DE3616785A1 - METHOD FOR PROCESSING CARBON-CONTAINING WASTE AND BIOMASS - Google Patents

Abstract

1. A process for the production of hydrocarbons from carbonbearing wastes by the hydrogenating separation of the carbon-bearing wastes with hydrogen and/or hydrogen-bearing gases and/or compounds which give off hydrogen, characterised in that the hydrogenating separation operation is effected at 250 to 900 degrees C and 5 to 280 bars in a fluidised bed.

Description

It is known in the public and in the professional world that the global waste is an increasingly larger Represents pollution of the environment.

Waste has been used in landfills for decades, e.g. in abandoned gravel pits, mine pits and others Places stored. For a long time you have the chemical Structure of the waste and its long-term impact Soil and groundwater disregarded. More recently certain waste is stored in so-called special landfills. Here, efforts are made to protect the landfill from groundwater and seal the floor.

The professional world has therefore been intensively looking around for some time endeavors to process or process the waste sometimes to protect the environment and secondly to usable To win products from waste.

So in "The Oil and Gas Journal", Dec. 25, 1978, p. 80, described a pilot plant in which by pyrolysis art substances can be converted into gases and oils.

In "Hydrocarbon Processing", Aprilil 1979, p. 183, a Incineration plant be especially for special waste wrote.

The biochemical degradation of plastics was also under addiction (see e.g. "European Chemical News", Sept. 10, 1979, P.28).  

In "Chemical Engineering", August 13, 1979, p. 41 described a process according to which hazardous waste in hardening materials, e.g. Cement to be poured.

An overview of the most important procedures is in "Chemical and Engineering News", Oct. 01, 1979, p. 34, shown. Here, in particular, the gasification of organic mass, namely wood waste and the like to carbon monoxide and hydrogen. On p. 36, left column of this Scripture also becomes a test program for the implementation of crushed wood suspended in water, with hydrogen in Presence of Raney nickel, described as a catalyst.

In "Europa Chemie", 25, 1979, p. 417, a method is described described after the unsorted plastic waste plasticized and pressed.

The fluidized bed incineration of waste is in "Chemical Industry", XXXII, April 1980, p. 248 ben. The conversion of waste and biomass by Er heating with water and alkalis is described in "Chemistry Interna tional ", 1980 No. 4, p. 20.

Numerous other publications are also known become.

In recent times, combustion in the most modern plants, in particular, has been further developed and large plants have been built that use this process. Although dust removal and flue gas scrubbing are integrated in such systems, pollutants escape into the atmosphere in small proportions even when carefully cleaned, such as heavy metals, SO ₂ , NO _x and others.

Pyrolysis is now also being used on a technical scale driven (see, for example, "United Business Services GmbH ", October 4, 1985, p. 9). However, pyrolysis has Disadvantages of the predominant formation of gaseous products and a heavily contaminated coke residue.

The problem of waste and biomass processing is according to this state the technology therefore still not solved satisfactorily. A surprising, compared to the prior art we considerably cheaper solution to this problem, especially in With regard to the extraction of very high shares more valuable Products are disclosed by the present invention, thereby indicates that carbon-containing waste and / or Biomass in the fluidized bed with hydrogen and / or Gases containing hydrogen and / or hydrogen donors Connections are implemented.

This method enables waste from which inorganic components such as glass, metals, stone materials and the like to be removed as far as possible without further sorting to produce valuable hydrocarbons, i.e. to C ₁ -C ₄ hydrocarbon gases, to boiling in the gasoline range Hydrocarbons and medium and heavy oils that can be used as diesel oil and for heating purposes.

It is also of particular advantage that the feed products Little crushing needs to make the products practical are olefin-free and that heterocouples as hydrogen compounds are accrued that are easily absorbed according to the state of the art can be worked.

Pre-sorted materials can also be processed according to this procedure, in particular in such a way that mixtures of carbonaceous wastes are synthe table of origin, such as plastics, or plastic mixtures, Rubber, tires, textile waste and the like from the vegetable portion or biomass fraction are at least roughly separated and then undergo a separate hydrating treatment, possibly together with industrial waste,  such as. Paint and paint residues and organic chemicals, Industrial production wastes, organic synthetic Shredder waste from the automotive industry, sewage sludge or with Used oils and The like. Sometimes other waste such as paper, food scraps, agriculture and forestry wastes, wood, plants and the like be separated, but also to a certain extent in synthetic Share remain.

