic compounds
comprising con-
jugated double bonds comprise one or more organic compounds according to
formula (I)
R1R201=02R3-03R4=x (1)
wherein =X is =0, =S, =NR5, or =C4R6R7, preferably =C4R6R7;
wherein preferably R1, R2, R3, R4, R5 are, independently of each other, H,
alkyl having
from 1 to 6 carbon atoms, alkenyl having from 1 to 6 carbon atoms, or aryl
having from 5
to 10 carbon atoms, more preferably H;
wherein preferably R6 and R7 are, independently of each other, H, alkyl having
from 1 to 6
carbon atoms, alkenyl having from 1 to 6 carbon atoms, or aryl having from 5
to 10 carbon
atoms, more preferably H; or wherein preferably either R4 and R5 or R4 and R7
are linked
together, thus forming, together with C3=C4, an aromatic ring preferably
having 5 or 6
members;
wherein the one or more organic compounds according to formula (I) more
preferably
comprise one or more of butadiene, isoprene, dienes having 5 or 6 carbon
atoms, styrene,
methylstyrene, indene, substituted styrene, substituted indene, and 3-methyl-2-
butenal,
more preferably comprise one or more of butadiene, isoprene, dienes having 5
or 6 car-
bon atoms, styrene, methylstyrene, indene, and 3-methyl-2-butenal;
wherein more preferably the one or more organic compounds according to formula
(I)
comprise styrene.
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4. The process of any one of claims 1 to 3, wherein the heterogeneous
hydrogenation cata-
lyst according to (ii) comprises an element of the groups 8 to 12, preferably
8 to 10, more
preferably 9 and 10, of the periodic table of elements, preferably an element
selected from
the group consisting of Ni, Pd and Co, more preferably from the group
consisting of Ni and
Pd;
wherein the heterogeneous hydrogenation catalyst according to (ii) preferably
further
comprises a support material for said element of the groups 8 to 12 of the
periodic table of
elements, wherein the support material is more preferably selected from the
group con-
sisting of an oxidic material and carbon, wherein the oxidic material is more
preferably one
or more of alumina, silica, magnesia, zirconia, titania, a zeolitic material,
a silica-alumina
phosphate (SAPO) material, zinc oxide, sodium oxide, mixed silica-alumina,
zeolite and
calcium oxide, more preferably alumina.
5. The process of any one of claims 1 to 4, wherein (ii) comprises
(ii.1) introducing a gas stream GO into Z1, the gas stream comprising H2;
(ii.2) introducing the stream SO into Z1;
(ii.3) bringing SO in contact with GO and the heterogeneous hydrogenation
catalyst com-
prised in Z1, obtaining a stream S1 being depleted, compared to SO, in the one
or
more organic compounds comprising conjugated double bonds;
(11.4) removing S1 from Z1;
wherein the gas stream GO is preferably introduced at a pressure in the range
of from 10
to 100 bar(abs), more preferably from 15 to 90 bar(abs), more preferably from
20 to 80
bar(abs), more preferably in the range of from 20 to 55 bar(abs).
6. The process of claim 5, wherein the gas stream GO has a temperature in
the range of 100
to 250 C, preferably from 120 to 220 C, more preferably from 140 to 200 C.
7. The process of any one of claims 1 to 6, preferably of any claim as far
as being dependent
on claim 2, wherein the stream S1 obtained from (ii) and subjected to
dehalogenation in
(iii) comprises the one or more organic compounds comprising conjugated double
bonds
in a total amount in the range of from 0 to 3 g(I2)/100 g, preferably from 0
to 2 g(I2)/100g,
more preferably from 0 to 1 g(I2)/100 g, preferably from 0 to 0.25 g(I2)/100
g, more pref-
erably from 0 to 0.1 g(I2)/100 g of the stream S1.
8. The process of any one of claims 1 to 7, wherein the stream S1 subjected
to dehalogena-
tion in (iii) has a temperature in the range of from 150 to 450 C, preferably
from 200 to
400 C, more preferably from 250 to 350 'C.
9. The process of any one of claims 1 to 8, wherein (iii) comprises
(iii.1) introducing a gas stream G1 into Z2 preferably being an adsorption
zone, preferably
a gas stream comprising one or more of hydrogen and nitrogen, more preferably
hydrogen;
(iii.2) introducing the stream S1 obtained from (ii) into Z2;
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(iii.3) bringing S1 in contact with G1 and a heterogeneous adsorbent material
suitable for
adsorbing halide comprised in at least one of the one or more halogenated
organic
compounds comprised in Z2, obtaining a stream S2 being depleted, compared to
S1, in the one or more halogenated organic compounds;
(iii.4) removing S2 from Z2.
10. The process of claim 9, wherein the gas stream G1 has a temperature in
the range of 250
to 500 C, preferably in the range of from 300 to 400 'C;
wherein the gas stream G1 is preferably introduced at a pressure in the range
of from 1 to
1 0 1 00 bar(abs), more preferably in the range of from 5 to 80 bar(abs),
more preferably in the
range of from 10 to 50 bar(abs).
11. The process of any one of claims 1 to 8, wherein the dehalogenation
zone Z2 according to
(iii) comprises, preferably is a catalytic zone, preferably comprising a
heterogeneous
dehalogenation catalyst, said catalyst comprising one or more catalytically
active ele-
ments of groups 8 to 12 of the periodic system of elements.
12. The process of any one of claims 1 to 11, wherein the stream S2
obtained from (iii) has a
total chlorine content in the range of from 0 to 200 wppm (ppm by weight),
preferably from
0 to 160 wppm, more preferably from 0 to 130 wppm.
13. The process of any one of claims 1 to 12, further comprising
(iv) subjecting the stream S2 obtained from (iii) to hydroprocessing in at
least one reac-
tion zone Z3 downstream of Z2, Z3 comprising a heterogeneous hydroprocessing
catalyst; obtaining a stream S3;
wherein the stream S2 subjected to (iv) has a temperature in the range of from
150 to
400 C, preferably in the range of from 200 to 375 C, more preferably in the
range of from
250 to 350 C;
wherein the heterogeneous hydroprocessing catalyst used in (iv) preferably
comprises an
element of the groups 8 to 10, preferably 9 and 10 of the periodic table of
elements, more
preferably an element selected from the group consisting of Ni and Co, wherein
the hy-
drogenation catalyst more preferably comprises Ni;
wherein the heterogeneous hydroprocessing catalyst according to (iv) more
preferably
comprises Ni in an amount, calculated as NiO, in the range of from 0.5 to 10
weight-%,
more preferably in the range of from 1 to 6 weight-%, based on the weight of
the hydro-
genation catalyst.
14. The process of claim 13, wherein (iv) comprises
(iv.1) introducing a gas stream G2 into Z3, G2 comprising H2;
(iv.2) introducing the stream S2 obtained from (iii) into Z3;
(iv.3) bringing S2 in contact with G2 and a heterogeneous hydroprocessing
catalyst com-
prised in Z3, obtaining a stream S3;
(iv.4) removing S3 obtained in (iv.3) from Z3.
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15. The process of any one of claims 1 to 14, being a continuous or
semi-continuous process,
preferably a continuous process.
16. A production unit for carrying out the process for purifying a pyrolysis
oil according to any
one of claims 1 to 15, the unit comprising
at least one reaction zone Z1, Z1 comprising a heterogeneous hydrogenation
cata-
lyst;
an inlet means for introducing SO into Z1;
an outlet means for removing S1 from Z1;
at least one dehalogenation zone Z2, Z2 preferably comprising a heterogeneous
adsorption material or a heterogenous dehalogenation catalyst;
an inlet means for introducing S1 into Z2;
an outlet means for removing S2 from Z2;
wherein Z1 is located upstream of Z2;
and preferably an extraction zone to remove halides, preferably comprising one
or more
halides of N-containing organic compounds, said extraction zone preferably
being ar-
ranged downstream of Z2;
wherein the production unit preferably further comprising
at least one reaction zone Z3, Z3 comprising a heterogeneous hydroprocessing
cat-
alyst;
an inlet means for introducing S2 into Z3;
an outlet means for removing S3 from Z3;
wherein Z2 is located upstream of Z3.
17. A purified pyrolysis oil, obtainable or obtained by a process
according to any one of claims
1 to 12 and 15 or according to any one of claims 13 to 15.
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Description

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Process for purifying a pyrolysis oil
The present invention relates to a process for purifying a pyrolysis oil
comprising a hydrogena-
tion step prior to a dehalogenation step, a production unit for carrying out
said process and a
purified pyrolysis oil obtained or obtainable by said process.
Currently, plastic waste is still largely landfilled or incinerated for heat
generation. Chemical re-
cycling is an attractive way to convert waste plastic material into useful
chemicals. An important
technique for chemically recycling plastic waste is pyrolysis. The pyrolysis
is a thermal degrada-
tion of plastic waste in an inert atmosphere and yields value added products
such as pyrolysis
gas, liquid pyrolysis oil and char (residue), wherein pyrolysis oil is the
major product. The pyrol-
ysis gas and char can be used as fuel for generating heat, e.g. for reactor
heating purposes.
The pyrolysis oil can be used as source for syngas production and/or processed
into chemical
feedstock such as ethylene, propylene, C4 cuts, etc. for example in a (steam)
cracker.
Typically, the plastic waste is mixed plastic waste composed of different
types of polymers. The
polymers are often composed of carbon and hydrogen in combination with other
elements such
as chlorine, bromine, fluorine, sulfur, oxygen and nitrogen that complicate
recycling efforts. The
elements other than carbon and hydrogen may be harmful during the further
processing of the
crude pyrolysis oil, since they may deactivate or poison catalysts used in the
further processing
of the pyrolysis oil. During (steam) cracking, halogen-containing compounds
can damage the
cracker by corrosion in that they release hydrogen halide. Sulfur-containing
compounds can
deactivate or poison catalysts used in the cracker, or can contaminate the
cracker products.
Nitrogen containing impurities may also poison downstream catalysts. In
addition, they may
cause a safety problem by forming explosive NOx when heated. When mixed
plastics contain-
ing polyvinyl chloride (PVC) is thermally degraded, compounds having double
carbon bonds
and hydrogen chloride is formed. The hydrogen chloride liberated from PVC
attacks the com-
pounds having carbon-carbon double bonds leading to the formation of
chlorinated organic
compounds. Plastic waste typically contains heteroatom containing additives
such as stabilizers
and plasticizers that have been incorporated to improve the performance of the
polymers. Such
additives also often comprise nitrogen, halogen and sulfur containing
compounds and heavy
metals. For example, waste engine oils, transformer oils, hydraulic oils and
machine oils may
contain heavy metal abrasion. The heavy metals are often toxic and the quality
of the pyrolysis
oil is reduced by the presence of heavy metal impurities. Furthermore, plastic
waste often may
be uncleaned plastics with residue that may also contain elements other carbon
and hydrogen.
Therefore, the reduction of the nitrogen, sulfur, halogen content in the
pyrolysis oil as well as
the heavy-metal content is essential for any profit-generating processing of
the pyrolysis oil.
Especially, a high quality pyrolysis oil rich in carbon and hydrogen and low
in elements other
than carbon and hydrogen is preferred as feedstock to prevent catalyst
deactivation and corro-
sion problems in downstream refinery processes.
WO 2017/083018 Al discloses a process for reducing chloride content of a
hydrocarbon feed
stream. Further, FR 3 103 822 discloses a process for treating pyrolysis oil
for subsequent
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steam cracking, said process comprises a hydrogenation step prior to a
hydroprocessing step.
However, there is still a need to provide improved process for purifying
pyrolysis oil obtained
from plastic waste.
Therefore, there is a need to provide a process for purifying pyrolysis oils,
preferably obtained
from plastic waste, in particular by reducing the diene content as well as
chlorine, nitrogen and
sulfur contents. Indeed, there is a need to provide high value purified
pyrolysis oils while using
an economic process.
It was surprisingly found that the process of the present invention permits to
reduce the diene
content as well as chlorine, nitrogen and sulfur contents, such reduced
amounts being particu-
larly adapted for subsequent steam cracking. Further, it was surprisingly
found that the process
of the present invention was an economic process providing high value purified
pyrolysis oils.
Further, it was found that dehalogenation of pyrolysis oil may turn out to be
an essential step to
sustain steady reactor downstream operation. A reason for the instability is
believed to be the
formation of ammonium halide such as ammonium chloride which may desublimate
upon lower-
ing the temperature of the effluent of a hydroprocessing step. As nitrogen is
typically present in
larger amounts in the pyrolysis oil feed than halogene such as chlorine, and
can only be re-
moved via hydroprocessing and then is present as ammonia, it is believed to be
essential to
lower the halogen content upstream of a hydroprocessing step, thus avoiding
desublimation of
ammonium halide and and reducing its absolute content.
Furthermore, it is believed that corrosive attack of technical equipment can
be reduced as e.g.
HCI is produced from organic chlorides under hydroprocessing conditions.
Ammonium chloride
itself may cause corrosion, too.
Yet further, it was found that at operations as dechlorination and/or
hydroprocessing, catalytic
and/or adsorbent performance suffers from increased contents of dienes and/or
conjugated ar-
omatic olefins. Their oligomerization respective polymerization is believed to
be caused by in-
creased temperature and/or radical forming compounds as e.g. peroxides or
other impurities as
acids or metal salts acting such as lewis acids. It was found that such oligo-
or polymerization
can coke the catalyst and/or the adsorbent or block their pore system reducing
accessibility of
reactants to the catalyst and/or adsorbent.
Therefore, the present invention relates to a process for purifying a
pyrolysis oil, the process
comprising:
(i) providing a stream SO comprising a pyrolysis oil, the pyrolysis oil
comprising one or more
halogenated organic compounds and one or more organic compounds comprising
conju-
gated double bonds;
(ii) subjecting the stream SO provided in (i) to hydrogenation in at least
one reaction zone Z1
containing a heterogeneous hydrogenation catalyst, obtaining a stream Si being
deplet-
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ed, compared to SO, in the one or more organic compounds comprising conjugated
dou-
ble bonds;
(iii) subjecting the stream Si obtained from (ii) to dehalogenation in at
least one dehalogena-
tion zone Z2 downstream of Z1, obtaining a stream S2 being depleted, compared
to Si, in
the one or more halogenated organic compounds.
