Note: Descriptions are shown in the official language in which they were submitted.
A PROCESS FOR THE REPROCESSING OF CARBON
CONTAINING WASTES AND BIOMASS
Abstract of the dlsclosure
This invention relates to a process for the reprocesslng
of carbon containiny wastes and blomass by hydrogenation of the
same at elevated temperature and at least 1 bar hydrogen pressure.
Back~round of the invention
It is known ln the publlc and to the artisan that
wastes, whlch accumulate worldwide, reprasent an lncreasing
problem with regard to envlronment.
For many years waste~ have been disposed o~ by
land~illing, for example in abandoned pits and remote areas. For
a long time the chemical ~truature of wastes and lts longterm
ef ~eats on ~oil and ground-wa~er have not been taken into
consideratlon. During recent years hazardous waste~ have been
dispo~ed o~ at special ~ites where measures have been taken to
prevent leaking into the ground. In the ~uture however
environmental contamination of these sltes is likely to be the
sub~ect of concern.
Consequently extensive endeavours have been undertaken
in order to reproaes~ waste~ and to obtaln on the one hand
improvement~ with regard to envlronmental contaminations and on
the other hand ~3eful product~ from wastes.
In "The Oil and Gas Journal" of Dec. 25, 1~78, page 80,
for example a pilot plan~ i~ de~crlbed ~or the pyrolysis of
plastics, whereby gases and fuel oils are ob~ained.
C
~ 2~
- 2 - UK 357a
In "Hydrocarbon Processing", April 1979, page 183, an
incineration system is described, which is particularly
suited for burning hazardous wastes.
Also the biQchemical degradation of plastics has been
investigated ~see for example: European Chemical News,
Sept. 10~ 1979, page 28). In "Chemical Engineering",
August 13, 1979, page 41 the solidification of hazardous
wastes is described by mixing wastes with solidifying
materials like cement.
A survey of the most important processes for handling waste
materials is presented in"Chemical and Engineeriny News",
October 1, 1979, page 34. Particular emphasis is given
to gasification of biomass, for example of wood and
related feedstocks. Products are essentially carbon
monoxide and hydrogen.
On page ~6, left column, a test program ls disclosed for
the conversion of waod suspended ln water, in the presence
of hydrogen and Raney-nickel.
In "Europa Chemie", 25, 1979, page 417, a process for the
plastification and molding of mixed plastic waste is
described. The fluidized bed incineration of wastes is
described in "Chemische Industrie", XXXII, April 1980,
page 248.
The conversion of wastes and biomass by treatment with
water and alkali is described in "Chemistry International'l,
1980, No. 4, page 20. Numerous additional publications
in the field of waste treatment are known. ~
236
3 25118-70
,
In recent years in partlcular waste incineration has
been developed and large-sized technical units have been
constructed. Although dust removal and flue gas scrubbing have
been integrated in~o these units, the converslon of wastes to
carbon dioxide (and water) is an inevitable accompanying problem.
In particular with respect to the accumulation of CO2 in the
atmosphere, the production of CO2 is undesirable. Furthermore
~ontaminatlons llke heavy metals, SO2, NOx and others escape lnto
the atmosphere even under vexy advanced operatlng condi~ions.
Pyrolysis is in the meantime alsQ carried ou~ on a
technical scale ~see for example, "Vereinlgte Wirtschaftsdienste
GmbH", October 4, 1985, page 9). Di~advantages of pyrolysis are
the predomlnant ~ormation of gase~ and o~ a strongly contamlnated
coke residue.
The description of the state of the art indicates that
the problem of reproaeRsing of was~es and biomass has hitherto not
been solved satisfactorily.
SummarY of the Invention
A non-obvious, much more favourable ~olution to thls
problem compared to the state of the art in particular with regard
to high yields of valuable liquid products, is dlsclosed in the
present lnvention. The invention concerns a process for producing
hydroearbons predominantly boiling ln the naphtha and gas oil
ranqe by hydro0eDative cleava~e of carbon containing waste
materialæ wlth the exception of waste rubber, the improvement
23~
3a 25118-70
comprising reacting mixtures of carbon containing waste materials
of synthetic or predominantly synthetic origin with molecular
hydrogen at a temperature of 200 - 540 C, a pressure of 50 - 549
bar and a residence time of 15 minutes to 6 hours.
~,i
j ~ 3~ 9~3~ 23769-39
-~.~,
According to one aspect the invention provides a
process for the hydrogenative reprocessing of carbon containing
waste materials, which may contain vulcanized rubber, wherein
mixtures of carbon containing waste materials of synthetic or
predominantly synthetic origin are treated with hydrogen and/or
hydrogen containing gases and/or hydrogen transferring solvents
(hydrogen donor solvents) at a temperature of 200 to 600 C, a
pressure of 30 to 500 bar and a residence time of l minute to 8
hours.