Accordingly, household waste can be processed in such a way, for example the fact that the plastics, rubber, textile remnants and the like, at least roughly separated and subjected separately to the hydrating treatment or e.g. together with used tires and / or plastics and / or chemicals wastes from industry and / or waste oils and. The like the synthetic individual components are among the fiction very good with valuable liquid products processable.

The procedure is also very suitable for the common hydrating treatment of the waste or waste ge mix with coal, coal components, such as Coal oil residues, coal oils, pyrolysis oils, petroleum, petroleum residues, other petroleum components, oil shale, oil slate components, oil sands, bitumen and similar or the mixtures of these materials.

According to the present invention, the carbon-containing wastes and / or biomass to be reacted with hydrogen and / or hydrogen-containing gases and / or hydrogen-releasing compounds are reacted with these gases in a fluidized bed, the fluidized bed being at least partially produced or using the gases mentioned. on being maintained. The gases can additionally contain other components, such as N ₂ , CO, CO ₂ , CH ₄ or water vapor. However, Gesamt 25% by volume of hydrogen is contained in the total amount of gases. As fluidized bed reactors, both state-of-the-art reactors and further developed fluidized bed reactors can be used.

Suitable reactors are, for example, those as in the Coal gasification, fluidized bed combustion plants or lime incinerators are used, but the reactors may need to be adapted to the input product.

The solid, carbon-containing waste used and / or biomass can depend on the gas supply be crushed to different material sizes, or can also be used without shredding. The latter recommends yourself especially when using an additional solid Backing material that is used both in the straight passage can also be at least partially recycled can. Such materials can be inert, for example Materials such as sand, gravel, corundum, ceramics, clay, coke or similar, these materials also as heat carriers can serve. However, it can also act catalytically be solid materials such as Fe, Mo, Ni, Co, W and other hydrogenation-active metals and / or their compounds containing catalysts, these consisting of individual or can also consist of at least two of these components and the metals and / or their compounds on supports can be applied, e.g. on aluminum oxide, silicon dioxide, aluminum silicates, zeolites, the above solid additional materials and other known to those skilled in the art Carriers or of carrier mixtures. However, you can also without Carrier can be used. Certain zeolites as such are suitable.

Other suitable catalysts can be so-called disposable catalysts sensors, such as hearth coke, Winklerver Gassing dusts, dusts and ashes that are used in the hydrating Gasification of coal to methane occur (HKV dusts) also containing iron oxides and other iron compounds Mixtures such as red mud, Bavarian mass, Lux mass, dusts from the iron industry and others, these Materials also with hydration-active metals and / or metal  compounds can be doped, especially with heavy high salts, e.g. Iron salts or salts of chromium, Zinc, molybdenum, tungsten, manganese, nickel, cobalt, further also with alkali, alkaline earth, etc. as well as with mixtures of these Links.

The catalysts can at least z. Part of sulfidizing pass be acting.

It is understood that all of the carrier materials mentioned and catalysts both individually and in mixtures can be set.

Solid as well as liquid waste and / or biomass are used, the gas supply being adjusted accordingly is. Examples are solid waste, both individually and can be used in a mixture, called:

Plastics, rubber, tires, textiles, shredder waste, in particular from the automotive industry, paper, solid vegetable waste, wood, vegetable and other cellulose-containing waste, other solid organic synthesis industrial waste. Solid additives to this waste can be: coal, such as lignite or hard coal, peat, Oil shale, bitumen, or their mixtures. But others too wastes not mentioned here containing solid carbon can be valuable under the conditions of the invention Products.

Examples of liquid waste are:

Waste oils, residual oils from mineral oil and coal processing processing, pyrolysis oils, crude oils, oil shale and oil sand oils, liquid organic-synthetic residues, bio-sludge. But also other liquid inserts not mentioned here Products or waste products can be invented according to the conditions for valuable products.

The conditions of the hydrogenating reaction according to the invention can vary depending on the products used Limits can be varied. So the temperature is included 300 ° C to 900 ° C, preferably at 350 ° C to 800 ° C and particularly preferably at 400 ° C to 600 ° C.  

The pressure is 1 to 320 bar, preferably 5 to 280 bar and particularly preferably at 8 to 240 bar.