The term "dehalogenation" as used in the context of the present invention
generally comprises
"dechlorination", "debromination" as well as "defluorination". According to
the present invention,
the term "dehalogenation" preferably comprises "dechlorination". If, e.g., the
pyrolysis oil to be
subjected to the process according to the present invention does not contain
brominated organ-
ic compounds and fluorinated organic compounds, but only chlorinated compounds
as halogen-
ated organic compounds, the term "dehalogenation" would be directed to
"dechlorination", and
the process of the invention would a process for purifying a pyrolysis oil,
the process compris-
ing:
(i) providing a stream SO comprising a pyrolysis oil, the pyrolysis oil
comprising one or more
chlorinated organic compounds and one or more organic compounds comprising
conju-
gated double bonds;
(ii) subjecting the stream SO provided in (i) to hydrogenation in at least
one reaction zone Z1
containing a heterogeneous hydrogenation catalyst, obtaining a stream Si being
deplet-
ed, compared to SO, in the one or more organic compounds comprising conjugated
dou-
ble bonds;
(iii) subjecting the stream Si obtained from (ii) to dechlorination in at
least one dechlorination
zone Z2 downstream of Z1, obtaining a stream S2 being depleted, compared to
Si, in the
one or more chlorinated organic compounds;
wherein a preferred step (iii) would comprise
(iii.1) introducing a gas stream G1 into Z2 preferably being an adsorption
zone, more preferably
a gas stream comprising one or more of hydrogen and nitrogen, more preferably
hydro-
gen;
(iii.2) introducing the stream Si obtained from (ii) into Z2;
(iii.3) bringing Si in contact with G1 and a heterogeneous adsorbent material,
suitable for ad-
sorbing chloride comprised in at least one of the one or more chlorinated
organic com-
pounds, comprised in Z2, obtaining a stream S2 being depleted, compared to Si,
in the
one or more chlorinated organic compounds;
(iii.4) removing S2 from Z2.
Generally, the pyrolysis oil comprised in SO can be a non-treated crude
pyrolysis oil. Further,
the pyrolysis oil comprised in SO can be a suitably pretreated crude pyrolysis
oil. Such suitable
pretreatment procedures are non-hydrogenation methods and include, but are not
restricted to,
distillation, dilution, precipitation, filtration, and extraction. The said
crude pyrolysis oil can be
subjected to one suitable pretreatment procedure, or to two or more suitable
pretreatment pro-
cedures.
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If the pretreatment is, for example, a distillation, it is possible to enrich
the pyrolysis oil with re-
spect to at least one of the one or more organic compounds comprising
conjugated double
bonds, or with respect to at least one of the one or more halogenated organic
compounds, or
with respect to at least one of the one or more organic compounds comprising
conjugated dou-
ble bonds and at least one of the one or more halogenated organic compounds.
If the pretreat-
ment is, for example, a dilution, it is possible to add one or more alkanes.
By doing so, it may be
possible to precipitate one or more asphaltenes from the mixture resulting
from dilution which
may then be removed by filtration. If the pretreatment is, for example, an
extraction, it is possi-
ble to use an aqueous extraction medium, such as an acidic aqueous extraction
medium or a
basic extraction medium.
Generally, from 1 to 100 weight-% or from 5 to 100 weight-% or from 10 to 100
weight-% or
from 20 to 100 weight-% or from 30 to 100 weight-% or from 40 to 100 weight-%
or from 50 to
100 weight-% or from 60 to 100 weight-% or from 70 to 100 weight-% or from 80
to 100 weight-
% or from 90 to 100 weight-% of SO may consist of pyrolysis oil.
Preferably from 95 to 100 weight-%, more preferably from 98 to 100 weight-%,
more preferably
from 99 to 100 weight-%, of SO consist of pyrolysis oil.
It is possible that from 99.5 to 100 weight-% or from 99.8 to 100 weight-% or
from 99.9 weight-
% of SO consist of pyrolysis oil.
Preferably the pyrolysis oil according to (i) comprises the one or more
organic compounds com-
prising conjugated double bonds in a total amount in the range of from 0.1 to
75 g(I2)/100 g,
more preferably from 0.4 to 60 g(I2)/100 g, more preferably from 1 to 30
g(I2)/100 g of the py-
rolysis oil, determined as described in Reference Example 1.
Preferably the one or more organic compounds comprising conjugated double
bonds comprise
one or more organic compounds according to formula (I)
R1R2C1=C2R3-C3R4=X (I)
wherein =X is =0, =S, =NR5, or =C4R6R7, preferably =C4R6R7.
Preferably R1, R2, R3, R4, R5 are, independently of each other, H, alkyl
having from 1 to 6 carbon
atoms, alkenyl having from 1 to 6 carbon atoms, or aryl having from 5 to 10
carbon atoms, more
preferably H.
Preferably R6 and R7 are, independently of each other, H, alkyl having from 1
to 6 carbon at-
oms, alkenyl having from 1 to 6 carbon atoms, or aryl having from 5 to 10
carbon atoms, more
preferably H.
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Alternatively, preferably either R4 and R6 or R4 and R1 are linked together,
thus forming, togeth-
er with C3=C4, an aromatic ring more preferably having 5 or 6 members.
Preferably the one or more organic compounds according to formula (1) comprise
one or more
of butadiene, isoprene, dienes having 5 or 6 carbon atoms, styrene, methyl
styrene, indene,
substituted styrene, substituted indene, and 3-methyl-2-butenal, more
preferably comprise one
or more of butadiene, isoprene, dienes having 5 or 6 carbon atoms, styrene,
methyl styrene,
indene, and 3-methyl-2-butenal.
As to the one or more organic compounds according to formula (1), it is
preferred that they com-
prise styrene.
Preferably the pyrolysis oil according to (i) has a styrene content in the
range of from 0.2 to 30
Area%, more preferably in the range of from 1 to 20 Area%, determined as
described in Refer-
ence Example 8.
Any halogenated organic compounds can be comprised in the pyrolysis oil
comprised in SO
provided in (i). Preferably the one or more halogenated organic compounds
comprise one or
more of mono-, oligo- or polyhalogenated aromatic compounds, alkyl halides and
alkenyl hal-
ides.
In the context of the present invention, the pyrolysis oil to be purified can
have any chlorine con-
tent. It is however preferred that the pyrolysis oil has a total chlorine
content in the range of
from 30 to 3,000 wppm (ppm by weight), more preferably from 30 to 500 wppm,
more preferably
from 30 to 200 wppm, determined as described in Reference Example 2.1.
In the context of the present invention, the pyrolysis oil to be purified can
have any chloride con-
tent. It is however preferred that the pyrolysis oil has a chloride content of
at most 100 wppm,
more preferably in the range of from 0 to 30 wppm, determined as described in
Reference Ex-
ample 2.2.
In the context of the present invention, the pyrolysis oil to be purified can
have any nitrogen con-
tent. It is however preferred that the pyrolysis oil has a nitrogen content in
the range of from 50
to 20,000 wppm (ppm by weight), more preferably from 50 to 5,000 wppm, more
preferably from
100 to 4,000 wppm, determined as described in Reference Example 3.
In the context of the present invention, the pyrolysis oil to be purified can
have any sulfur con-
tent. It is however preferred that the pyrolysis oil has a sulfur content in
the range of from 50 to
30,000 ppm by weight (wppm), preferably from 50 to 5,000 wppm, more preferably
from 100 to
3,000 wppm, determined as described in Reference Example 4.
In the context of the present invention, the pyrolysis oil is preferably
obtained from plastic waste.
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In the context of the present invention, the "plastic waste" to be pyrolyzed
typically is mixed or
pre-sorted plastic waste. However, it is also possible to use plastic waste
resulting from tires,
plastic waste which is pure polymeric plastic waste, or film waste, including
soiling, adhesive
materials, fillers, residues, etc. The pyrolysis oil to be purified can
typically comprise a solid
phase and a liquid phase, wherein the liquid phase includes an organic phase
and an aqueous
phase. For example, a weight ratio between the aqueous phase and the organic
phase in the
liquid phase of the pyrolysis oil can be in the range of from 0.01:1 to 3.2:1,
preferably in the
range of from 0.05:1 to 3:1.0
In the context of the present invention, the stream SO is preferably a liquid
stream. It is conceiv-
able that the pyrolysis oil is at least partially in the form of a wax which,
prior to be subjected to
the process of the present invention, is suitably liquefied.
Pre-Hydrogenation
As to (ii), the stream SO subjected to hydrogenation in (ii) has preferably a
temperature in the
range of from 60 to 250 C, more preferably from 80 to 220 C, more preferably
from 100 to 200
'C.
In the context of the present invention, any heterogeneous hydrogenation
catalyst can be used
as far as it permits to hydrogenate (pre-hydrogenation) according to (ii) the
stream SO compris-
ing the pyrolysis oil to be purified prior to the dehalogenation according to
(iii). Preferably, the
heterogeneous hydrogenation catalyst according to (ii) comprises an element of
the groups 8 to
12, more preferably 8 to 10, more preferably 9 and 10, of the periodic table
of elements, more
preferably an element selected from the group consisting of Ni, Pd and Co,
more preferably
from the group consisting of Ni and Pd.
Preferably, the heterogeneous hydrogenation catalyst according to (ii) further
comprises a sup-
port material for said element of the groups 8 to 12 of the periodic table of
elements, wherein
the support material is preferably selected from the group consisting of an
oxidic material and
carbon, wherein the oxidic material is more preferably one or more of alumina,
silica, magnesia,
zirconia, titania, a zeolitic material, a silica-alumina phosphate (SAPO)
material, zinc oxide,
sodium oxide, mixed silica-alumina, zeolite and calcium oxide, more preferably
alumina.
As to the heterogeneous hydrogenation catalyst according to (ii), it is
preferred that said catalyst
comprises Ni, more preferably in an amount, calculated as NiO, in the range of
from 0.5 to 70
weight-%, more preferably from 0.75 to 45 weight-%, more preferably from 1 to
20 weight-%,
based on the total weight of the hydrogenation catalyst.
Preferably, the heterogeneous hydrogenation catalyst according to (ii) further
comprises an el-
ement of the group 6 of the periodic table of elements, wherein the element of
the group 6 is
more preferably one or more of Mo and W, more preferably Mo.
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Preferably, the heterogeneous hydrogenation catalyst according to (ii)
comprises from 1 to 40
weight-%, more preferably from 2 to 35 weight-%, more preferably from 3 to 30
weight-% of an
oxide of said element of the group 6, more preferably Mo oxide or W oxide,
based on the total
weight of the hydrogenation catalyst.
Preferably, the heterogeneous hydrogenation catalyst according to (ii)
comprises Ni and Mo
supported on a support material, more preferably a support material as defined
in in the forego-
ing. More preferably, the hydrogenation catalyst comprises Ni and Mo supported
on alumina.
As to the heterogeneous hydrogenation catalyst according to (ii), it is
alternatively preferred that
said catalyst comprises Pd, more preferably in an amount, calculated as
elemental Pd, in the
range of from 0.01 to 5 weight-%, more preferably from 0.1 to 1 weight-%, more
preferably from
0.15 to 0.8 weight-%, based on the total weight of the catalyst.
Preferably, the heterogeneous hydrogenation catalyst according to (ii) further
comprises a pro-
nnoter, the promoter more preferably being one or more of an element of the
groups 10 and 11
of the periodic table of elements, preferably one or more of Cu, Au, Ag, and
Pt, more preferably
one or more of Ag and Pt, more preferably Ag.
Preferably, the atomic ratio of the element of groups 8 to 12 of the periodic
table, more prefera-
bly Pd, relative to the promoter is in the range of from 0.1:1 to 10:1, more
preferably from 2:1 to
7:1, more preferably from 2.5:1 to 6:1.
Preferably, the heterogeneous hydrogenation catalyst according to (ii)
comprises Pd supported
on a support material, preferably a support material as defined in the
foregoing, wherein the
support material is more preferably alumina or carbon, more preferably
alumina.
In the context of the present invention, the heterogeneous hydrogenation
catalyst according to
(ii) preferably is in the form of extrudates, pellets, rings, spherical
particles or spheres, more
preferably spherical particles or extrudates.
Preferably, (ii) comprises
(ii.1) introducing a gas stream GO into Z1, the gas stream comprising H2;
(ii.2) introducing the stream SO into Z1;
(ii.3) bringing SO in contact with GO and the heterogeneous hydrogenation
catalyst comprised
in Z1, obtaining a stream Si being depleted, compared to SO, in the one or
more organic
compounds comprising conjugated double bonds;
(ii.4) removing Si from Z1.
Preferably, the gas stream GO has a temperature in the range of 100 to 250 C,
more preferably
from 120 to 220 C, more preferably from 140 to 200 C.
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Preferably, the gas stream GO is introduced at a pressure in the range of from
10 to 100
bar(abs), more preferably from 15 to 90 bar(abs), more preferably from 20 to
80 bar(abs), more
preferably in the range of from 20 to 55 bar(abs).
Preferably, from 70 to 100 weight-%, more preferably from 80 to 100 weight-%,
more preferably
from 90 to 100 weight-%, of the gas stream GO consists of H2. Further
conceivable ranges are
from 92 to 100 weight-% or from 94 to 100 weight-% or from 96 to 100 weight-%
or from 98 to
100 weight-%.
According to (ii.1), GO is preferably introduced continuously or semi-
continuously, more prefera-
bly continuously into Zl.
According to (ii.2), SO is preferably introduced semi-continuously or
continuously, more prefera-
bly continuously, into Zl.
Preferably, GO is introduced into Z1 according to (ii.1) for a period Lt prior
to introducing SO into
Z1 according to (ii.2).
In particular in case the hydrogenation catalyst comprises Ni, it may
preferred to suffidize the
catalyst, preferably after drying, before it is employed as hydrogenation
catalyst. Drying may be
accomplished by subjecting the catalyst to a gas atmosphere, preferably
containing nitrogen
such as technical nitrogen, the gas atmosphere preferably having a temperature
in the range of
from 150 to 25000 such as from 170 to 23000 or from 190 to 210 C. If drying
is carried out
semi-continuously or continuously, the gas hourly space velocity may be in the
range of from
1,000 to 3,000
such as from 1,500 to 2,500 or from 1,800 to 2,200 ft'. After drying, H2S
is
dosed preferably until saturation with sulfur is achieved, preferably at a
temperature in the range
of from 300 to 400 C such as from 325 to 375 C.