According to another aspect the invention provides a
process for the hydrogenative reprocessing of carbon containing
waste materials, which may contain vulcanized rubber, wherein
the process is carri.ed out in the presence of a hydrogen donor
solvent at a temperature of 75 to 500 C, a pressure of 1 to 300
bar and a residence time of l minute to 8 hours.
~ ccording to still another aspect the lnvention
provides a process for the hydrogenative reprocessing of carbon
containing waste materials, which may contain vulcanized rubber,
wherein in a first stage with or without a hydrogen donor
solvent, the hydrotreating is carried out in the presence of
protic solvents, at a pressure of 1 to 150 bar and a temperature
of 75 to 500 C and in a second stage at a temperature of 200
to 600 C and a pressure of 30 ~o 500 bar.
~z~
' - 4 - UK 357a
Preferred Embodiment
The inventive process permits, after separation of
inorganic components like glass, metals, stone materials
and others, to convert waste mat~rials without further
separation into valuable hydrocarbons. These are C1- C4
gaseous hydrocarbons, li~uid hydrocarbons in the naphtha
range, as well as middle distillates and heavy oils, which
can be used as heating oils and diesel fuel. According to
the invention preclassified waste materials can also be
converted, in particular in such a way, that carbon
containing waste of synthetic origin, like for example
plastics and mixtures of plastics, rubber, waste tires,
textile waste, is at least roughly separated from the
vegetable or biomass portion and subsequently submitted
to a separate hydrotreatment, or combined with industrial
wastes,like coatings and paint resids or organic chemicals~,
was~es o' l~ustri~l ~roduction, or~anic synthetic shreddin~,
waste of the motor-vehicle industry, sewa~e sludge
or used-oils. Other waste material like paper, food
residues, farm and wood wastes, plant residues and others
can roughly be separated or remain in the synthetic portion
to a certain extent.
Garbage can for example be reprocessed according to the
invention in such a way that plastics, rubber, textiles
and other synthetic materials are roughly separated and
separately submitted to hydrotreating, or combin~d with
waste tires and or industrial chemical and plastic waste
and or used-oils and o~hers.
The process according to the invention is also very well
suited for hydrotreatment of the above-named wastes resp.
waste mixtures in combination (mixed) with coal, coal
components like for example residual oils derived from coal, ¦
coal oils, pyrolys- oils, cru~e oil, resi~ oils derive~
from crude oil, other
- 5 -
,.
36
UK 357a
- 5
crude oil components, oil shale and oil ~hale components,
oil sand extracts, asphalt and bitumen and similar materials,
as well as with mixtures of these materials.
The separation of the above-named inorganic materials from
carbon containing waste materials can be carried out according
to the state of the art. These irorganic materials can be
disposed of by landfill for example, i they are not
recycled and reprocessed. Crushing or shredding and
separation of waste material and biomass can be carried
out according to the state of the art.If the conskruction of
the processing devices is not prohibitive, the inventive
process can also be carried out in the presence of inorganic
materials.
Waste components, which can not be converted into
hydrocarbons, like ~or example sulfur, nitrogen,oxygen and
halogens in the form of their compounds are aonverted into
their gaseous hydrogen compounds, i.e. H2S, NH3, HCl.H20 and
others. These compounds can be separated by gas scrubbing
and be further processing according to the state of the art.
In addition, the formation of hazardous compounds, which
are obtained by waste incineration, like NOx, 50X or of
dioxines is avoided according to the instant invention.
Furthermore plastics like polyvinylchloride, which are
difficult to incinerate, can be converted without risk
according to the invention.
: .
The inventive hydrogenation of carbon containing waste
materials can b~ carried out with very good results in the
absence of catalysts. However even improved results can
- 6
~29a~;~36
- 6 - 25118-70
be obtained with regard to conversion and selectivity of the for-
mation of certain hydrocarbon fractions, in the presence of cata-
lysts, like for example in the presence of Fe, Mo, Ni, Co, W and
other metals and/or their compounds active in hydrogenation,
whereby these catalysts can consist of a single component or a
mixture of at least two of the components and whereby these compo-
nents may be applied on catalyst carriers for example on alumina,
silica, aluminum silicate, zeolites, other carriers which are
known to the artisan as well as mixtures of these carriers or
without carriers. Certain zeolites are active by themselves as
catalysts.