The ratio of hydrogen to the feed product is particularly due to the amount of gas required for certain or grain size of the solid feed product is determined to Maintaining the fluidized bed is necessary. The gas speed can be, for example, with so-called stationary Wir bedding at 0.05 to 1.5 m / sec., preferably at 0.2 to 1 m / sec. , but can also be in the case of so-called fast risers Fluid beds up to 30 m / sec. to reach.

However, it must be taken into account here that Zu sets of other gases and by adding water vapor, the Maintaining the fluidized bed is also determined.

All hydrogen qualities can be used as hydrogenation gas, also with admixtures such as CO, CO ₂ , H ₂ S, methane, ethane, water vapor, etc.

Hydrogen qualities, such as those which arise in the gasification reactions of carbon-containing materials with water vapor, are very suitable. Such materials can be residues from the processing of mineral oils or coal, wood, peat or residues from coal processing, for example hydrogenation. Biomass or the vegetable parts separated from household waste are also suitable. Of course, pure H ₂ qualities such as hydrogen electrolysis are also very suitable. For example, according to the invention, domestic waste can first be separated into the vegetable and synthetic portions and then the vegetable portion for hydrogen generation can be fed to gasification, while the synthetic portion is subjected to the hydrogenating treatment.

The vegetable portion can also be a fermentation or be processed.

Also transfer a solvent treatment with hydrogen solvents can be the hydrating treatment can be switched, then a separation in Ge dissolved and unsolved occur and the unsolved to the Fluidized bed hydrogenation reactor (s) are fed.

In this process variant, too, the feed product can be used in Mixture with coal and / or coal components and / or earth oil residues and / or petroleum etc. be hydrogenated.

Suitable solvents are e.g. Tetralin, anthracene oil, Oils containing isopropanol, cresol, decalin, naphthalene, Tetrahydrofuran, dioxane, but also, for example, petroleum Sturdy hydrocarbon or hydrocarbon originating from the plant itself hydrocarbons containing substances and oils and oxygen and oils. Finally, water or steam can also be added will.

According to the procedure mentioned, waste mixtures can also be used in are processed in such a way that mixtures of vegetable and synthetic waste, if applicable with the addition of biomass in various stages under Be conditions are implemented, on the one hand, essentially Lichen the hydrolytic and / or hydrating reaction Vegetable or paper and biomass share and others on the other hand, the hydrogenating implementation of the synthetic orga African waste occurs.

For example, in the 1st stage, a hydrogenating Be act in the presence of hydrogenation catalysts and a pressure of 1 bar to 150 bar, preferably 25 - 60 bar take place, preferably in the presence of water and  other protic solvents such as alcohol len is being worked on.

Then the predominantly from the vegetable Abge receiving oils abge by solvent extraction are separated, after which the non-hydrolytically split portion in the 2nd stage under conditions already described in the fluidized bed can be split by hydrogenation.

The gradual processing can also take place in such a way that vegetable portions or paper portions or biomass be hydrolytically split in the first stage, for example wise in the presence of alkalis or acids, this Um may take place in the presence of CO and be preferably in the presence of water and / or other protic Solvents such as alcohols and in 2nd stage of the synthetic or predominantly synthetic type part in the fluidized bed is implemented hydrogenating.

Alternatively, the waste and / or the biomass can be previously in a vegetable portion and a synthetic portion be separated and ge under the conditions described to be processed separately.

In these cases too, both with and without catalyze are worked. If necessary. can ge before the 2nd stage be dried.

According to the invention, the waste to be hydrogenated and / or the biomass in the presence of or containing hydrogen tendency gases and / or in the presence of hydrogen Compounds, in particular so-called hydrogen donor solvents but also in the presence of inert gases, i.e. thermally in mixed devices, esp  in particular in extruders and mixing / kneading devices deln.

Numerous other mixing devices such as Kneading disc screw presses, kneaders, hollow screw Heat exchanger, screw kneader, kneading extruder, stirrer doors, continuous mixers, reaction mixers, kneaders, grinding machines directions or mills such as pearl, hammer or vibrating mills are suitable for the pretreatment according to the invention.