Alternatively, a hydrogenation catalyst comprising Ni can be presulfidized
according to the fol-
lowing (or a similar) method: the catalyst is dried at 200 C (temperature
increase rate 1K/min)
for at least 2 h under flow of nitrogen(GHSV=2000/h) at atmospheric pressure
until no water is
condensed anymore downstream. Afterwards the catalyst is cooled down to 135 C
and hydro-
gen is fed to the reactor at a GHSV=2000/h and the reactor is pressurized
(lbar/min). After lh
hexadecane spiked with 2 weight-% dimethyldisulfide is dosed with LHSV=2/h for
1 h. After-
wards temperature is increased with 0.25K/min to 350 C and kept for 2h.
Afterwards, tempera-
ture and pressure are adjusted before hexadecane solution dosing is stopped
and feed is
dosed.
If the hydrogenation catalyst comprises Pd, it may be preferred that it is
activated under flow of
hydrogen (GHSV=1000/h) at 50 to 130 C (1K/min), for example for 6 to 24 h
such as 12 h,
preferably at atmospheric condition. Upon catalyst reduction in larger
reactor, hydrogen can be
diluted by nitrogen to avoid excess temperature.
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During At, GO is preferably brought in contact with the heterogeneous
hydrogenation catalyst
comprised in Z1, wherein GO has a temperature in the range of 50 to 250 C,
more preferably
from 120 to 220 C, more preferably from 140 to 200 C.
In Z1, the liquid hourly space velocity (LHSV) is preferably in the range of
from 0.2 to 10
m3/(m3h), more preferably in the range of from 0.3 to 5 m3/(m3h), more
preferably in the range of
from 0.5 to 2 m3/(m3h), wherein the LHSV is defined as the volume flow of SO
through Z1 (in
m3/h) per volume of heterogeneous hydrogenation catalyst comprised in Z1 (in
m3).
Generally, according to the present invention, it is possible to recycle a
portion of Si, Si', ob-
tained from (ii) and removed from Z1, back to Z1 as part of the starting
material subjected to
hydrogenation. In this case, not only the stream SO is subjected to
hydrogenation, but also the
additional stream Si'. As far as Si' is concerned, its LHSV in Z1, relative to
the LHSV of SO,
LHSV(S1'):LHSV(S0), corresponding to the recycle ratio, is preferably in the
range of from 1:1
to 20:1, such as fronn 1:1 to 5:1 or from 5:1 to 10:1 or from 10:1 to 15:1 or
from 15:1 to 20:1.
Generally, Si' can be admixed with SO at every suitable position in the
process, preferably up-
stream of Z1. If a portion of Si is recycled, the remaining portion of Si is
referred to herein as
the stream Si which is subjected to dehalogenation according to (iii).
Generally, it is preferred that the process further comprises
(ii.5) removing a gas stream GO' from Z1, the gas stream GO' comprising H2.
Generally, according to the present invention, it is possible to recycle a
portion of GO', GO", ob-
tamed from (ii) and removed from Z1, back to Z1 as part of the starting
materials. In this case,
not only the stream GO' is introduced into Z1, but also the additional stream
GO". As far as GO"
is concerned, its hourly space velocity, GHSV, in Z1, relative to the GHSV of
GO,
LHSV(GO"):LHSV(G0), corresponding to the recycle ratio, is preferably in the
range of from 1:1
to 20:1, such as from 1:1 to 5:1 or from 5:1 to 10:1 or from 10:1 to 15:1 or
from 15:1 to 20:1.
Preferably, the reaction zone Z1 is comprised in a continuous stirred tank
reactor (CSTR) or a
fixed bed reactor, more preferably in a fixed bed reactor, wherein the fixed
bed reactor is more
preferably a trickle bed reactor.
According to (ii), two or more reaction zones Z1 are preferably employed which
are arranged
serially and/or in parallel, wherein more preferably, one single reaction zone
Z1 is employed
according to (ii).
Preferably, the stream Si obtained from (ii), and subjected to dehalogenation
in (iii), comprises
a reduced amount of the one or more organic compounds comprising conjugated
double bonds
of from 50 to 100%, more preferably from 70 to 100 %, more preferably from 75
to 100 %, com-
pared to SO. The total amount of the one or more organic compounds comprising
conjugated
double bonds is determined as described in Reference Example 1.
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Preferably, the stream Si obtained from (ii) and subjected to dehalogenation
in (iii) comprises
the one or more organic compounds comprising conjugated double bonds in a
total amount in
the range of from 0 to 3 g(I2)/100 g, preferably from 0 to 2 g(I2)/100g, more
preferably from 0 to
1 g(I2)/100 g, more preferably from 0 to 0.25 g(I2)/100 g, more preferably
from 0 to 0.1
g(I2)/100 g of the stream Si, determined as described in Reference Example 1.
Preferably, the stream Si obtained from (ii), and subjected to dehalogenation
in (iii), comprises
a reduced styrene amount from 50 to 100%, more preferably from 70 to 100 %,
more preferably
from 75 to 100 %, compared to SO. The styrene amount is determined as
described in Refer-
ence Example 8.
Preferably, the stream Si obtained from (ii) and subjected to dehalogenation
in (iii) has a sty-
rene content in the range of from 0 to 1.5 Area%, more preferably in the range
of from 0 to 0.1
Area%, determined as described in Reference Example 8.
Dehalogenation
Preferably, the stream Si subjected to dehalogenation in (iii) has a
temperature in the range of
from 150 to 450 C, more preferably from 200 to 400 C, more preferably from 250
to 350 'C.
Adsorption zone Z2
Preferably, the dehalogenation zone Z2 according to (iii) comprises, more
preferably consists of
an adsorption zone, more preferably comprising a heterogeneous adsorbent
material suitable
for adsorbing halide comprised in at least one of the one or more halogenated
organic com-
pounds, preferably comprised all of the one or more halogenated organic
compounds.
In the context of the present invention, any heterogeneous adsorbent material
can be used ac-
cording to (iii) as far as it permits to adsorb halide comprised in at least
one of the one or more
halogenated organic compounds. Preferably the heterogeneous adsorbent material
according
to (iii) comprises one or more of a carbon-containing adsorbent material and
an aluminum-
containing adsorbent material, more preferably an aluminum-containing
adsorbent material.
The carbon-containing adsorbent material is preferably a carbon-containing
molecular sieve,
more preferably activated charcoal. The aluminum-containing adsorbent material
is preferably
an alumina, an aluminum-containing molecular sieve, a silicoaluminophosphate,
a silica-
alumina hydrate or a hydrotalcite. The aluminum-containing molecular sieve is
preferably an
aluminosilicate, more preferably having a molar ratio of Si:Al, calculated as
Si02:A1203, in the
range of from 2:1 to 10:1, more preferably from 2:1 to 4:1. The silica-alumina
hydrate preferably
has weight ratio A1203:Si02 in the range of from 1:1 to 10:1, more preferably
from 1:1 to 2:1. The
hydrotalcite is preferably an aluminum and magnesium containing hydrotalcite,
more preferably
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an aluminum-magnesium hydroxycarbonate, preferably having a Mg0:A1203 weight
ratio in the
range of from 63:37 to 70:30.
Preferably, the heterogeneous adsorbent material comprises an hydrotalcite as
defined in the
foregoing.
It is also conceivable that the heterogeneous adsorbent material according to
(iii) comprises an
element of the groups 1, 2, 11 and 12.
Preferably, the aluminosilicate mentioned above contains one or more of
potassium oxide, sodi-
um oxide, magnesium oxide and calcium oxide.
Preferably, according to the present invention, from 0 to 0.001 weight-%,
preferably from 0 to
0.0001 weight-%, more preferably from 0 to 0.00001 weight-%, of the
heterogeneous adsorbent
material according to (iii) consist of Ni.
Preferably, the heterogeneous adsorbent material according to (iii) comprises
particles charac-
terized by a particle size distribution having a D50 value in the range of
from 1 to 6,500 microm-
eters, more preferably from 2 to 2,000 micrometers, more preferably from 8 to
500 micrometers,
more preferably from 10 to 50 micrometers or from 3 to 9 micrometers, the D50
particle size
being determined as described in Reference Example 5.
More preferably, the heterogeneous adsorbent material being an hydrotalcite
defined in the
foregoing comprises particles characterized by a particle size distribution
having a D50 value in
the range of from 3 to 9 micrometers, the D50 particle size being determined
as described in
Reference Example 5.
In the context of the present invention, the heterogeneous adsorbent material
according to (iii)
has preferably an average pore volume in the range of from 0.1 to 5 ml/g, more
preferably in the
range of from 0.15 to 2 ml/g, the average pore volume being determined as
described in Refer-
ence Example 6.
Preferably, the heterogeneous adsorbent material according to (iii) has a BET
specific surface
area in the range of from 50 to 1,000 m2/g, more preferably in the range of
from 100 to 900
m2/g, more preferably in the range of from 150 to 600 m2/g, the BET specific
surface area being
determined as described in reference Example 7.
According to the present invention, the adsorbent material can be suitably
regenerated, if so
desired.
Preferably, (iii) comprises
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(iHi ) introducing a gas stream G1 into Z2 preferably being an adsorption
zone, more preferably
a gas stream comprising one or more of hydrogen and nitrogen, more preferably
hydro-
gen;
(iii.2) introducing the stream Si obtained from (ii) into Z2;
(iii.3) bringing Si in contact with G1 and a heterogeneous adsorbent material,
suitable for ad-
sorbing halide comprised in at least one of the one or more halogenated
organic com-
pounds, comprised in Z2, obtaining a stream S2 being depleted, compared to Si,
in the
one or more halogenated organic compounds;
(111.4) removing S2 from Z2.
Preferably, the gas stream G1 has a temperature in the range of 250 to 500 C,
more preferably
in the range of from 300 to 400 C.
Preferably, the gas stream G1 is introduced at a pressure in the range of from
1 to 100
bar(abs), more preferably in the range of from 5 to 80 bar(abs), more
preferably in the range of
from 10 to 50 bar(abs).
Preferably, in Z2, the liquid hourly space velocity (LHSV) is in the range of
from 0.2 to 10
m3/(m3h), more preferably in the range of from 0.3 to 5 m3/(m3h), more
preferably in the range of
from 0.5 to 2 m3/(m3h), wherein the LHSV is defined as the volume flow of Si
through Z2 (in
m3/h) per volume of adsorbent material comprised in Z2 (in m3).
Preferably, from 90 to 100 weight-%, more preferably from 95 to 100 weight-%,
more preferably
from 98 to 100 weight-%, of the gas stream G1 consists of H2. Alternatively,
preferably from 90
to 100 weight-%, more preferably from 95 to 100 weight-%, more preferably from
98 to 100
weight-%, of the gas stream G1 consists of nitrogen.
According to (iii.1), G1 is preferably introduced continuously or semi-
continuously, more prefer-
ably continuously, into Z2 and wherein according to (iii.2) Si is introduced
continuously or semi-
continuously, more preferably continuously, into Z2.
Preferably, the adsorption zone Z2 is comprised in a continuous stirred tank
reactor (CSTR) or
a fixed bed reactor, more preferably in a fixed bed reactor, more preferably a
trickle bed reactor,
the reactor preferably comprising an adsorption bed comprising the
heterogeneous adsorbent
material.
According to (iii), two or more reaction zones Z2 are preferably employed
which are arranged
serially and/or in parallel or one single reaction zone Z2 is preferably
employed according to (iii),
more preferably one single reaction zone Z2 is employed according to (iii).
Preferably, the stream S2 obtained from (iii) has a reduced total chlorine
content of from 50 to
100 %, preferably 60 to 100 %, more preferably from 75 to 100%, compared to SO
and Si.
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Preferably, the stream S2 obtained from (iii) has a total chlorine content in
the range of from 0 to
200 wppm (ppm by weight), more preferably from 0 to 160 wppm, more preferably
from 0 to 130
wppm, determined as described in Reference Example 2.1.
Preferably, the stream S2 obtained from (iii) has a chloride content of at
most 40 wppm (ppm by
weight), more preferably from 0 to 30 wppm, more preferably from 0 to 20 wppm,
more prefer-
ably from 0 to 1 wppm, determined as described in Reference Example 2.2.
Preferably, the stream S2 obtained from (iii) comprises the one or more
organic compounds
comprising conjugated double bonds in a total amount in the range of 0 to 3
g(I2)/100 g, more
preferably from 0 to 2 g(I2)/100 g, more preferably from 0 to 1 g(I2)/100 g,
more preferably from
0 to 0.25 g(I2)/100 g, more preferably from 0 to 0.1 g(I2)/100 g of the stream
S2, determined as
described in Reference Example 1.
Preferably, the stream S2 obtained from (iii) has a nitrogen content in the
range of from 50 to
20,000 ppm by weight wppm, more preferably from 50 to 5,000 wppm, more
preferably from
100 to 4,000 wppm, determined as described in Reference Example 3.
Preferably, the stream S2 obtained from (iii) has a sulfur content in the
range of from 50 to
30,000 ppm by weight (wppm), more preferably from 50 to 5,000 wppm, more
preferably from
100 to 3,000 wppm, determined as described in Reference Example 4.
Preferably, the stream S2 has a chlorine content, a nitrogen content, a sulfur
content and a total
amount of the one or more organic compounds comprising conjugated double bonds
as defined
in the foregoing.
Catalytic zone Z2
Alternatively, the dehalogenation zone Z2 according to (iii) comprises, more
preferably is a cata-
lytic zone, the catalytic zone more preferably comprising a heterogeneous
dehalogenation cata-
lyst, said catalyst preferably comprising one or more catalytically active
elements of groups 8 to
12 of the periodic system of elements.
In this case, (iii) preferably comprises
(iii.1') introducing a gas stream G1 into Z2 being a catalytic zone, more
preferably introducing a
gas stream comprising hydrogen and nitrogen, more preferably hydrogen;
(iii.2') introducing the stream Si obtained from (ii) into Z2;
(iii.3') bringing Si in contact with G1 and a heterogeneous dehalogenation
catalyst comprised in
Z2, obtaining a stream S2 being depleted, compared to Si, in the one or more
halogenat-
ed organic compounds;
(iii.4') removing S2 from Z2;
(iii.5') more preferably cooling S2 removed according to (iii.4').