Other catalysts which can be used according to the in-
vention are once-through catalysts like hearth furnace coke
(~lerdofenkolcs), Winkler-gasification dusts, for example high-
temperature-Wi~kler dust (HTW dust), dusts and ashes obtained by
the gasification of coal in the presence of hydrogen, whereby
methane is formed (HKV-dust), furthermore catalysts, which contain
iron oxides, like so-called red mud, Bayer-mass, Lux-mass, dusts
from the steel industry and others. These materials can be used
as such or be doped with metals or metal compounds active in
hydrogenation, in particular with heavy metals and/or their com-
pounds, like Fe, Cr, Zn, Mo, W, Mn, Ni, Co, furthermore alkali and
alkaline earths like Li, Na, K, Rb, Be, Mg, Ca, Sr, or Ba, as well
as mixtures of these metals and/or metal compounds.
The catalysts can be sulfidized before or during use.
The inventive hydrotreatment can take place in wide
ranges of temperature and pressure depending on the feed material,
9~3-~i
7 25118-70
The hydrotreatment with or without cataly3t, of mixtures
of synthetlc waste materials like plastics respectively plastic
mixkures, rubber, waste tlres, textile wastes, industrial chemlcal
wastes, waste oils, used-oils and others, ls carried out at
pressures of 50-450 bar, at temperatures of 200-540C, and at
residence times of 15 mlnutes to 6 hours. Pasting oils can be
added to the feed as well as coal, coal components, crude oil,
crude oil components and residues, oil shale and oil shale
components, oil sand extracts and their components, bi~umen,
asphalt, ashaltenes and simllar materlals. The feed respectively
feed mixture oan al80 be pretreated wlth a solvent and
subsequently the extract led to the hydrotreatment.
The hydrogenating gas can be of different quality, it
may contain for example besides hydrogen, cer~ain quantities of
C0, C02, ~2S, methane, ethane, ~team etc.
Approprlate hydrogen qualitles are for example those,
which are ~ormed in gasifica~ion~ of carbon containlng materials.
Such materials may be resldues ~rom the processlng of crude oil
and other oils of mineral oil origin, or aoal as for example
lignite, wood, peat, or resldue~ of coal processing operations as
for example coal hydro~enation. Approprlate gaslfication
materials may also be blomass and the vegetable portion of
yarbage. Of course pure hydrog~n qualiti~s a~ ~or example
hydrogen produced electrolytically are also well suited.
Thus, according to the invention, for example garbage
can be first separated into a vegetable and into a syn~hetic
portion and subseyuen~ly the ve~etable portlon can be
~,,.J
129~23~
UK 357a
gasified in order to produce hydrogen to be used in the
process, whereas the synthetic portion is treated with
hydrogen.
The vegetable portion may alternatively be fed to a
fermentation.
The feed to be hydrogenated in general isessentially freed ~rom
inorganic materials and may be dried, shredded, ground,
molten and mixed with pasting oil or other materials, then
heated to reaction temperature and subse~uently txeated with
hydrogen without or with catalyst.
In those cases, where at elevated temperature already in
the mixing device a pumpable slurry or paste is obtained,
the feed can be pumed into the hydrogenating reactor. In
order to obtaln a pumpable paste or slurry, a pasting oil
may be used or example originating from various sources
from the hydrogenation process. Pasting oils may
alternatively be materials from other sources than the
hydrogenating unit. Also watex or steam may be added. A
pumpable slurry or paste may for example also be obtained
by addition of crude oil or crude oil components or coal
components or bitumen, asphalt and similar materials.
The feed can also be introduced into the unit respectively
hydrogenating reactor by employing conveyers for example
screw conveyers or other conveying devices.
. ~ 9 ~
236
- 9 - 25118-70
The reaction zone consists of one or several reactors
which are arranged parallel or in series. The reactor(s) is(are)
preferably followed by a hot catchpot, as known for example from
the sump phase hydrogenation~ In the hot catchpot the portion
which is gaseous at the temperature of the hot catchpot is separa-
ted from the sump.
The gaseous portion is cooled, whereby liquid hydro-
carbons are obtained, which are further processed according to the
state of the art, for example by cracking, in particular by hydro-
cracking, by refining and distillation. The products may in partbe recycled to the hydrogenating unit and used as a pasting oil.
The products, which are gaseous at normal temperature and pres~
sure, like hydrogen, methane, ethane and C3 to C4 hydrocarbons may
be scrubbed in order to liberate them from H2S, NH3, HCl, CO or
CO2 .
