CA1294236C - Process for the hydrogenative reprocessing of carbon containing waste materials of synthetic or predominantly synthetic origin - Google Patents

Abstract

A PROCESS FOR THE REPROCESSING OF CARBON
CONTAINING WASTES AND BIOMASS

Abstract of the disclosure This invention relates to a process for the reprocessing of carbon containing wastes and biomass by hydrogenation of the same at elevated temperature and at least 1 bar hydrogen pressure.

Description

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.

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- 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. ~

, 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.

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' - 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 ,.

UK 357a 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.
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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 ~29a~;~36 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 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.

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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 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.

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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 .

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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.

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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:.

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UK 357a 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 ~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 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.

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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 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 lZ94~3!6 ~

UK 357a 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.

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,, 1~2~6 ~ UK 357a 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 : ~ ~

: .

3L;~94~36 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~

4 89,5 28,5 47 14 10,5 L _ ~ 65 .`

1 ,'~4236 UK 357a 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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lZ94:~36 UK 357a 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.

1;~9~36 UK 357a 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 _ ~ :. ~ _ ~--__ _ , lZ9~23fi UK 357a ~ 25 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.
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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 :

,, lZ9~236 UK 357a 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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129~;~36 UK 357a 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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~Z~3~Z36 UK 357a 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.

Claims (8)

1. In a process for production of hydrocarbons predominantly boiling in the naphtha and gas oil range by hydrogenative cleavage of carbon containing waste materials with the exception of waste rubber, the improvement comprises 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 50-450 bars and a residence time of 15 minutes to 6 hours.

2. Process according to claim 1 wherein the waste materials of synthetic or predominantly synthetic origin are reacted with molecular hydrogen at a temperature of 200-540°C, at a pressure of 50-450 bars and at a residence time of 15 minutes to 6 hours and wherein the ratio of the product fraction boiling in the range of naphtha to the product fraction boiling in the range of gas oil is adjusted by the use of a catalyst.

3. Process according to claim 2 wherein the hydrogenative cleavage is carried out in the presence of a oncethrough catalyst.

4. Process according to claim 2 wherein the catalyst is hearth furnace coke, Winkler dusts and ashes, or HKV-dust and ashes doped with metals or metallic compounds active in hydrogenating.

5. Process according to claim 2 wherein the catalyst is an iron containing catalyst undoped or doped with further metals or metallic compounds.

6. Process according to claim 2 wherein the hydrogenative cleavage is carried out in the presence of Ni, Mo, W, Co or mixtures thereof applied on catalyst carriers.

7. Process according to claim 1 wherein the products or the hydrogenative cleavage are subjected to hydrogenative refining.

8. Process according to claim 1 wherein after the residence time, the product is withdrawn from the reactor and fed into a hot catch-pot and a gaseous hydrocarbon material is withdrawn from the top of the hot catch-pot and a heavy residue is withdrawn from the bottom of the hot catch-pot.