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Preferably, the stream S2 obtained from (iii), prior to being subjected to
hydroprocessing ac-
cording to (iv) as defined in the following, is subjected to extraction, more
preferably using an
aqueous extraction medium, obtaining a stream S2 being depleted in one or more
dissolved
halides comprised in S2 obtained from the dehalogenation zone Z2, said halides
more prefera-
bly comprising one or more halides of N-containing organic compounds.
Hydroprocessing
The process of the present invention preferably further comprises, after
(iii),
(iv) subjecting the stream S2 obtained from (iii) to hydroprocessing in at
least one reaction
zone Z3 downstream of Z2, Z3 comprising a heterogeneous hydroprocessing
catalyst; ob-
taining a stream S3;
wherein the stream S2 subjected to (iv) has a temperature in the range of from
150 to 400 C,
more preferably in the range of from 200 to 375 C, more preferably in the
range of from 250 to
350 C.
As to the heterogeneous hydroprocessing catalyst according to (iv), any
heterogeneous hydro-
processing catalyst can be used as far as it permits to obtain a stream S3.
Preferably, the het-
erogeneous hydroprocessing catalyst according to (iv) comprises an element of
the groups 8 to
10, more preferably 9 and 10 of the periodic table of elements, more
preferably an element se-
lected from the group consisting of Ni and Co, wherein the hydroprocessing
catalyst more pref-
erably comprises Ni.
Preferably, the heterogeneous hydroprocessing catalyst according to (iv)
comprises Ni in an
amount, calculated as NiO, in the range of from 0.5 to 10 weight-%, more
preferably in the
range of from 1106 weight-%, based on the weight of the hydroprocessing
catalyst.
Preferably, the heterogeneous hydroprocessing catalyst according to (iv)
further comprises a
support for the element of the groups 8 to 10 of the periodic table of
elements, wherein the sup-
port preferably is an oxidic material. Preferably, the oxidic material is one
or more of alumina,
silica, magnesia, zirconia, zinc oxide, calcium oxide, mixed silica-alumina,
zeolite, Mo-doped
alumina and titania, more preferably alumina, zeolite and silica-alumina, more
preferably alumi-
na.
Preferably, the heterogeneous hydroprocessing catalyst according to (iv)
further comprises an
element of the group 6 of the periodic table of elements, wherein the element
of the group 6 is
more preferably one or more of Mo and W. Preferably the hydroprocessing
catalyst comprises
in the range of from 1 to 40 weight-%, more preferably from 3 to 30 weight-%,
of an oxide of
said element of the group 6, more preferably Mo oxide or W oxide, based on the
weight of the
hydroprocessing catalyst.
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Preferably the heterogeneous hydroprocessing catalyst according to (iv)
comprises Ni and Mo
on a support, more preferably a support as defined in in the foregoing,
wherein the hydropro-
cessing catalyst more preferably comprises Ni and Mo on alumina.
According to the present invention, the hydroprocessing catalyst, in
particular the hydropro-
cessing catalyst comprising Ni, may comprise from 0.1 to 5 weight-%,
preferably from 0.1 to 4
weight-%, more preferably from 0.1 to 3 weight phosphorus, calculated as P205
and based on
the total weight of the catalyst.
A hydroprocessing catalyst comprising Ni can be presulfidized, prior to being
used, according to
the following (or a similar) method: the catalyst is dried at 200 C
(temperature increase rate
1K/min) for at least 2 h under flow of nitrogen (GHSV=2000/h) at atmospheric
pressure until no
water is condensed anymore downstream. Afterwards the catalyst is cooled down
to 135 C and
hydrogen is fed to the reactor at a GHSV=2000/h and the reactor is pressurized
(lbar/min). Af-
tel lh hexadecane spiked with 2 weight-% dinnethyldisulfide is dosed with
LHSV= ,2/h for 1 h.
Afterwards temperature is increased with 0.25 K/min to 350 C and kept for 2h.
Afterwards tem-
perature and pressure are adjusted before hexadecane solution dosing is
stopped and feed is
dosed.
Preferably, (iv) comprises
(iv.1) introducing a gas stream G2 into Z3, G2 comprising H2;
(iv.2) introducing the stream S2 obtained from (iii) into Z3;
(iv.3) bringing S2 in contact with G2 and a heterogeneous hydroprocessing
catalyst comprised
in Z3, obtaining a stream S3;
(iv.4) removing S3 obtained in (iv.3) from Z3.
Preferably, the gas stream G2 has a temperature in the range of 250 to 550 C,
more preferably
in the range of from 300 to 450 C, more preferably in the range of from 325
to 400 C.
Preferably the gas stream G2 is introduced at a pressure in the range of from
20 to 150 bar
(abs), more preferably in the range of from 30 to 90 bar(abs), more preferably
in the range of
from 40 to 80 bar(abs), more preferably in the range of from 45 to 60
bar(abs).
Preferably, in Z3 the liquid hourly space velocity (LHSV) is in the range of
from 0.1 to 10
m3/(m3h), more preferably in the range of from 0.15 to 5 m3/(m3h), more
preferably in the range
of from 0.2 to 2 m3/(m3h), wherein the LHSV is defined as the volume flow of
S2 through Z3 (in
m3/h) per volume of heterogeneous hydroprocessing catalyst comprised in Z3 (in
m3).
According to the present invention, G2 may preferably be recycled from the
stream obtained
from hydroprocessing.
Preferably, from 50 to 100 weight-%, more preferably from 70 to 100 weight-%,
more preferably
from 90 to 100 weight-%, of the gas stream G2 consists of H2. Further
conceivable ranges are
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from 92 to 100 weight-% or from 94 to 100 weight-% or from 96 to 100 weight-%
or from 98 to
100 weight-%.
According to (iv.1), G2 is preferably introduced continuously or semi-
continuously, more prefer-
ably continuously, into Z3.
According to (iv.2), S2 is preferably introduced continuously or semi-
continuously, more prefer-
ably continuously, into Z3.
Preferably, the reaction zone Z3 is comprised in a reactor, more preferably
comprising n serially
coupled catalyst beds B(i), i= 1..., n, n 2, wherein a catalyst bed B(i)
comprises a heterogene-
ous hydroprocessing catalyst, more preferably 2 <n 10, more preferably 2 < n
5; wherein
B(1) is the most upstream catalyst bed and B(n) is the most downstream
catalyst bed.
More preferably, (iv) comprises
(iv.1')introducing a gas stream G2 into Z3, G2 comprising Hz;
(iv.2') introducing the stream S2 obtained from (iii) into Z3;
(iv.3')n successive process stages P(i), i=1...n,
wherein in P(1)
- the gas stream G2 is introduced into a catalyst bed B(1) and brought in
contact with
the stream 82 obtained from (iii) and a heterogeneous hydroprocessing catalyst
in
B(1), obtaining a stream Sp(1);
wherein in each P(i), when i=2. ..n-1,
- a gas stream F(i-1), comprising Hz, is introduced into a catalyst bed
B(i) and brought in
contact with Sp(I-1) and a heterogeneous hydroprocessing catalyst in B(i),
obtaining a
stream Sp(i);
- removing Sp(i) from B(i); and
wherein in P(n),
- a gas stream F(n-1) is introduced into a catalyst bed B(n) and brought in
contact with
Sp(n-1) and a heterogeneous hydroprocessing catalyst in B(n), obtaining a gas
stream
S3;
(iv.4')removing 33 obtained in (iv.3') from Z3.
Preferably, the gas stream G2 has a temperature in the range of 250 to 550 C,
more preferably
in the range of from 300 to 450 C, more preferably in the range of from 325
to 400 C.
Preferably, the gas stream G2 is introduced at a pressure in the range of from
20 to 150
bar(abs), more preferably in the range of from 30 to 90 bar(abs), more
preferably in the range of
from 40 to 80 bar(abs), more preferably in the range of from 45 to 60
bar(abs).
Preferably, from 50 to 100 weight-%, more preferably from 70 to 100 weight-%,
more preferably
from 90 to 100 weight-%, of the gas stream G2 consists of H2. Further
conceivable ranges are
from 92 to 100 weight-% or from 94 to 100 weight-% or from 96 to 100 weight-%
or from 98 to
100 weight-%.
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Preferably, in Z3, the liquid hourly space velocity (LHSV) is in the range of
from 0.1 to 10 h-1,
preferably in the range of from 0.1 to 5 h-1, more preferably in the range of
from 0.2 to 2 h-1,
wherein the LHSV is defined as the volume flow of S2 or Sp(i) through Z3 (in
m3/h) per volume
of heterogeneous hydroprocessing catalyst comprised in Z3 (in m3).
According to (iv.1'), G2 is preferably introduced continuously or semi-
continuously, more prefer-
ably continuously, into Z3.
According to (iv.2'), S2 is preferably introduced continuously or semi-
continuously, more prefer-
ably continuously, into Z3.
Preferably, from 50 to 100 weight-%, more preferably from 70 to 100 weight-%,
more preferably
from 90 to 100 weight-%, of the gas stream F(i) consists of H2. Further
conceivable ranges are
from 92 to 100 weight-% or from 94 to 100 weight-% or from 96 to 100 weight-%
or from 98 to
100 weight-%.
Preferably, the gas stream F(i) is introduced at a pressure in the range of
from 20 to 150
bar(abs), more preferably in the range of from 30 to 90 bar(abs), more
preferably in the range of
from 40 to 80 bar(abs), more preferably in the range of from 45 to 60
bar(abs).
Preferably, the n serially coupled catalyst beds B(i) are fixed catalyst beds.
Alternatively, the reaction zone Z3 is comprised in a reactor comprising one
catalyst bed,
wherein the catalyst bed comprises a heterogeneous hydroprocessing catalyst.
In the context of the present invention, the reaction zone Z3 is preferably
comprised in a contin-
uous stirred tank reactor (CSTR) or a fixed bed reactor, more preferably in a
fixed bed reactor,
more preferably a trickle bed reactor.
Preferably, the stream S3 obtained from (iii) has a reduced total chlorine
content of from 90 to
100 %, more preferably of from 95 to 100 %, more preferably of from 99 to
100%, more prefer-
ably of from 99.5 to 100%, compared to SO and Si.
Preferably, the stream S3 obtained from (iv) has a total chlorine content in
the range of from 0
to 50 wppm (ppm by weight), more preferably from 0 to 30 wppm, more preferably
from 0 to 20
wppm, more preferably from 0 to 10 wppm, more preferably from 0 to 5 wppm,
more preferably
from 0 to 2 wppm, determined as described in Reference Example 2.1.
Preferably, the stream S3 obtained from (iv) has a chloride content in the
range of from at most
40 wppm (ppm by weight), preferably from 0 to 30 wppm, more preferably from 0
to 20 wppm,
more preferably from 0 to 1 wppm, determined as described in Reference Example
2.2.
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Preferably, the stream S3 obtained from (iii) has a reduced nitrogen content
of from 80 to 100
%, more preferably of from 85 to 100 %, more preferably of from 90 to 100%,
compared to SO,
Si and S2.
Preferably, the stream S3 obtained from (iv), more preferably after removing
dissolved NH3, has
a nitrogen content in the range of from 0 to 200 ppm by weight (wppm), more
preferably in the
range of from 0 to 100 wppm, more preferably from 0 to 50 wppm, more
preferably from 0 to 10
wppm, determined as described in Reference Example 3.
Preferably, the stream S3 obtained from (iii) has a reduced sulfur content of
from 80 to 100 %,
more preferably of from 85 to 100 %, more preferably of from 90 to 100%,
compared to SO, Si
and S2.
Preferably, the stream S3 obtained from (iv), more preferably after removing
dissolved H2S, has
a sulfur content in the range of from 0 to 200 ppm by weight (wppm), more
preferably from 0 to
100 wppm, more preferably from 0 to 50 wppm, determined as described in
Reference Example
4.
Preferably, the stream S3 obtained from (iii) comprises the one or more
organic compounds
comprising conjugated double bonds in a total amount in the range of 0 to 3
g(I2)/100 g, more
preferably from 0 to 2 g(I2)/100 g, more preferably from 0 to 1 g(I2)/100 g,
more preferably from
0 to 0.25 g(I2)/100 g, more preferably from 0 to 0.1 g(I2)/100 g of the stream
83 obtained from
(iv), determined as described in Reference Example 1.
Preferably, the stream S3 has a chlorine content, a nitrogen content, a sulfur
content and a total
amount of the one or more organic compounds comprising conjugated double bonds
as defined
in the foregoing.
Preferably, the stream S3 obtained from (iv), preferably prior to being
subjected to (v) as de-
fined in the following, is depleted in one or more nitrogen-containing
compounds and sulfur-
containing compounds compared to S2.
As mentioned in the introductory part of the invention, polymers comprised in
plastic waste may
contain oxygen. Such oxygen is preferably removed in the above-described
hydroprocessing
step.
Steps downstream of (iv)
The process of the present invention preferably further comprises, after
(iii), or (iv) as defined in
the foregoing,
(v) one or more of a steam cracking step, hydrocracking step, distillation,
stripping, and an
aqueous extraction.
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Preferably, the process of the present invention is a continuous or semi-
continuous process,
more preferably a continuous process.
Preferably, the process of the present invention consists of (i), (ii), (iii),
more preferably of (i), (ii),
(iii) and (iv), more preferably of (i), (ii), (iii), (iv) and (v).
The present invention further relates to a production unit for carrying out
the process for purify-
ing a pyrolysis oil according to the present invention, the unit comprising
at least one reaction zone Z1, Z1 comprising a heterogeneous hydrogenation
catalyst;
- an inlet means for introducing SO into Z1;
an outlet means for removing Si from Z1;
at least one dehalogenation zone Z2, Z2 preferably comprising a heterogeneous
adsorp-
tion material or a heterogenous dehalogenation catalyst;
an inlet means for introducing Si into Z2;
- an outlet means for removing S2 from Z2;
wherein Z1 is located upstream of Z2.
Preferably, the production unit further comprises an extraction zone to remove
halides, more
preferably comprising one or more halides of N-containing organic compounds,
said extraction
zone more preferably being arranged downstream of Z2.
Preferably, the production unit further comprises
at least one reaction zone Z3, Z3 comprising a heterogeneous hydroprocessing
catalyst;
an inlet means for introducing S2 into Z3;
- an outlet means for removing S3 from Z3;
wherein Z2 is located upstream of Z3.