The hydrogen portion in general is recycled into the
hydrogenating reactor (s). The gaseous hydrocarbons may be con-
verted into additional hydrogen by steam reforming. The products
obtained from the gas phase of the hot catchpot, in particular the
products which are liquid at normal conditions can be treated, as
mentioned above, in a refining unit, which in general is operated
under hydrogenating conditions. In this step small amounts of
compounds which contain hetero atoms can be completely destructed,
leading to hydrocarbon productsr which are essentially free from
sulfur, nitrogen and halogens. Higher boiling portions may be fed
into at least one cracking unit, in particular into a hydrocrack-
ing unit. Certain portions of the products thus obtained may be
.~
~29~ 3Ei
- 10 - 25118-70
at least in part recycled to the hydrogenating reactor and be used
as pasting oils or solvents.
The sump of the hot catchpot may be worked up in differ-
ent ways, for example by vacuum distillation, whereby the sump of
the vacuum distillation may be fed into a gasification unit, lead-
ing to hydrogen and carbon monoxide~ These gases may be advan-
tageously processed in the above mentioned gas scrubbing and gas
processing unit. Alternatively the residue of the vacuum distill-
ation may be processed in a coXing unit, for example delayed cok-
ing unit or may be processed in a deasphalting unit or other pro-
cesses according to the s-tate of the art. The residues and ashes,
which contain the metal contaminations may be disposed of in land
fill depots according to the state of the art or may be worked up
in the metallurgic industry or may be used partially as ca.alyst
in the waste hydrogenation. Furthermore the sump of the hot
catchpot may be txeated by supercritical extraction, for example
with propane, butane and higher boiling hydrocarbons, which can be
taken from streams of the waste hydrogenating unit. The extrac-
tion agent may at least in part be introduced into the hydrogena-
ting reactor itself.
The hottoms of the hot catchpot and/or the vacuum dis-
til1ation residue in particular after deasphalting may also be
used at least in part as a pasting oil.
In Figure 1 an example of the inventive process is shown
with examples of subsequent processing
steps.
,~
~ 3~
UK 357a
In Figure 2 an example of the inventive process is
shown with preceeding solvent treatment.
In Figure 3 a combination of used-oil refining and
inventive process is shown.
In Figure 4 the dependence of the yield of the
individual fractions from the temperature
is shown.
Ex~ es
With the aid of Figure 1 the inventive process is
explained in detail:
The waste materials are fed into mixing device (1)
after shredding or grinding,if necessary an additional
grinding may take place after mixing of the feed materials
In addition, a pasting oil may be added either through
line ~2) originating rom streams of the same unit or
through line ~2a) from an outside source.
Furthermore catalyst may be added to ~1) through line ~3)0
The feed is hydrogenated in reactor ~5) by adding
hydrogen or hydrogen containing gases. Instead of reactor
(5)~several hydrogenating reactors can be installed,
which~ are either arranged parallel~ or in series. The
hydrogenated~product is transferred to hot catchpot (6).
In (6) he gaseous products ~7)~ are separated from the
: ~ ~5U~p. The gaseous products are cooled in~heat exchangex
(8) and fed lnto separator (9). In (9) the li~uid
products are separated from the gaseous products, which
are drawn off overhead. The llquid products are
- 12 -
.
~ 3~
UX 357a
processed according to the state of the art, for
example by distillation, hydrocracking of the heavier
fraction and refining. The gaseous products are liberated
from impurities like H2S, NH3, HCl, C02 and others in
(10). Hydrogen is recycled to the hydrogenating reactor.
Gaseous hydrocarbons are separated and may, at least
in part, be converted into hydrogen and carbon monoxide
by steam reforming in ~11 ) .
The li~uid product of the hot catchpot may for example
be subjected to a vacuum distillation ~12), where
additional oils (13) are obtained, which may be used
in part as pasting oils.
The bottoms of the vacuum distillation can be subjected
to coking ~14), for example delayed coking. The products
(15) from ~14) are transerred to the gas and li~uid
processing units. Coke ~16) obtained in ~14), which
contalns ash components like metals and others may
be subjected to a gasiication unit (17) or can be
disposed of according to the state of the art or may
be used at least in part as catalyst depending on the
composition. Alternatively the bottom of ~12) may be
directly submitted to gasification in (17). The gases
~18) are transferred to the gas processing unit. Ashes
(19) respectively carbon black may be disposed of
according to the state of the art by incine~ation,
recycling to the metallurgic industry are may be used
at least in part as catalyst dependiny on the com-
position.
12~23~;
UK 357a
As a further alternative the bottoms of the hot catchpot
may be extracted by a supercritical extraction agent, for
example propane, butane, or higher boiling hydrocarbons.
The extract thus obtained is further processed according
to the state of the art. The remaining residue can be
processed analogously to the processing of the hot
catchpot bottoms. The extraction agent can, in
particular in the case of hydrogenating reactors,
which are installed in series, be fed at least in part
into the reactors themselves, or at least into one of
the reactors.