The method according to the invention allows only a little or to process pre-separated waste mixtures. It is desirable for apparatus reasons, anorga African materials such as stones, metals, glass and the like separate here, at least rough materials. It can also a pre-separation into predominantly vegetabili, for example cal or cellulose-containing and predominantly synthetic Materials are made, with the vegetable part separately such as processed in a fermentation can be.

The previous disadvantages of the prior art are ins especially overcome in an excellent way that despite the use of completely inconsistent waste mixtures valuable hydrocarbon oils obtained in high yields and the heterocouples present in the waste such as oxygen, sulfur, nitrogen, halogens to water substance compounds are implemented, according to the state of the Technology can be treated in a known manner.

This applies in particular to those containing chlorine, bromine or fluorine Waste. The problems of the Waste mixture disposal, especially the toxic and Halogenated waste is therefore risk-free according to the invention solved.  

Examples include polychlorobiphenyls, PVC, fluorine called solvents containing polymers or halogens.

According to the invention, petroleum, Petroleum components and derivatives, coal, coal inventory parts and derivatives, asphalts, bitumen, oils from pyro e.g. read from coking or waste pyrolysis, oil sand pro products, oil shale products, heavy residual oils and the like. added and processed together.

Even oils and residues that come from the plant itself can be used according to the invention.

According to the invention, metal-containing waste can in particular work up advantageous way, since the metals in shape of ashes accumulate after the hydrogenation and then can be supplied to a metal workup.

The reaction zone can be one or more behind other or parallel reactors exist. The resulting liquid hydrocarbons can State of the art to be processed accordingly for example by further hydrogenating splitting steps or Refining stages and separation by distillation.

The uncondensed gases are freed of H ₂ S, NH ₃ , HC1, and possibly also CO and CO ₂ by gas washing.

The hydrogen in the resulting gas can be used as a hydrogenation gas are returned to the hydrogenation reactor (s). A ver work the contained in the gaseous products lower hydrocarbons, for example by steam reforming also possible, with additional hydrogen being obtained becomes.

The liquid products can be fed to a refining stage  leads, which works generally hydrating. Here can still present small amounts of heteroatoms containing compounds completely hydrogenated be processed so that the products are then practical are free of sulfur, nitrogen and halogen. Higher boiling Shares can be fed to at least one cracker the, especially a hydrocracking plant. From the processing If necessary, certain portions can be processed again back into the waste hydrogenation or before the waste hydrogenation be performed.

The method according to the invention can also be used with others Waste hydrogenation processes, such as a sump phase Hydrogenation can be combined.

Examples example 1

A waste mixture of the green bin, consisting of foils, hard plastics, textile and paper parts, which had been obtained after the previous separation of the reusable components such as metals, glass and paper, was at 470 ° C and 60 bar in the fluidized bed (quartz sand ) implemented with hydrogen. The products obtained were a gas phase (9% by weight), 75% liquid products in the boiling range up to 390 ° C and 16% residue (inert materials, carbon black and high boilers). In addition to C ₁ -C ₄ hydrocarbons, the gas phase contained 2% CO and CO ₂ .

Similar results were obtained with hearth coke as Trä germ material instead of quartz sand.

Example 2

Example 1 was repeated, the starting product being calcium oxide was added. At within the scope of the analysis accuracy unchanged product composition became an HCl-free gas  received phase. The released from the PVC components HCl was thus almost completely bound.

Example 3

A mixture of synthetic waste, which consisted of daily samples from several waste separation plants, was reacted with hydrogen at 480 ° C and 100 bar in the fluidized bed (cobalt / molybdenum catalyst on Al ₂ O ₃ ) without further purification. The hydrogenation was practically quantitative, but a higher gas content was obtained compared to Example 1, which is due to the higher paper and biomass content. A product was obtained which consisted of 17% gas phase, 70% liquid product in the boiling range up to 390 ° C. and 13% residue (carbon black, inert materials).

Example 4

"Light goods" from shredders, which is essentially art substances, rubber and upholstery materials became hydrogenating implemented in a quartz sand fluidized bed. The reaction he followed at 460 ° C and 30 bar.

A product was obtained which contained 64% hydrocarbons in the boiling range up to 390 ° C. The gas phase, which was 12% of the total product, contained 3.5% CO / CO ₂ . The residue consisted essentially of inert materials such as metals, fillers, etc. and carbon black.