The present invention further relates to a purified pyrolysis oil, obtainable
or obtained by a pro-
cess according to the present invention comprising (i), (ii) and (iii), or
(i), (ii), (iii) and (iv).
When the process according to the present invention comprises (i), (ii) and
(iii), the purified py-
rolysis oil has preferably a chlorine content and a total amount of the one or
more organic com-
pounds comprising conjugated double bonds as defined in the foregoing for the
stream S2,
more preferably a chlorine content, a nitrogen content a sulfur content and a
total amount of the
one or more organic compounds comprising conjugated double bonds as defined in
the forego-
ing for the stream S2.
When the process according to the present invention comprises (i), (ii), (iii)
and (iv), the purified
pyrolysis oil has preferably a chlorine content, a nitrogen content a sulfur
content and a total
amount of the one or more organic compounds comprising conjugated double bonds
as defined
in the foregoing for the stream S3.
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Preferably, the purified pyrolysis oil has a total chlorine content in the
range of from 0 to 50
wppm (ppm by weight), more preferably from 0 to 30 wppm, more preferably from
0 to 20
wppm, more preferably from 0 to 10 wppm, more preferably from 0 to 5 wppm,
more preferably
from 0 to 2 wppm, determined as described in Reference Example 2.1.
Preferably, the purified pyrolysis oil has a chloride content in the range of
from at most 40 wppm
(ppm by weight), preferably from 0 to 30 wppm, more preferably from 0 to 20
wppm, more pref-
erably from 0 to 1 wppm, determined as described in Reference Example 2.2.
Preferably, the purified pyrolysis oil has a nitrogen content in the range of
from 0 to 200 ppm by
weight (wppm), more preferably in the range of from 0 to 100 wppm, more
preferably from 0 to
50 wppm, more preferably from 0 to 10 wppm, determined as described in
Reference Example
3.
Preferably, the purified pyrolysis oil has a sulfur content in the range of
from 0 to 200 ppm by
weight (wppm), more preferably from 0 to 100 wppm, more preferably from 0 to
50 wppm, de-
termined as described in Reference Example 4.
Preferably, the purified pyrolysis oil comprises the one or more organic
compounds comprising
conjugated double bonds in a total amount in the range of 0 to 3 g(I2)/100 g,
more preferably
from 0 to 2 g(I2)/100 g of the purified pyrolysis oil, determined as described
in Reference Ex-
ample 1.
The present invention is further illustrated by the following set of
embodiments and combina-
tions of embodiments resulting from the dependencies and back-references as
indicated. In
particular, it is noted that in each instance where a range of embodiments is
mentioned, for ex-
ample in the context of a term such as "The process of any one of embodiments
1 to 4", every
embodiment in this range is meant to be explicitly disclosed for the skilled
person, i.e. the word-
ing of this term is to be understood by the skilled person as being synonymous
to "The process
of any one of embodiments 1, 2, 3 and 4". Further, it is explicitly noted that
the following set of
embodiments represents a suitably structured part of the general description
directed to pre-
ferred aspects of the present invention, and, thus, suitably supports, but
does not represent the
claims of the present invention.
1. A process for purifying a pyrolysis oil, the process comprising:
(i) providing a stream SO comprising a pyrolysis oil, the pyrolysis oil
comprising one or
more halogenated organic compounds and one or more organic compounds com-
prising conjugated double bonds;
(ii) subjecting the stream SO provided in (i) to hydrogenation in at least
one reaction
zone Z1 containing a heterogeneous hydrogenation catalyst, obtaining a stream
Si
being depleted, compared to SO, in the one or more organic compounds
comprising
conjugated double bonds;
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(iii) subjecting the stream Si obtained from (ii) to dehalogenation in at
least one dehalo-
genation zone Z2 downstream of Z1, obtaining a stream S2 being depleted, com-
pared to Si, in the one or more halogenated organic compounds.
2. The process of embodiment 1, wherein from 95 to 100 weight-%, preferably
from 98 to
100 weight-%, more preferably from 99 to 100 weight-%, of SO consist of
pyrolysis oil.
3. The process of embodiment 1 or 2, wherein the pyrolysis oil according to
(i) comprises the
one or more organic compounds comprising conjugated double bonds in a total
amount in
the range of from 0.1 to 75 g(I2)/100 g, preferably from 0.4 to 60 g(12)/100
g, more prefer-
ably from 1 to 30 g(I2)/100 g of the pyrolysis oil, determined as described in
Reference
Example 1.
4. The process of any one of embodiments 1 to 3, wherein the one or more
organic corn-
pounds comprising conjugated double bonds comprise one or more organic
compounds
according to formula (I)
R2c1=c2R3_c3R4=x (I)
wherein =X is =0, =S, =NR5, or =04R6R7, preferably =c4R6R7.
5. The process of embodiment 4,
wherein R1, R2, R3, Ra, R5 are, independently of each other, H, alkyl having
from 1 to 6
carbon atoms, alkenyl having from 1 to 6 carbon atoms, or aryl having from 5
to 10 carbon
atoms, more preferably H;
wherein R6 and R7 are, independently of each other, H, alkyl having from 1 to
6 carbon at-
oms, alkenyl having from 1 to 6 carbon atoms, or aryl having from 5 to 10
carbon atoms,
more preferably H; or wherein either R4 and R6 or R4 and R7 are linked
together, thus
forming, together with C=C, an aromatic ring preferably having 5 or 6 members.
6. The process of embodiment 5, wherein the one or more organic compounds
according to
formula (I) comprise one or more of butadiene, isoprene, dienes having 5 or 6
carbon at-
oms, styrene, methylstyrene, indene, substituted styrene, substituted indene,
and 3-
methy1-2-butenal, more preferably comprise one or more of butadiene, isoprene,
dienes
having 5 or 6 carbon atoms, styrene, methylstyrene, indene, and 3-methyl-2-
butenal.
7. The process of embodiment 6, wherein the one or more organic compounds
according to
formula (1) comprise styrene.
8. The process of any one of embodiments 1 to 7, wherein the one or more
halogenated
organic compounds comprise one or more of mono- oligo- or polyhalogenated
aromatic
compounds, alkylhalides and alkenylhalides.
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9. The process of any one of embodiments 1 to 8, wherein the pyrolysis oil
according to (i)
has a total chlorine content in the range of from 30 to 3,000 wppm (ppm by
weight), pref-
erably from 30 to 500 wppm, more preferably from 30 to 200 wppm, determined as
de-
scribed in Reference Example 2.1;
wherein the pyrolysis oil according to (i) has a chloride content of at most
40 wppm, more
preferably in the range of from 0 to 30 wppm, determined as described in
Reference Ex-
ample 2.2.
10. The process of any one of embodiments 1 to 9, wherein the pyrolysis oil
according to (i)
has a nitrogen content in the range of from 50 to 20,000 wppm (ppm by weight),
prefera-
bly from 50 to 5,000 wppm, more preferably from 100 to 4,000 wppm, determined
as de-
scribed in Reference Example 3.
11. The process of any one of embodiments 1 to 10, wherein the pyrolysis
oil according to (i)
has a sulfur content in the range of from 50 to 30,000 ppm by weight (wppm),
preferably
from 50 to 5,000 wppm, more preferably from 100 to 3,000 wppm, determined as
de-
scribed in Reference Example 4.
12. The process of any one of embodiments 1 to 11, wherein the pyrolysis
oil is obtained from
plastic waste.
13. The process of any one of embodiments 1 to 12, wherein the stream SO is
a liquid stream.
14. The process of any one of embodiments 1 to 13, wherein the stream SO
subjected to hy-
drogenation in (ii) has a temperature in the range of from 60 to 250 C,
preferably from 80
to 220 C, more preferably from 100 to 200 C.
15. The process of any one of embodiments 1 to 14, wherein the
heterogeneous hydrogena-
tion catalyst according to (ii) comprises an element of the groups 8 to 12,
preferably 8 to
10, more preferably 9 and 10, of the periodic table of elements, preferably an
element se-
lected from the group consisting of Ni, Pd and Co, more preferably from the
group consist-
ing of Ni and Pd.
16. The process of embodiment 15, wherein the heterogeneous hydrogenation
catalyst ac-
cording to (ii) further comprises a support material for said element of the
groups 8 to 12
of the periodic table of elements, wherein the support material is preferably
selected from
the group consisting of an oxidic material and carbon, wherein the oxidic
material is pref-
erably one or more of alumina, silica, magnesia, zirconia, titania, a zeolitic
material, a sili-
ca-alumina phosphate (SAPO) material, zinc oxide, sodium oxide, mixed silica-
alumina,
zeolite and calcium oxide, more preferably alumina.
17. The process of embodiment 15 or 16, wherein the heterogeneous
hydrogenation catalyst
according to (ii) comprises Ni, preferably in an amount, calculated as NiO, in
the range of
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from 0.5 to 70 weight-%, more preferably from 0.75 to 45 weight-%, more
preferably from
1 to 20 weight-%, based on the total weight of the hydrogenation catalyst.
18. The process of any one of embodiments 15 to 17, wherein the
heterogeneous hydrogena-
tion catalyst used in (ii) further comprises an element of the group 6 of the
periodic table
of elements, wherein the element of the group 6 is preferably one or more of
Mo and W,
more preferably Mo;
wherein the hydrogenation catalyst preferably comprises from 1 to 40 weight-%,
more
preferably from 2 to 35 weight-%, more preferably from 3 to 30 weight-% of
said element
of the group 6, based on the total weight of the hydrogenation catalyst.
19. The process of embodiment 17 or 18, wherein the heterogeneous
hydrogenation catalyst
according to (ii) comprises Ni and Mo supported on a support material,
preferably a sup-
port material as defined in embodiment 16, wherein the hydrogenation catalyst
preferably
comprises Ni and Mo supported on alumina.
20. The process of embodiment 15 or 16, wherein the heterogeneous
hydrogenation catalyst
according to (ii) comprises Pd, preferably in an amount, calculated as
elemental Pd, in the
range of from 0.01 to 5 weight-%, preferably from 0.1 to 1 weight-%, more
preferably from
0.15 to 0.8 weight-%, based on the total weight of the catalyst.
21. The process of embodiment 20, wherein the heterogeneous hydrogenation
catalyst ac-
cording to (ii) further comprises a promoter, the promoter preferably being
one or more of
an element of the groups 10 and 11 of the periodic table of elements,
preferably one or
more of Cu, Au, Ag, and Pt, more preferably one or more of Ag and Pt, more
preferably
Ag.
22. The process of embodiment 21, wherein the atomic ratio of the element
of groups 8 to 12
of the periodic table, preferably Pd, relative to the promoter is in the range
of from 0.1:1 to
10:1, preferably from 2:1 to 7:1, more preferably from 2.5:1 to 6:1.
23. The process of any one of embodiments 20 to 22, wherein the
heterogeneous hydrogena-
tion catalyst according to (ii) comprises Pd supported on a support material,
preferably a
support material as defined in embodiment 16, wherein the support material is
preferably
alumina or carbon, more preferably alumina.
24. The process of any one of embodiments 1 to 23, wherein the
heterogeneous hydrogena-
tion catalyst according to (ii) is in the form of extrudates, pellets, rings,
spherical particles
or spheres, preferably spherical particles or extrudates.
25. The process of any one of embodiments 1 to 24, wherein (ii) comprises
(11.1) introducing a gas stream GO into Z1, the gas stream comprising H2;
(ii.2) introducing the stream SO into Z1;
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(ii.3) bringing SO in contact with GO and the heterogeneous hydrogenation
catalyst com-
prised in Z1, obtaining a stream Si being depleted, compared to SO, in the one
or
more organic compounds comprising conjugated double bonds;
(ii.4) removing Si from Z1.
(ii.5) optionally removing a gas stream G1 from Z1, G1 comprising H2.
26. The process of embodiment 25, wherein the gas stream GO has a
temperature in the
range of 100 to 250 'C, preferably from 120 to 220 "C, more preferably from
140 to 200
'C.
27. The process of embodiment 25 or 26, wherein the gas stream GO is
introduced at a pres-
sure in the range of from 10 to 100 bar(abs), preferably from 15 to 90
bar(abs), more pref-
erably from 20 to 80 bar(abs), more preferably in the range of from 20 to 55
bar(abs).
28. The process of any one of embodiments 25 to 27, wherein from 70 to 100
weight-%, pref-
erably from 80 to 100 weight-%, more preferably from 90 to 100 weight-%, of
the gas
stream GO consists of H2.
29. The process of any one of embodiments 25 to 28, wherein according to
(ii.1), GO is intro-
duced continuously or semi-continuously, preferably continuously into Z1, and
wherein
according to (ii.2), SO is introduced semi-continuously or continuously,
preferably continu-
ously, into Zl.
30. The process of embodiment 29, wherein GO is introduced into Z1
according to (ii.1) for a
period At prior to introducing SO into Z1 according to (ii.2).
31. The process of embodiment 30, wherein during At, GO is brought in
contact with the het-
erogeneous hydrogenation catalyst comprised in Z1, wherein GO has a
temperature in the
range of 50 to 250 C, preferably from 120 to 220 C, more preferably from 140
to 200 C.
32. The process of any one of embodiments 25 to 31, wherein in Z1, the
liquid hourly space
velocity (LHSV) is in the range of from 0.2 to 10 m3/(m3h), preferably in the
range of from
0.3 to 5 m3/(m3h), more preferably in the range of from 0.5 to 2 m3/(m3h),
wherein the
LHSV is defined as the volume flow of SO through Z1 (in m3/h) per volume of
heterogene-
ous hydrogenation catalyst comprised in Z1 (in m3).
33. The process of any one of embodiments 1 to 32, wherein the reaction
zone Z1 is com-
prised in a continuous stirred tank reactor (CSTR) or a fixed bed reactor,
preferably in a
fixed bed reactor, wherein the fixed bed reactor is preferably a trickle bed
reactor.
34. The process of any one of embodiments 1 to 33, wherein according to
(ii), two or more
reaction zones Z1 are employed which are arranged serially and/or in parallel,
or wherein
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one single reaction zone Z1 is employed according to (ii), preferably
according to (ii), one
single reaction zone Z1 is employed.