In the case of feed material with comparatively high
amounts of hetero atoms like sulfur, nitrogen or
halogens, the li~uid product rom separator ~9) may be
submitted to refining ~20), in general to hydrogenative
refining. The refined product ls distilled in
distillation ~21), however alternatively the fractions
originating from ~21) may be submitted to refining.
The bottom o the distillation may be cracked in a
cracking unit ~22) in order to obtain additional lower
boiling products ~23).
It is to be emphasized that the process diagram shown
in Figure 1 is to be considered as an example and not
as a limitation of the inventive process of hydrogenative
treatment of waste materials and /-or bioma6s. It is known
to the artisan that products originating from
hydrogenating reactors can be processed by various other
proce:sing :tep: and combination: of proce::ing :tep:.
~ 2,3~
UK 357a
- 14
In the lnventive process also used-oil and;used-oil
residues resulting from used-oil refining and
redistillation can be treated, as shown examplarily .
in Figure 3.
For example used-oil can be taken from storage tank (1)
and chaxged to a physical and/or ch~nical separating resp.purifi-
cation unit(2)in o.rder to separate solids, water and other
undesirab}e materials. The prepuriied product thus
obtained, can be fed through line (3) to a hydrogenating
reactor (4) or to the refining unit (7).
Gaseous respectively liquid products from hot catchpot
(5) resulting from the hydrogenation can be fed through
line (6) to the refining unit (7). The bottoms of the
distillation ~8) of the refined used-oil can be
subjected to hydrogenation in reactor ~4) through line
~g) .
Waste materials from storage ~10) to be hydrogenated
are introduced into a shredding and mixing unit (11).
This material is fed into (4) through line (12).
A~ditional materials like for example heavy oils from
mineral oil or coal origin can be added through line (13).
Bottoms of the hot catchpot can for example be subjected
: to gasification ~15) through line 114)-
:
According to the invention also a treatment with
suîtable soIvents, in particular hydrogen donor solvents
~can preceed the actual hydrogenatlon. Subsequently
di~solved and undissolved material are separated from
each other:and separately subjected to hydrogenation in
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~2~3~23~
UK 357a
the hydrogenating reactor. B~ subsequent distillation
the solvent can be separated and recycled. The
undissolved material can alternatively be subjected
to gasification or coking.
Again in this inventive process variant the waste
material feed can be mixed with coal and coal
components, crude oil and crude oil components and
other materials as mentioned previously.
Again for this inventive processing of waste materials
a variety of devices and processing steps are
possible as known from the state of the art.
Suitable solvents are for example tetraline,anl:hracene oil,isopropa-
nol ,cresols containing oils, decaline, naphthaline,
tetrahydrofurane, dioxane and also other hydrocarbons
from mineral oil and coal origine or hydrocarbons
originating from the hydrogenating unit, as well as
oxygen containing hydrocarbons and oils. Finally
also water or steam can be added.
Th~ inventive application of solvents is explained
in more detail with the aid of Figure 2. In device ~1)
the shredded or ground Eeed material is at least partially
dissolved resD.suspended at elevated temperature.In separating
device (2~ undissolved material can be separated from
the solution. The undissolved portion can be further
procesRed in coking unit ~3) or gasification unit (4).
129~2~6
UK 357a
- 16
The dissolved xesp. suspended material is hvdrotreated in the
hydrogenating reactor (s) (5). Preferably hydrogen
donor solvents are used like tetraline, decaline,
anthracene oil, creosote oil or other higher boiling oils. .
Thu~ the hydrogenation can be carried out at low hydrogen
pressures, even at 1 bar.
Residence time and hydrogen pressure are adjusted with
respect to each other. The hydrogenated product can be
worked up as usual, for example by distillation (6).
In a further example of the hydrogeneration of waste materials in the
~resence of hydrogen donor solventsr anthracene oil is used
as a solvent. The material to be hydrotreated,
possibly mixed with coal or mineral oil materials, is
dissolved at 370 - 420C in the presence of strong acids,
for example of p-toluene sulfonic acid and/ or hydrogen
fluoride and subsequently, if necessary after separation of
undissolved materials, hydrogenated in the presence
of hydrogen fluoride respectively hydrogen chloride and
of salts like SbC15, SbF5 which axe capable of forminq
stronq coordinated acids, at temperatures of 75 - 220C,
preferably of 150 - 200C and hydroqen pressures of 1 - 5
bar Preferably of 1 - 2 bar. In a subsequent hydroqenatinq
step unsaturated products are converted into saturated
products.
Also under conditions of the SRC coal hydrogenation
(solvent refined coal),waste materials including biomass
can be converted into distillable oils in high yields.