Example 5

A plastic-containing waste mixture consisting of 30% cable sheathing, 40% light material from shredder systems and 30% old tires was converted to aluminum oxide doped with molybdenum oxide. After hydrogenation at 490 ° C and 120 bar, the 80 wt .-% liquid products up to 390 ° C boiling ends were obtained, which contained only small amounts of olefinic hydrocarbons. The gas phase, which was 6% by weight, contained essentially saturated C ₁ -C ₄ hydrocarbons.

Example 6

Synthetic-organic waste components including PVC from a daily sample of a waste separation plant were together with residues of mineral oil processing in the fluidized bed reactor introduced. The plastic content in use was 60% by weight. The fluidized bed consisted of iron compounds impregnated aluminum silicate.

After reaction at 470 ° C. and 200 bar, 84% by weight of oil in the boiling range up to 390 ° C. with a high aromatic content and 11% by weight of high-boiling products and residues were obtained. The reaction gas (5 wt .-%) contained only traces of CO and CO ₂ and the corresponding amounts of HCl used PVC.

When the experiment was repeated and calcium oxide was added no HCl can be detected in the exhaust gas.

Example 7

A mixture of PVC-containing plastic waste from a rubbish Sorting system was used along with chlorine-contaminated oils and organic chemical residues containing 1% by weight of chlorine stopped, placed in the fluidized bed reactor. The plastic proportion was 60% by weight. On aluminum silicates that nickel / mo Contained lybdenum, this mixture was at 480 ° C and 50 bar implemented with hydrogen.

In addition to the gas phase (9% by weight) and 6% higher-boiling products the main fraction was an oil in the boiling range in 85% yield maintained up to 390 ° C. The chlorine content of this fraction was included 3800 ppm.

By hydrogenating refining these oil fractions at 50 bar and 280 ° C in a fixed bed reactor a product was obtained in which chlorine was no longer detectable.

Similar results were obtained with undoped hearth coke as Receive catalyst.  

Example 8

A mixture of tire waste, paint residue and wood waste was implemented without a carrier at 490 ° C and 120 bar.

The product obtained was 54% by weight of oils boiling at 390 ° C., 25% by weight of gases, including small amounts of CO and CO _2, and 21% by weight of solids (metal residues, soot, pigment components).

Claims (12)

1. Process for the processing of carbon-containing waste and / or biomass, characterized in that the carbon-containing waste and / or biomass with hydrogen and / or hydrogen-containing gases and / or hydrogen-containing compounds in the fluidized bed are reacted. 2. Process for processing carbon-containing waste and / or biomass, characterized in that mixtures of carbon containing waste and / or biomass with hydrogen and / or Giving off hydrogen-containing gases and / or hydrogen the compounds in the fluidized bed. 3. The method according to claims 1 and 2, characterized records that at a temperature of 300 to 900 ° C, preferably at 350 to 800 ° C and particularly preferably at 400 to 600 ° C works. 4. The method according to claims 1 to 3, characterized records that at a pressure of 1 to 320 bar, be preferably at 5 to 280 bar and particularly preferably at 8 works up to 240 bar. 5. The method according to claims 1 to 4, characterized in net that mixtures of synthetic waste are used.   6. The method according to claims 1 to 5, characterized in net that in the presence of (an) additional festival (s) hydrogenated substances (s) in the fluidized bed, which if necessary. with hydrogenation-active metals and / or their compounds are endowed. 7. The method according to claims 1 to 6, characterized in net that you hydrie without catalyst in the fluidized bed implemented. 8. The method according to claims 1 to 7, characterized in net that one in the presence of catalysts in the vortex reacted layer hydrating. 9. The method according to claims 1 to 6 and 8, characterized records that in the presence of so-called disposable catalysts is working. 10. The method according to claims 1 to 6 and 8, characterized shows that one works in the presence of catalysts, which contain hydrogen-active metals, in particular Fe, Mo, W, Ni, Co. 11. The method according to claims 1 to 10, characterized in net that the waste to be hydrogenated and / or biomass in Mixture with petroleum and / or petroleum components, in particular Oil residues and / or coal and / or coal components and / or oil shale and / or oil shale components and / or Oil sand extracts and / or bitumen and / or asphalt and as phalthenes are implemented. 12. The method according to claims 1 to 11, characterized in that the proportion of hydrogen in the feed gases in the fluidized bed ≧ 25% by volume.