35. The process of any one of embodiments 1 to 35, preferably of any
embodiment as far as
being dependent on embodiment 3, wherein the stream Si obtained from (ii) and
subject-
ed to dehalogenation in (iii) comprises the one or more organic compounds
comprising
conjugated double bonds in a total amount in the range of from 0 to 3
g(I2)/100 g, prefer-
ably from 0 to 2 g(I2)/100g, more preferably from 0 to 1 g(I2)/100 g, more
preferably from
0 to 0.25 g(I2)/100 g, more preferably from 0 to 0.1 g(I2)/100 g of the stream
Si, deter-
mined as described in Reference Example 1.
36. The process of any one of embodiments 1 to 35, wherein the stream Si
subjected to
dehalogenation in (iii) has a temperature in the range of from 150 to 450 C,
preferably
from 200 to 400 C, more preferably from 250 to 350 'C.
37. The process of any one of embodiments 1 to 36, wherein the
dehalogenation zone Z2
according to (iii) comprises, preferably is an adsorption zone, preferably
comprising a het-
erogeneous adsorbent material suitable for adsorbing halide comprised in at
least one of
the one or more halogenated organic compounds, preferably in all of the one or
more hal-
ogenated organic compounds.
38. The process of embodiment 37, wherein the heterogeneous adsorbent
material according
to (iii) comprises one or more of a carbon-containing adsorbent material and
an alumi-
num-containing adsorbent material, preferably an aluminum-containing adsorbent
materi-
al;
wherein the carbon-containing adsorbent material is preferably a carbon-
containing mo-
lecular sieve, more preferably activated charcoal;
wherein the aluminum-containing adsorbent material is preferably an alumina,
an alumi-
num-containing molecular sieve, a silicoaluminophosphate, a silica-alumina
hydrate or a
hydrotalcite;
wherein the aluminum-containing molecular sieve is preferably an alumina, an
aluminosili-
cate, preferably having a molar ratio of Si:Al, calculated as Si02:A1203, in
the range of
from 2:1 to 10:1, more preferably from 2:1 to 4:1;
wherein the silica-alumina hydrate preferably has weight ratio A1203:Si02 in
the range of
from 1:1 to 10:1, more preferably from 1:1 to 2:1;
wherein the hydrotalcite is preferably an aluminum and magnesium containing hy-
drotalcite, more preferably an aluminum-magnesium hydroxycarbonate, preferably
having
a Mg0:A1203 weight ratio in the range of from 63:37 to 70:30;
wherein the heterogeneous adsorbent material more preferably comprises the hy-
drotalcite;
wherein the heterogeneous adsorbent material according to (iii) preferably
comprises an
element of the groups 1, 2, 11 and 12.
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39. The process of any one of embodiments 1 to 38, wherein the
heterogeneous adsorbent
material according to (iii) comprises particles characterized by a particle
size distribution
having a D50 value in the range of from 1 to 6,500 micrometers, preferably
from 2 to
2,000 micrometers, more preferably from 8 to 500 micrometers, more preferably
from 10
to 50 micrometers or from 3 to 9 micrometers, the D50 particle size being
determined as
described in Reference Example 5.
40. The process of any one of embodiments 1 to 39, wherein the
heterogeneous adsorbent
material according to (iii) has an average pore volume in the range of from
0.1 to 5 ml/g,
preferably in the range of from 0.15 to 2 ml/g, the average pore volume being
determined
as described in Reference Example 6.
41. The process of any one of embodiments 1 to 40, wherein the
heterogeneous adsorbent
material according to (iii) has a BET specific surface area in the range of
from 50 to 1,000
m2/g, preferably in the range of from 100 to 900 m2/g, more preferably in the
range of from
150 to 600 m2/g, the BET specific surface area being determined as described
in refer-
ence Example 7.
42. The process of any one of embodiments 1 to 41, wherein (iii) comprises
(iii.1) introducing a gas stream G1 into Z2 preferably being an adsorption
zone, preferably
a gas stream comprising one or more of hydrogen and nitrogen, more preferably
hydrogen;
(iii.2) introducing the stream Si obtained from (ii) into Z2;
(iii.3) bringing Si in contact with G1 and a heterogeneous adsorbent material
comprised
in Z2, obtaining a stream S2 being depleted, compared to Si, in the one or
more
halogenated organic compounds;
(iii.4) removing S2 from Z2.
43. The process of embodiment 42, wherein the gas stream G1 has a
temperature in the
range of 250 to 500 C, preferably in the range of from 300 to 400 'C.
44. The process of embodiment 42 or 43, wherein the gas stream G1 is
introduced at a pres-
sure in the range of from 1 to 100 bar(abs), preferably in the range of from 5
to 80
bar(abs), more preferably in the range of from 10 to 50 bar(abs).
45. The process of any one of embodiments 42 to 44, wherein in Z2, the
liquid hourly space
velocity (LHSV) is in the range of from 0.2 to 10 h-1, preferably in the range
of from 0.310
5 h-1, more preferably in the range of from 0.5 to 2 h-1.
46. The process of any one of embodiments 42 to 45, wherein from 90 to 100
weight-%, pref-
erably from 95 to 100 weight-%, more preferably from 98 to 100 weight-%, of
the gas
stream G1 consists of H2; or
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wherein from 90 to 100 weight-%, preferably from 95 to 100 weight-%, more
preferably
from 98 to 100 weight-%, of the gas stream G1 consists of nitrogen.
47. The process of any one of embodiments 42 to 46, wherein according to
(iii.1), G1 is intro-
duced continuously or semi-continuously, preferably continuously, into Z2 and
wherein
according to (iii.2) Si is introduced continuously or semi-continuously,
preferably continu-
ously, into Z2;
wherein the adsorption zone Z2 is preferably comprised in a continuous stirred
tank reac-
tor (CSTR) or a fixed bed reactor, preferably in a fixed bed reactor, more
preferably a
trickle bed reactor, the reactor preferably comprising an adsorption bed
comprising the
heterogeneous adsorbent material.
48. The process of any one of embodiments 1 to 47, wherein, according to
(iii), two or more
reaction zones Z2 are employed which are arranged serially and/or in parallel,
wherein
preferably, one single reaction zone Z2 is employed according to (iii).
49. The process of any one of embodiments 1 to 48, wherein the stream S2
obtained from (iii)
has a total chlorine content in the range of from 0 to 200 wppm (ppm by
weight), prefera-
bly from 0 to 160 wppm, more preferably from 0 to 130 wppm, more preferably
from 0 to
120 wppm, determined as described in Reference Example 2.1;
wherein the stream S2 obtained from (iii) has a chloride content of at most 40
wppm (ppm
by weight), preferably from 0 to 30 wppm, more preferably from 0 to 20 wppm,
more pref-
erably from 0 to 1 wppm, determined as described in Reference Example 2.2.
50. The process of any one of embodiments 1 to 49, preferably of any
embodiment as far as
being dependent on embodiment 3, wherein the stream S2 obtained from (iii)
comprises
the one or more organic compounds comprising conjugated double bonds in a
total
amount in the range of 0 to 3 g(I2)/100 g, preferably from 0 to 2 g(I2)/100 g,
more prefera-
bly from 0 to 1 g(I2)/100 g, more preferably from 0 to 0.25 g(I2)/100 g, more
preferably
from 0 to 0.1 g(I2)/100 g of the stream S2, determined as described in
Reference Exam-
ple 1.
51. The process of any one of embodiments 1 to 50, wherein the stream S2
obtained from (iii)
has a nitrogen content in the range of from 50 to 20,000 ppm by weight wppm,
preferably
from 50 to 5,000 wppm, more preferably from 100 to 4,000 wppm, determined as
de-
scribed in Reference Example 3; and
wherein the stream S2 obtained from (iii) has a sulfur content in the range of
from 50 to
30,000 ppm by weight (wppm), preferably from 50 to 5,000 wppm, more preferably
from
100 to 3,000 wppm, determined as described in Reference Example 4.
52. The process of any one of embodiments 1 to 36, wherein the
dehalogenation zone Z2
according to (iii) comprises, preferably is a catalytic zone, preferably
comprising a hetero-
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geneous dehalogenation catalyst, said catalyst comprising one or more
catalytically active
elements of groups 8 to 12 of the periodic system of elements.
53. The process of any one embodiments 1 to 52, wherein the stream S2
obtained from (iii),
prior to being subjected to hydroprocessing according to (iv) as defined in
embodiment 54,
is subjected to extraction, preferably using an aqueous extraction medium,
obtaining a
stream S2 being depleted in one or more dissolved halides comprised in S2
obtained from
the dehalogenation zone Z2, said halides preferably comprising one or more
halides of N-
containing organic compounds.
54. The process of any one of embodiments 1 to 53, further comprising
(iv) subjecting the stream S2 obtained from (iii) to hydroprocessing in at
least one reac-
tion zone Z3 downstream of Z2, Z3 comprising a heterogeneous hydroprocessing
catalyst; obtaining a stream S3;
wherein the stream S2 subjected to (iv) has a temperature in the range of from
150 to
400 C, preferably in the range of from 200 to 375 C, more preferably in the
range of from
250 to 350 C.
55. The process of embodiment 54, wherein the heterogeneous hydroprocessing
catalyst
used in (iv) comprises an element of the groups 8 to 10, preferably 9 and 10
of the period-
ic table of elements, preferably an element selected from the group consisting
of Ni and
Co, wherein the hydroprocessing catalyst more preferably comprises Ni;
wherein the heterogeneous hydroprocessing catalyst according to (iv) more
preferably
comprises Ni in an amount, calculated as NiO, in the range of from 0.5 to 10
weight-%,
more preferably in the range of from 1 to 6 weight-%, based on the weight of
the hydro-
processing catalyst.
56. The process of embodiment 55, wherein the heterogeneous hydroprocessing
catalyst
according to (iv) further comprises a support for the element of the groups 8
to 10 of the
periodic table of elements, wherein the support preferably is an oxidic
material;
wherein the oxidic material preferably is one or more of alumina, silica,
magnesia, zirco-
nia, zinc oxide, calcium oxide, mixed silica-alumina, zeolite, Mo-doped
alumina and tita-
nia, more preferably alumina, zeolite and silica-alumina, more preferably
alumina.
57. The process of embodiment 55 or 56, wherein the heterogeneous
hydroprocessing cata-
lyst according to (iv) further comprises an element of the group 6 of the
periodic table of
elements, wherein the element of the group 6 is preferably one or more of Mo
and W;
wherein the hydroprocessing catalyst preferably comprises in the range of from
1 to 40
weight-%, more preferably from 3 to 30 weight-%, of an oxide of said element
of the group
6, preferably Mo oxide or W oxide, based on the weight of the hydroprocessing
catalyst.
58. The process of embodiment 57, wherein the heterogeneous
hydroprocessing catalyst
according to (iv) comprises Ni and Mo on a support, preferably a support as
defined in
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embodiment 53, wherein the hydroprocessing catalyst preferably comprises Ni
and Mo on
alumina.
59. The process of any one of embodiments 53 to 58, wherein (iv) comprises
(iv.1) introducing a gas stream G2 into Z3, G2 comprising Hz;
(iv.2) introducing the stream S2 obtained from (iii) into Z3;
(iv.3) bringing S2 in contact with G2 and a heterogeneous hydroprocessing
catalyst com-
prised in Z3, obtaining a stream S3;
(iv.4) removing S3 obtained in (iv.3) from Z3.
60. The process of embodiment 59, wherein the gas stream G2 has a
temperature in the
range of 250 to 550 C, preferably in the range of from 300 to 450 C, more
preferably in
the range of from 325 to 400 C.
61. The process of embodiment 59 or 60, wherein the gas stream G2 is
introduced at a pres-
sure in the range of from 20 to 150 bar (abs), preferably in the range of from
30 to 90
bar(abs), more preferably in the range of from 40 to 80 bar(abs), more
preferably in the
range of from 45 to 60 bar(abs).
62. The process of any one of embodiments 59 to 61, wherein in Z3 the
liquid hourly space
velocity (LHSV) is in the range of from 0.1 to 10 h-1, preferably in the range
of from 0.1 to
5 h-1, more preferably in the range of from 0.2 to 2
63. The process of any one of embodiments 59 to 62, wherein from 50 to 100
weight-%, pref-
erably from 70 to 100 weight-%, more preferably from 90 to 100 weight-%, of
the gas
stream G2 consists of H2.
64. The process of any one of embodiments 59 to 63, wherein according to
(iv.1) G2 is intro-
duced continuously or semi-continuously, preferably continuously, into Z3.
65. The process of any one of embodiments 59 to 64, wherein according to
(iv.2) S2 is intro-
duced continuously or semi-continuously, preferably continuously, into Z3.
66. The process of any one of embodiments 1 to 65, wherein the reaction
zone Z3 is com-
prised in a reactor, preferably comprising n serially coupled catalyst beds
B(i), i= 1 n, n
2, wherein a catalyst bed B(i) comprises a heterogeneous hydroprocessing
catalyst,
preferably 2 5 n 5 10, more preferably 2 5 n 5 5; wherein B(1) is the most
upstream cata-
lyst bed and B(n) is the most downstream catalyst bed.
67. The process of embodiment 66, wherein (iv) comprises
(iv.1')introducing a gas stream G2 into Z3, G2 comprising H2;
(iv.2') introducing the stream S2 obtained from (iii) into Z3;
(iv.3')n successive process stages P(i), i=1...n,
wherein in P(1)
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- the gas stream G2 is introduced into a catalyst bed B(1) and brought in
contact
with the stream S2 obtained from (iii) and a heterogeneous hydroprocessing
catalyst in B(1), obtaining a stream Sp(1);
wherein in each P(i), when i=2. ..n-1,
a gas stream F(i-1), comprising Hz, is introduced into a catalyst bed B(i) and
brought in contact with Sp(i-1) and a heterogeneous hydroprocessing catalyst
in B(i), obtaining a stream Sp(i);
- removing Sp(i) from B(i); and
wherein in P(n),
- a gas stream F(n-1) is introduced into a catalyst bed B(n) and brought in
contact
with Sp(n-1) and a heterogeneous hydroprocessing catalyst in B(n), obtaining a
gas stream S3;
(iv.4')removing S3 obtained in (iv.3') from Z3.
68. The process of embodiment 67, wherein the gas stream G2 has a temperature
in the
range of 250 to 550 C, preferably in the range of from 300 to 450 C, more
preferably in
the range of from 325 to 400 C.