- 17
~ 23~
UK 357a
Again coal and mineral oil components may be added.
Suitable conditions in the dissolving step are 380 - 480C.
In the hydrogenating step in general temperatures of
350 - 450C are applied and pressures of 110 - 250 bar,
preferably of 120 - 220 bar, whereby the previously
named catalysts may be added.
The investigations of applicant have shown that processes,
wh~ch have been developed for the hydrogenative treatment
of coal and crude oil residues can also be applied to the
hydrogenative cleavage of carbon containing waste
materials even of very different structure and origine.
This is in particular the case if synthetic waste materials
are hydrotreated,although in individual cases modified
conditions may be applied. Again coal and mineral oil
and their components, in particular residues can be added.
Examples, which are not limitative, of such processes
are the H~Oil process (HRI Inc. and Texaco Development
Corp.), the Canmet process ~Partec Lavalin Inc./Petro
Canada), the LC-Fining process (Lummus crest.Inc.)~ the
VE~A Combicracking process (VEBA), the VEBA LQ Cracking
process (VEBA), the RCD Unibon process (UOP Process
Division of UOP Inc.), the Isomax process (Chevron
Research Co. / UOP Co.), the Residfining process (Exxon
Research and Engineering Co.), the Unicracking and
Unicracking / HDS process (Union Oil Co. of Calif.),
the ~C Unibon process tUOP Process Division of UOP Inc.),
the Isocracking process ~Chevron Research Co.), the Heavy
Oil Cracking process (Phillips Petroleum), the
Dynacracking process (Hydrocarbon Research Inc.), the
Linde-Hydroconvort~r process and others.
1~94236
UK 357a
- 18
In the cases where these processes are fixed bed catalyst
processes at least dissolved waste materials, for example
in coal oil and crude oil resp. their components, can be
hydrotreated according to the invention.
According to the instant invention waste materials can
also be hydrotreated in such a way that mixtures of
vegetable / biomass / cellulose wastes and synthetic
wastes are converted in several steps under conditions,
whereby in one step, essentially by hydrolysis and
hydrogenation, the vegetable / biomass-portion including
cellulose containing materials like paper is converted,
whereas in a second step the hydrogenative conversion of
the synthetic portion takes place. Both steps can also
be carried out in the presence of solvents, for example
a hydrogen donor solvent~ As an example in the first step
the hydrotreatment with or without catalyst is carried
out at a pressure o 1 - 150 bar, preerably at 25 - 60 bar
whereby preerably protic solvents like water and/or
alcobols are present. Subsequently oils, essentially
obtained by the conversion o the vegetable / biomass /
cellulose portion are separated for example by extraction
and the remaining essentially synthetic portion is then
hydrotreated under conditions outlined previously.
The stepwise conversion can alternatively be carried out
in such a way, that in the first step the vegetable /
biomass / cellulose portion is essentially cleaved hydro-
lytically, for example in the presence of bases or acids,
whereby this conversion may be carried out in the presence
of carbon monoxide and preferentially in the presence of
water and/ or other protic solvents like alcohols, whereas
in the second step the essentially synthetic portion is
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lZ94~3!6 ~
UK 357a
- 19
hydrotreated.
Alternatively the waste material can be first separated
into a vegetable/biomass / cellulose portion and a
synthetic portion and both portions can be converted
separately under the conditions described.
Also in these cases catlysts may be used. Furthermore
between first and second step a drying step may be
installed.
"Steps" are to be understood in the present invention
in such a way, that a certain step, as for example the
irst step named above for the hydrolytic conversion of
the vegetable / biomass / cellulose portion may itself
consist of several steps arranged parallel or in series.
Further examples are disclosed in table 1. The results
have been obtained at a pressure of 100 bar (cold), a
temperature of 450 C and a residence time of 4 hours.
As a pasting oil a crack vacuum fraction was mixed with
the waste material at a ratio of oil to waste of 3 : 7.
No catalyst was applied. At a variety of conditions
different from the conditions of the table, but within
temperatures of 200 - 600C and pressures of 50 - 500 bar
also good resultc wer- obtained.
.
- 20
,,
1~2~6
~ UK 357a
- 20
Table 1
_______ .
_ _ _ _ _. . _ _
Hydrocarbons
Feed Conversion CO/CO2 Cl-C4 - Bp. Bp. . .
material <390C ~390C
weight% weight% weight%
. . ~ . _
Plastic waste 99,5 0,5-3 1-6 42-930,5-56,5
. _ _
Green Tun2 99,3 2 2 82 14
. _ . .