69. The process of embodiment 67 or 68, wherein the gas stream G2 is
introduced at a pres-
sure in the range of from 20 to 150 bar (abs) , preferably in the range of
from 30 to 90
bar(abs), more preferably in the range of from 40 to 80 bar (abs), more
preferably in the
range of from 45 to 60 bar(abs).
70. The process of any one of embodiments 67 to 69, wherein from 50 to 100
weight-%, pref-
erably from 70 to 100 weight-%, more preferably from 90 to 100 weight-%, of
the gas
stream G2 consists of H2.
71. The process of any one of embodiments 67 to 70, wherein in Z3 the
liquid hourly space
velocity (LHSV) is in the range of from 0.1 to 10 h-1, preferably in the range
of from 0.1 to
5 h-1, more preferably in the range of from 0.2 to 2 h-1.
72. The process of any one of embodiments 67 to 71, wherein according to
(iv.1') G2 is intro-
duced continuously or semi-continuously, preferably continuously, into Z3.
73. The process of any one of embodiments 67 to 72, wherein according to
(iv.2') S2 is intro-
duced continuously or semi-continuously, preferably continuously, into Z3.
74. The process of any one of embodiments 67 to 73, wherein from 50 to 100
weight-%, pref-
erably from 70 to 100 weight-%, more preferably from 90 to 100 weight-%, of
the gas
stream F(i) consists of H2.
75. The process of embodiment 74, wherein the gas stream F(i) is introduced
at a pressure in
the range of from 20 to 150 bar(abs), preferably in the range of from 30 to 90
bar(abs),
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more preferably in the range of from 40 to 80 bar (abs), more preferably in
the range of
from 45 to 60 bar(abs).
76. The process of any one of embodiments 67 to 75, wherein the n
serially coupled catalyst
bed B(i) are fixed catalyst beds.
77. The process of any one of embodiments 1 to 76, wherein the
reaction zone Z3 is com-
prised in a continuous stirred tank reactor (CSTR) or a fixed bed reactor,
preferably in a
fixed bed reactor, more preferably a trickle bed reactor.
78. The process of any one of embodiments 53 to 77, wherein the
stream S3 obtained from
(iv) has a total chlorine content in the range of from 0 to 50 wppm (ppm by
weight), pref-
erably from 0 to 30 wppm, more preferably from 0 to 20 wppm, more preferably
from 0 to
10 wppm, more preferably from 0 to 5 wppm, more preferably from 0 to 2 wppm,
deter-
mined as described in Reference Example 2.1;
wherein the stream S3 obtained from (iv) has a chloride content in the range
of from at
most 40 wppm (ppm by weight), preferably from 0 to 30 wppm, more preferably
from 0 to
wppm, more preferably from 0 to 1 wppm, determined as described in Reference
Ex-
ample 2.2.
79. The process of any one of embodiments 53 to 78, wherein the
stream S3 obtained from
(iv), preferably after removing dissolved NH3, has a nitrogen content in the
range of from 0
to 200 ppm by weight (wppm), preferably in the range of from 0 to 100 wppm,
more pref-
erably from 0 to 50 wppm, more preferably from 0 to 10 wppm, determined as
described
in Reference Example 3.
80. The process of any one of embodiments 53 to 79, wherein the
stream S3 obtained from
(iv), preferably after removing dissolved H2S, has a sulfur content in the
range of from 0 to
200 ppm by weight (wppm), preferably from 0 to 100 wppm, more preferably from
0 to 50
wppm, determined as described in Reference Example 4.
81. The process of any one of embodiments 1 to 80, preferably of any
embodiment as far as
being dependent on embodiment 3, wherein the stream S3 obtained from (iii)
comprises
the one or more organic compounds comprising conjugated double bonds in a
total
amount in the range of 0 to 3 g(12)/100 g, preferably from 0 to 2 g(I2)/100 g,
more prefera-
bly from 0 to 1 g(I2)/100 g, more preferably from 0 to 0.25 g(I2)/100 g, more
preferably
from 0 to 0.1 g(I2)/100 g of the stream S3 obtained from (iv), determined as
described in
Reference Example 1.
82. The process of any one of embodiments 1 to 81, further comprising, after
(iii), or (iv) as
defined in any one of embodiments 53 to 81,
(v) one or more of a steam cracking step, hydrocracking step,
distillation, stripping, and
an aqueous extraction.
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83. The process of any one of embodiments 1 to 82, being a
continuous or semi-continuous
process, preferably a continuous process.
84. The process of any one of embodiments 1 to 83, consisting of (i), (ii),
(iii), preferably (i),
(ii), (iii) and (iv), more preferably (i), (ii), (iii), (iv) and (v).
85. A production unit for carrying out the process for purifying a
pyrolysis oil according to any
one of embodiments 1 to 84, the unit comprising
at least one reaction zone Z1, Z1 comprising a heterogeneous hydrogenation
cata-
lyst;
an inlet means for introducing SO into Z1;
an outlet means for removing Si from Z1;
at least one dehalogenation zone zone Z2, Z2 preferably comprising a heteroge-
neous adsorption material or a heterogenous dehalogenation catalyst;
an inlet means for introducing Si into Z2;
an outlet means for removing S2 from Z2;
wherein Z1 is located upstream of Z2;
and preferably an extraction zone to remove halides, preferably comprising one
or more
halides of N-containing organic compounds, said extraction zone preferably
being ar-
ranged downstream of Z2.
86. The production unit of embodiment 85, further comprising
at least one reaction zone Z3, Z3 comprising a heterogeneous hydroprocessing
cat-
alyst;
an inlet means for introducing S2 into Z3;
an outlet means for removing S3 from Z3;
wherein Z2 is located upstream of Z3.
87. A purified pyrolysis oil, obtainable or obtained by a process according to
any one of em-
bodiments 1 to 53 or according to any one of embodiments 54 to 81.
Examples
Reference Example 1 Measurement of the total amount of the one or more
organic com-
pounds comprising conjugated double bonds
The diene content is determined by U0P326-17. In this procedure dienes are
reacted with ma-
leic anhydride (MA) and the consumption of MA is determined (by titration of
the remainder
MA). It can be expressed as g(12)/100g(sample) or alternatively as
g(MA)/100g(sample). The
unit can be interconverted by multiplying the MA-value (MAV) by a factor 2.59
to obtain the val-
ue expressed with g(12)/100g(sample) corresponding to the molar weight of 12
and MA. Accord-
ingly, 1wt% Styrene or 0.52 wt.-% Butadiene correspond to 0.94g(MA)/100g or
2.43g(12)/100g.
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Reference Example 2 .1 Measurement of total chlorine content (wppm)
The sample is filtered with a 0.45pnn syringe filter before analysis. The
chlorine content is de-
termined by combustion of the respective sample at 1050 C. Resulting
combustion gases, i.e.,
hydrogen chloride, are led into a cell in which coulometric titration is
performed.
Reference Example 2.2 Measurement of chloride content (wppm)
The sample is filtered with a 0.45pm syringe filter before analysis.The
chloride content is deter-
mined by ion chromatography. Apparatus: Ion chromatograph 850 Professional
(Metrohm) (Pre
column: Metrosep A Supp4/5 S-Guard and Analytical column: Metrosep A Supp 5
250/4; Flow:
0.7 mL/min; Column temperature: 30 C; Detector temperature: 40 C; Inject
volume: 25 pL;
Suppressor MSM HC Rotor A). As Eluant: 3.2 mmol/L Na2CO3 ; 1.0 mmol/L NaHCO3
and as
Suppressor regenerant: 50 mmol/L sulfuric acid were used.
Sample preparation: 0.2 g - 0.4 g of the sample were weighed and dissolved in
10 mL toluene.
For analyte extraction, 10 mL deionized water were added. After
centrifugation, the aqueous
phase was extracted and analyzed. Samples with a concentration below the limit
value of the
method were spiked with 20 pg/L chloride standard solution (corresponding to a
limit value of 1
mg/kg chloride in the sample) to check the recovery rate.
Reference Example 3 Measurement of N content (wppm)
The nitrogen content is determined by combustion of the respective sample at
1000 C. NO contained in resulting combustion gases reacts with ozone so that
NO2 4 is
formed. Relaxation of excited nitrogen species is detected by
chennilunninescence detectors
according to ASTM D4629 (N). Calibration range is from 0.5 wppm to 50 wppm.
Samples with
higher concentrations are diluted with xylene to be in calibration range.
Reference Example 4 Measurement of S content (wppm)
The sulfur content is determined by combustion of the respective sample at
1000 C.
Sulfur dioxide which is contained in resulting combustion gases is excited by
UV
(ultraviolet) light. Light which is emitted during relaxation is detected by
UV fluorescence
detectors according to ASTM D5453 (S). Calibration range is from 0.5 wppm to
50 wppm. Sam-
ples with higher concentrations are diluted with xylene to be in calibration
range.
Reference Example 5 Particle size (D50)
The D50 particle size was determined by optical methods or by an air sieve,
for example by
various instruments, namely, Cilas Granulometer 1064 supplied by Quantachrome,
Malvern
Mastersizer or Luftstrahlsieb (air sieve) supplied by Alpine.
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Reference Example 6 Determination of the average pore volume
Pore volume can be derived from BET measurements (for micro and nnesopores) or
alternative-
ly Hg porosimetry (for macropores). The Determination of Pore Volume and Area
Distributions
in Porous Substances. I. Computations from Nitrogen Isotherms JACS 1951 (73)
373-380 E.P.
Barret, L.G. Joyner, P.P. Halenda.
Reference Example 7 Determination of the BET specific surface
area
The BET surface area of the adsorbent material is measured by using an
instrument supplied
by Quantachrome (Nova series) or by Micromeritics (Gemini series). The method
entails low
temperature adsorption of nitrogen at the BET region of the adsorption
isotherm.
Reference Example 8 Determination of the styrene content
GC method with a nonpolar, 100% dimethylpolysiloxane phase column and FID-
detector. Final
column temperature and inlet temperature are 330 C and 320 C, respectively.
Integrated area
signal of Styrene as ratio of all integrated peaks times 100% is Area%. Area%
roughly corre-
lates with wt.%.
Reference Example 9 Determination of the total acid number (TAN)
The total acid number was determined by titration with KOH according to ASTM
D3242.
Reference Example 10 Reactor loading and test setup
All reaction steps of the examples were conducted in reactors with inner
diameter of lOmm and
were operated in trickle bed mode (downflow). The reactor (80cm in length) is
loaded with co-
rundum (WSK F46; commercial corundum) from the bottom such that the lower 25cm
are filled
with inert corundum (cooling zone). On top of this the 30cm long catalyst or
adsorbents bed is
placed from 25 to 55cm and in this zone the reaction temperature is
maintained. In case of
shaped catalysts as P-doped NiMo-catalyst and E-157 SDU catalyst, the void
spaces of the
catalyst bed are filled with corundum (WSK F46; commercial corundum) as well.
On top of the
catalyst resp. adsorbents bed corundum (WSK F46; commercial corundum) is
filled from 55 to
80cm. In this corundum zone the feed is preheated to the reaction temperature
whereas in the
lower corundum filled zone the product stream is cooled from the reactor
temperature down to
the trace heating temperature.
Example 1 Process for purifying a pyrolysis oil according to the present
invention
A feed stream SO comprising a pyrolysis oil having a MAV of 9.01 g(12)/100g ,
a styrene content
of 6.1 Area% determined by GC, a total chlorine content of 560 wppm, a
chloride content of 1
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wppm, a nitrogen content of about 3260 wppm, a sulfur content of about 2630
wppm, a total
acid number (TAN) of 3.69 mg(KOH/g(feed) and a density of 0.8653 g/ml was
subjected to hy-
drogenation in a reactor comprising an activated Pd-catalyst (Catalyst E-157
SDU 1/8" com-
mercially available from BASF: 0.7wt.-%Pd on 1/8" alumina beads) with H2 at 50
bar and at a
temperature of 195 C. The Pd-catalyst was activated in hydrogen flow with
GHSV=1000/h at
ambient pressure with heating to 195 C at a ramp of 0.5K/min. After 12h at 195
C GHSV was
reduced to 500/h and pressure was increased to 50 bar within lh and kept for
2h before addi-
tion of SO started with LHSV=1/h. The resultant feed stream Si had a MAV
reduced by about
80% to 1.75 g(12)/100g and the styrene content was reduced to 1.1 Area% (> 80%
conversion),
the N- and S-contents were not changed compared to SO. Also, the chlorine
content was basi-
cally unaltered (cf. Table 1).
Table 1 Chlorine and chloride contents for SO and Si
total chlorine content chloride content
[wPPrri]
Feed SO 560 <1
Feed Si (product from hydro-
genation) 510 50
The stream Si was then subjected to dechlorination in a reactor comprising a
Cl-adsorbent (hy-
drotalcite: aluminum-magnesium hydroxycarbonate powder having a Mg0:A1203
weight ratio of
70:30) in the presence of H2 at 350 C and at a pressure of 50 bar. Before
use, the adsorbent
was compacted, then crushed and sieved to an average particle size of 500-1000
micrometers.
Further, it was calcined at 450 C for 5h in air and equilibrated in ambient
air overnight. Prior to
entering Si in the reactor, the obtained Cl-adsorbent was dried at 100 C and
200 C at a gas
hourly space velocity (GHSV) =2000/h in nitrogen under ambient pressure for 1
hour each while
ramping temperature with 1 K/min. At 200 C, gas was switched from N2 to H2 and
the pressure
was increased to 50 bar within 1 hour. After the pressure was attained, the
GHSV was reduced
to 475/h and the reactor was heated to 350 C with 1K/min. Once 350 C were
attained, Si was
introduced in the reactor at a liquid hourly space velocity (LHSV) =0.95/h.
The resultant product
stream was analyzed as shown in Table 2.1 and had a reduced total chlorine
content (at the
beginning of the operation reduced by about 90 %).
Table 2.1 Chlorine and chloride contents for Si and product stream
from dechlorination at
various time on stream (TOS)
total chlorine content chloride
content
TOS[h] [wppm] [wPPrri]
Feed Si 510
50
product stream (S2) 30 50
<1
product stream (S2) 55 110
<1
product stream (S2) 86 160
<1
product stream (S2) 130 150
<1
product stream (S2) 159 140
<1
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The intermediate products (S2) within the course of the reaction were combined
to form the
feed S2.