Plastic Foam 98 19 10 52 19
....... ,.............. _ _
Waste carpet 97 1 - 6 10-35 35-5~ 7 - 54
_ _ . _ _
Blend of
Polye~hylene 99,7 0,S 193 5,5
Polystyrene
____ ____
Blend of .
Pclyethy;ene 98,5 3 458 35
Plexi~lass
~ - ~ _ , _
: .
1 Blend of Polyethylene, Polypropylene, Polyacrylate
Rubber, Waste.tires, Polystyrene
2 Synthetic waste components, Polyvinylchloride includPd
: from an average daily sample of a gar~age separating
unlt
3 polyurethane, polystyrene
: ~ ~
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UK 357a
Similar results were obtained at elevated hydrogen
pressure, whereby shorter residence times could be
adapted.
In table 2 results are summarized of the hydrogenation
of the synthetic portion obtained from a garbage
separating unit including a fraction of 15 weight %
of polyvinylchloride. The results show the dependence
of conversion and yields from the hydrogenating time at
450C at a pres~ure o~ 200 bar (cold).Pasting component was a
used machine oil in a ratio of waste to oil of 2,3 : 1.
No catalyst was used. In the last experiment a pasting
oil originating from the hydrogenating unit was used.
Table 2
_______
_.
Hydrocarbons
iling range
reactionconversio~ C1~C4 ~.180C 180-390C ~ 390C
time in %
hcurs HC's with
Bp. <390C weight% weight~ weigt% weight~
2 59 1 24 34 41
4 81 2 34 45 19
41 86 21 47 18 14
4 89,5 28,5 47 14 10,5
6 97 21 56 20 3
L _ ~ 65
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1 After 2 ~ours it was cooled, the pressure reduced
and then the H2 pressure again adjusted to
200 bar.
2 with bitumen added in a ratio of waste to bitumen
of 2 O 1
3 with pasting oil o the hydrogenating unit
(130-390C boiling range)
Table 2 shows that at constant pressure, the selectivity
to hydrocarbo~ boiling ~180C increases from 4 weight %
(2 hours) to 65 weight % (6 hours), whereas the portion
of high boiling fraction (~390C) decreases from 21
weight % to 1 weight ~. If the fraction with a boiling
range of 180 - 390C is used as pasting oil, blended
with waste material, the pasting oil is also practically
completely converted to low boiling hydrocarbons.
By subsequent hydrogenative reining the halogen content
in the product fractions can be eliminated practically
~uantitativeIy (~ lppm). Alternatively the total hydro-
carbon product can be refined hydroqenatively.
Thus for example a hydrocarbon fraction, boiling between
180 - 390C, obtained by hydrogenation of essentially
synthetic waste material from a"green tun" was refined
under hydrogenating conditions. The chlorine content
of the~feed was 2.400 ppm. After refining at 50 bar
hydrogen pressure and 270C ~ product was obtained, the
chlorlne content of whioh wac no longcr~detectable.
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- 23
Figure 4 represents the dependence of the yields of the
individual fractions on the temperature at a residence
time of 2 hours. Essentially similar results are obtained,
if synthetic waste material is hydrotreated without
addition of pasting oil. The same applies, if for
example crude oil residues are added. Again the waste
material is pxactically guantitatively converted and
at the same time the crude oil residue can be converted
by hydrogenative cleavage. Mixtures with lignite or hard
coal can also be hydrogenated with very good results
according to the inven~ion. This is also the case in
the presence of other oils of mineral origin.
The tables 3 and 4 represent results which were obtained
from the inventive hydrotreating of a mixture of synthetic
waste, including polyvinylchloride. The waste material
was an average daily sample of a garbage separating unit
with portions of 10 - 50 weight % of vegetable waste.
Another sample consisted of mixtures of synthetic waste
and 20 to 60 weight ~ waste paper~ The hydrogenation was
aarried out at 450C, a pressure of 200 bar and a
residence time o 4 hours. No catalyst was added. A
vacuum distillate from a coal hydrogenation oil was
added in a ratio of waste to VD of 3:1.
In addition to the products of the table water was
formed.
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Table 3
_____. _
, _
F eed 'onversion CO/C02 C1-C4 ~p Bp
Synthetic portion ~ 390C ~390C
tD vegetable
portion (moist) 1 weight% weight% weight% weight%
from a "green tun"
__.
9 : 1 99,5 3 3 79 15
_
8 ~ 2 99,6 4 5 74 17
.
1 : 1 99,6 7 10 63 20
_
2 : 8 78 5 16 50 29
vegetable portion
~redried
1 = Municipal garbage collectlng device
Table 4
__
F cd Conversion Co/oo2 C1-C4 Bp Bp
Synthetic portion . < 390C ~ 390C
: to waste paper ~
(m~ist) fr~m weight% weight% weight Iweight%
~ a "green~tun" _ :
: ~ : 5 65 25
: 80 : 20 99,5 5 .