The stream S2 was further washed with an equivalent volume of water and
analyzed (see Table
2.2). The N-, S-contents were not changed compared to Si.
Table 2.2 Chlorine and chloride contents of combined products (S2) before and
after washing
total chlorine con-
tent [wppm] chloride content [wppm]
combined intermediate products
(S2) 130
<1
S2 (washed combined intermedi-
ate products) 120
<1
Further, the (washed) stream S2 was subjected to hydroprocessing in a reactor
comprising an
activated P-doped NiMo-catalyst supported on alumina (4.75wt%NiO, 19.57wt%
Mo03,
2.89wt% P205 and 72.79% support resp. A1203; prepared according to US
4,409,131) in the
presence of H2 at 50 bar and temperatures ranging from 350-395 C. Before the
P-doped N iMo-
catalyst was activated by being dried at ambient pressure and GHSV=2000/h with
N2 upon
heating with 1K/min and dwelled for 2h at 200 C. Thereafter, for the catalyst
activation, temper-
ature was reduced to 135 C and the atmosphere was switched to H2. After lh,
the pressure was
increased to 50 bar within 1 hour. After another hour the dosing of
sulfidation feed was started
with LHSV=2/h and the GHSV was adjusted to 1000/h. Sulfidation feed consists
of hydrocarbon
fluids (commercial mixture of boiling point range of 176-209 C, such as
VarsolTM 60) spiked with
2 wt.% DM DS (Dimethyldisulfide). After 2 h, the temperature was further
increased with
0.25K/min up to 350 C. Then, the temperature was kept constant for lh, LHSV
was reduced to
1/h and GHSV was reduced to 500/h before the addition of S2 started in the
reactor at a
LHSV=1/h.
After 73h TOS, the temperature was increased to 395 C and the system was
operated another
49h resulting compared to comparative example 1 in longer operation times at
both tempera-
tures without any indication of increasing pressure drop. Afterwards LHSV and
GHSV were re-
duced by 50% for another day before pressure was increased to 110 bar. LHSV-
reduction and
pressure increase did increase the N- and S-conversion further.
The resultant feed stream S3 had in average a total chlorine content of below
2 wppm, a chlo-
ride content of below 1 wppm (see Table 2.3) and also greatly reduced N- and S-
contents of
from 3264 wppm up to about 31 wppm for N content and of from 2630 wppm up to
about 47
wppm for S content (see Table 3).
Table 2.3 Chlorine and chloride contents before and after hydroprocessing
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total chlo-
rine con- chloride
tent content
[wPPril] [wPPril]
Feed S2 120 <1
S3 (product from hydroprocessing) <2 <1
Table 3 Nitrogen and Sulfur contents before and after
hydroprocessing
TOS N content S
content T LHSV p
[h] [wppm] [wppm] [ c] [M]
[bar]
Feed S2 3260 2630
product stream (S3) 14.7 99 39 350 1
50
product stream (S3) 25.72 198 57 350 1
50
product stream (S3) 32.41 215 47 350 1
50
product stream (S3) 43.43 251 68 350 1
50
product stream (S3) 49.95 257 63 350 1
50
product stream (S3) 62.98 284 78 350 1
50
product stream (S3) 86.64 247 121 395 1
50
product stream (S3) 104.92 223 191 395 1
50
product stream (S3) 117.28 271 120 395 1
50
product stream (S3) 128.24 163 65 395
0.5 50
product stream (S3) 138.6 133 82 395
0.5 50
product stream (S3) 153.6 142 49 395
0.5 50
product stream (S3) 165.63 41 40 395
0.5 110
product stream (S3) 179.83 31 47 395
0.5 110
product stream (S3) 192.03 31 71 395
0.5 110
Comparative Example 1 Process for purifying a pyrolysis oil not
according to the present
invention (representative of FR 3 107 530)
A feed stream SO comprising a pyrolysis oil as the one in Example 1 was
subjected to hydro-
genation in a reactor comprising an activated Pd-catalyst (Catalyst E-157 SDU
1/8" commercial-
ly available from BASF: 0.7 wt.-%Pd on 1/8" alumina beads) with H2 at 50 bar
and at a tempera-
ture of 195 C. The Pd-catalyst was activated in hydrogen flow with
GHSV=1000/h at ambient
pressure with heating to 195 C at a ramp of 0.5K/min. After 12h at 195 C GHSV
was reduced to
500/h and pressure was increased to 50 bar within lh and kept for 2h before
addition of SO
started with LHSV=1/h. The resultant feed stream Si had a MAV reduced by about
80% to 1.75
g(12)/100g and the styrene content was reduced to 1.1 Area% (>80% conversion),
the N-, S-
contents were not changed compared to SO, i.e. the N-content was of about 3260
wppm and
the S-content was of about 2630 wppm. The chlorine and chloride contents are
in Table 4.
Table 4 Chlorine and chloride contents for SO and Si
total chlorine content chloride content
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[WPPM] [wPPrn]
Feed SO 560 <1
Feed Si (product from hydro-
genation) 510 50
Further, the stream Si was directly subjected to hydroprocessing in a reactor
comprising an
activated P-doped NiMo-catalyst supported on alumina (4.75wt%NiO, 19.57wt%
Mo03,
2.89wt% P205 and 72.79% support resp. A1203; the catalyst was prepared
according to a pro-
cess as described in US 4,409,131) in the presence of H2 at 50 bar and
temperatures ranging
from 350-395 'C. The catalyst activation was made as in Example 1. The
temperature in the
reactor was kept constant after the catalyst activation for lh, LHSV was
reduced to 0.95/h and
GHSV was reduced to 475/h before the addition of Si started in the reactor
with LHSV=1/h.
After 48h TOS, the reactor temperature was increased to 395 C but after about
70h TOS the
pressure drop in the reactor system increased above 10 bar so that the feed
dosing was
stopped and the reactor was cooled down. A first intermediate pressure drop
increase was ob-
served from 55 to 60h TOS.
To demonstrate that such pressure increase was due to plugged downstream
tubes, the tube
was exchanged as explained in the following. Indeed, to enable access to the
downstream sec-
tion, the system was depressurized and purged with nitrogen. A lm long thin
tubing heated to
40 C (as the complete following downstream section) with 1.5mm ID was located
after the
transfer line from the reactor (180 C, 4mm ID) and before the gas/liquid
separator. This tube
was exchanged. This change of tube permitted to decrease the pressure drop
across the reac-
tor system substantially so that it was not noticeable anymore.
Furthermore, 5mg of a solid were removed from the tube. By XRD, NI-14C1was
detected in the
solid as the main crystalline phase as can be seen in Figure 1.
After this tube exchange, the reactor was restarted with sulfidation feed and
hydrogen and
heated with 1K/min to 350 C. At this temperature the original feed was dosed
again allowing
another 15 h of hydroprocessing operation before again a pressure drop
increase was observed
so that the feed dosing was stopped after about 100h TOS. Despite intermediate
system plug-
ging, the catalyst still revealed a relatively good performance after restart
with N-conversion of
>90% (cf. Table 5). For the combined product streams a total chlorine content
<2 wppm and a
chloride content <1 wppm was determined suggesting that converted Cl is not
present in the
liquid product stream in dissolved form and noticeable amounts or is present
but as particulate
matter which is filtered off upon sample preparation for Cl-analysis.
Table 5 Nitrogen and Sulfur contents before and after
hydroprocessing
TOS N content S content T LHSV
[h] [wPPrn] [wPPrn] [ C] [/h] p
[bar]
Feed Si 3260 2630
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product stream (S3) 9.19 43 46 350 1
50
product stream (S3) 15.37 54 51 350 1
50
product stream (S3) 21.38 72 44 350 1
50
product stream (S3) 27.4 98 57 350 1
50
product stream (S3) 36.59 125 60 350 1
50
product stream (S3) 48 147 73 350 1
50
product stream (S3) 62.32 104 131 395 1
50
system plugging:
tube exchange & re- 71
start
product stream (S3) 80.18 133 89 350 1
50
product stream (S3) 86.36 242 98 350 1
50
product stream (S3) 92.38 260 77 350 1
50
product stream (S3) 98.39 256 92 350 1
50
Table 6 Comparison pressure drop after hydroprocessing of
prehydrogenated and
dechlorinated feed (Ex. 1) and after hydroprocessing of prehydrogenated feed
(C.
Ex. 1)
Pressure drop before hy- Pressure drop after hydro- Total
droprocessing processing TOS
(mbar 100mIn(N2)/min) (mbar@100nriln(N2)/min) (h)
Ex.1 35 71
193
C. Ex. 1 37 210
101
The pressure drop of the reactor is externally determined with 100mIn(N2)/min
at ambient outlet
pressure. Resulting values are given in Table 6.
Compared to the process of the present invention, the aforementioned process
(representative
of FR 3 107 530) which does not comprise a dechlorination step between the
hydrogenation
and hydroprocessing steps presents high pressure drop increase rates during
the reaction
course which do not allow stable operation unless water is injected downstream
which causes
serious corrosion issues. In addition, also increased pressure drop of the
reactors after the re-
action (210 mbar vs. 71 mbar with the inventive process; cf. Table 6) was
observed. Therefore,
the process of the present invention presents a great improvement compared to
this known pro-
cess in view of more stable operation regarding increasing pressure drop and
thus allowing in-
creased TOS, which permits to obtain an improved oil production in terms of
stability and dura-
tion.
Comparative Example 2 Process for purifying a pyrolysis oil according to
the present inven-
tion
As opposed to Example 1, the process was started with a dechlorination step. A
feed stream SO
comprising a pyrolysis oil as the one in Example 1 was subjected to
dechlorination in a reactor
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comprising a Cl-adsorbent (hydrotalcite: aluminum-magnesium hydroxycarbonate
powder hav-
ing a Mg0:A1203 weight ratio of 70:30) in the presence of H2 at 350 C and at
a pressure of 50
bar. Before use, the adsorbent was compacted, then crushed and sieved to an
average particle
size of 500-1000 micrometers. Further, it was calcined at 450 C for 5h in air
and equilibrated in
ambient air overnight. Prior to entering SO in the reactor, the obtained Cl-
adsorbent was dried at
100 C and 200 C at a gas hourly space velocity (GHSV) =2000/h in nitrogen
under ambient
pressure for 1 hour each while ramping temperature with 1 K/min. At 200 C, gas
was switched
from N2 to H2 and the pressure was increased to 50 bar within 1 hour. After
the pressure was
attained, the GHSV was reduced to 475/h and the reactor was heated to 35000
with 1K/min.
Once 350 C were attained, SO was introduced in the reactor at a liquid hourly
space velocity
(LH SV) =0.95/h.
After 165 h TOS, the pressure drop in the reactor system increased above 10
bar so that the
feed dosing had to be stopped and the reactor was cooled down, purged with
toluene and dried
with nitrogen. The pressure drop of the reactor is externally determined with
10OrnIn(N2)/rnin at
ambient outlet pressure resulting in 1102 mbar whereas the reactor's pressure
drop before test-
ing was determined with 37 mbar. The chlorine and chloride contents in the
obtained stream S2
are in Table 7.
Table 7 Chlorine and
chloride contents before and after dechlorination
TOS total chlorine content chloride
content
[h] [wPPrri] [wPPrri]
Feed SO 590
2
product stream (S2) 32 57
<1
product stream (S2) 57 150
<1
product stream (S2) 82 200
<1
product stream (S2) 129 290
<1
product stream (S2) 153 300
1
Table 8
Comparison pressure drop after dechlorination alone or after pre-
hydrogenation +
dechlorination
Pressure drop before
Pressure drop after dechlo- Total
dechlorination rination
TOS
(mbar 100mIn(N2)/min) (mbar
100mIn(N2)/min) (h)
Hydrogenation +
Dechlorination 29 38
165
steps in Ex.1
Dechlorination
37 1102
165
step in C. Ex. 2
After the reaction the reactors were unloaded. The different parts of the
reactor loading were
separated into the inert corundum material on top (preheating zone) and below
(cooling zone)
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the adsorbents zone and the adsorbent. Especially within the preheating zone
color gradients
were observed across the length. Therefore, samples were homogenized before
analysis.
Samples were heated in air up to 700 C and the resultant mass loss was
recorded by thermo-
gravinnetric analysis in conjunction with differential scanning calorinnetry
(device STA 449 F3
Jupiter from company Netzsch). For all samples obtained from comparative
example 2 the exo-
thermic mass loss was increased which is indicative of increased coke
formation. The relative
increase of coke formation to example 1 is most pronounced in the preheating
zone with rough-
ly 100% increase of the mass loss.
In Figures 2a and 2b the coloring of the corundum from the preheating zone can
be compared
showing a darker color for dechlorination only (C. Ex. 2 - 2a). After heating
in air, samples did
decolorize to white as in the fresh state.
Table 9 Comparison of the mass loss in wt.% upon heating corundum
of the preheating
zone in air after dechlorination or after pre-hydrogenation + dechlorination
Hydrogenation + Dechlorination steps in Ex.1 (Si) [wt/0] 1.83
Dechlorination step in C. Ex. 2 (SO) [weio] 3.68
As both dechlorination experiments in example 1 and comparative example 2 were
operated for
the same duration, conditions and with the same adsorbents and inert corundum
and showed
large differences in pressure drop of the reactors afterwards and mass loss in
heating up the
material of the preheating zone in air it can be derived that the coke build-
up in the dechlorina-
tion step is accelerated if feed is not prehydrogenated.
Therefore, based on this example, it has been demonstrated that a
hydrogenation step is man-
datory prior to the dechlorination step. Indeed, starting with dechlorination
directly results in ex-
tremely fast increase of pressure loss by coking which is not acceptable for
industrial plant op-
eration. In addition, the dechlorination efficiency (cf. Table 2.1 and 7) is
increased if the feed is
prehydrogenated before dechlorination.
Brief description of the figures
Figure 1 is the analysis by XRD of the solid obtained in Comp. Ex. 1
contained in the tube.
Reflexes of crystalline N H4CI are marked with asterisks.
Figure 2 a. is a picture of the corundum of the preheating zone for
Comparative Example 2
(black powder).
b. is a picture of the corundum of the preheating zone for Example 1 (powder
lighter
than in a.).
Cited literature
- WO 2017/083018 Al
- FR 3 103 822
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