. . _ _ .
. 66 : 34 ~ 99,5 7 11 49 33
~ _ : _ ~ :
40 : 60 99,513 9 41 37
_ ~ :. ~ _ ~--__ _ ,
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Table 5 represents conversions and yields of individual
fractions depending on the type of catalyst.
Hydrogenating conditions were 450C, 200 bar and a
residence time of 4 hours. A used spindle oil was added
in a ratio of spindle oil to waste of 1 : 2.
The conditions were selected in order to have a proper
comparison to previous tables. Similar results are
obtained, if the conditions are variied.
.
Table 5
__ _____
Boilinq ranqe
_ _ __
Catalyst Conversion Cl-C4 <180C 180-390C > 390C
to HC's
with Bp.
~390C weight% weight% weight% weight%
__
_ 81,4 2 38 45 15
Ni/Mo/~.2O3 88 1 41 46 12
_ ___ _ .
NilMb/Alw~um 98 14 58 26 2
silicate _
_ _ . ___
Fe (II~ acetyl- - 11 38 -43 8
acetonate
- ~ ~ _ _
Ni (II) acetate 92 9 33 50 8
_ _ 1 ~- -'
~ coke 90 6 53 31 10
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The table shsws that by using hydrogenating catalysts
like Ni/Mo/aluminumsilicate, also very high conversions
are achiev~d and at the same time high portions of
fractions with boiling xanges below 390C. Iron and
nickel catalysts lead to a particularly high portion
of compounds boiling between 180 - 390 C.
Catalysts like hearth furnace coke doped with FeSO4
lead to a high portion of a fraction boiling ~180C.
Variation of temperature, pressure and residence time
leads to variations of the portions of the individual
fractions.
In continuous experiments synthetic waste was
hydrogenated at a temperature of 450C and a pressure
of 200 bar. 2 kg/h of waste, mixed with crude oil
residue ~atmospheric distillation residue) at a ratio
of waste to oil of 3 7 were converted at a residence
time of 2 hours. Three experiments were carried out
for a period of 700 hours each, without catalyst, with
Ni/Mo/Aluminum silicate as catalyst and hearth furnace
coke, doped with 5 weight % of FeSO4 as catalyst.
Table 6 shows that the result of tables 2 and 5 could
be considerably improved.
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Table 6
____ .__
. . _ _ Boiling range .
. ~ ~ ,
Catalyst Conversion ~ -C <180C 180-390C >390C
b~ HC's with 1 4
Bp ~ 390C
: weight% weight% weight% weight%
_ , _
_ 88 1,5 39,547 12
_ . _ _ _
Ni/Mo/Aluminum .
silicate 99 10 65 24
_ _
hearth furnace
cc~e+5 weight% 93 4 58 31 7
FeS04 . _ _ I
Similar results were obtained with adcled used machine oil
instead of crude oil residue. Even better results were
obtained with a mixture of 25 weight % of crude oil
residue and 75 weight % of an oil from the hydrogenating
unit ~boiling range 180 - 390C). The results are
summaF1zou in tsble ~.
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:~:
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Table 7
_______
.__ __ _ ,
Boiling range
_ .
Catalyst ConversionC1-C4 ~180C 180-390C >390C
to HC's with
Ep ~ 390C
: weight~ weight% weight% weight%
_ 89 2 38 49 11
Ni/Mo/Aluminum
silicate 99 7 68 24
_.
hearth urnace
coke 5 weight~ I _ 3 62 30 S
Since hydrogen gains increasing importance and is
manu~actured already to-day ln numerous plants for
example by gasification of coal, crude oil residues
and other materials, by electrolysis and even photo-
electrolysis and since hydrogen can easily be transported
through pipelines over large distances, the instant
invention makes it~possible to erect; waste hydro-
genating:plants:at numerous places, in particular
in aereas~with a hlgh density of population. These
plantg would permit:to dispose of wastes of~such regions
without applying waste disposal methods o~ the state of
the~axt, like landfill, incineration:, pyrolysis and
others, which lead to additional problems.
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12~ 36
In contrast to incineration which results in high
amounts of C02 and additional hazardous emissions and in contrast
to pyrolysis units, which produce mainly gases, the instant
invention yields valuable liquid products, thus permitting
recycling of consumer goods in a superior manner.
~ hereas, as shown by the state of the art, the
artisan has made efforts in different directions, and has
hitherto not been able to offer a satisfactory solution to an
increasingly pressing problem, the instant invention discloses
a superior solution.
