CN101578234A - Process of conversion of organic and non-organic waste materials into useful products - Google Patents

Abstract

The present invention relates to the conversion of waste and low- value materials into useful products in reliable purities in a cost-effective and energy-efficient manner. More specifially, the invention provides processes that can handle mixed streams of various feedstocks, e.g. shredder residue, offal, animal manures, municipal sewage sludge, tires, and plastics, that otherwise have little commercial value, to useful products including gas, oil, specialty chemicals, and carbon solids. The process subjects the feedstock to heat and pressure, separates out various components, then further applies heat and pressure to one or more of those components, according to processes based on thermal or catalytic cracking. The invention further comprises an apparatus for performing a multi-stage process of converting waste materials into useful materials, and at least one oil product that arises from the process. Useful products can also be obtained or derived from materials diverted at differentpoints of the process.

Description

Organic and non-organic waste are depolymerized to useful products

The cross reference of related application

The application requires the right of priority of U.S. Patent application no.60/812275 that submits in the U.S. Patent application no.60/727491 that submits in the U.S. Patent application no.60/721836 that submitted on September 28th, 2005, on October 17th, 2005, the U.S. Patent application no.60/778034 that on February 28th, 2006 submitted to, on June 9th, 2006 and the U.S. Patent application no.60/840207 that submitted on August 25th, 2006, and wherein each piece of writing is introduced by reference in its entirety at this.

Invention field

The present invention relates generally to refuse or low value (low value) materials processing are become useful products.More specifically, industry, agricultural or other refuse that the present invention relates to contain the carbon compounds or low-value materials are converted into the method and apparatus of commercial useful product (for example fuel oil, fertilizer and special organic chemicals (specialtyorganic chemicals)).The present invention also reduces the potential environmental pollution that comes from the inorganic wastes logistics.

Background of invention

Early have recognized that many waste product that human society produces can finally resolve into a small amount of simple organic materials with its inherent value.If this transition energy is carried out with the mode of Energy Efficient and enough big scale, has very large benefit for society so.

The major part life material that uses in family and the commercial applications and most of synthesis of organic substance matter comprise the carbon base polymer of various compositions.Under suitable condition, the major part in this material (comprising timber, coal, plastics, tire and animal waste) can resolve into the mixture of gaseous product, oil and carbon.For example the material of agricultural waste also contains the inorganic substance that resolve into mineral products.No matter be organism or inorganics, nearly all these products can obtain newborn in a large amount of advantages and common favourable application.

The principle that is not only generation useful materials from useless refuse is attracting: the method that the circulation of waste material is tackled the main challenge of 21 century for population expansion is very important.Limited supply and reply that two kinds of basic challenges that the mankind face are reply material and energy reduce the growing threat of Global warming to environment.In fact, obtaining the popular intention fast is to retrieve the carbon class material in biosphere rather than develop new carbon source from underground petroleum, Sweet natural gas and coal storage, and this can alleviate Global warming.

Yet up to now, the industry that generates a large amount of waste product mainly include the machine material is in processing and storage of waste and use it in the maximum favourable purposes and face the challenge.

For example, the annual organic refuse that is rich in that produces tens pounds of worldwide food-processing industry.These refuses are relevant with processing animals and plant prod, and comprise the refuse that processing and breeding turkey, fish, chicken, pig and ox produce.Food-processing industry continues to increase, and its member faces remarkable economical and environmental stress comes to prepare some fertile article with their refuse.These waste product have been brought a large amount of key issues.One of problem is the generation of greenhouse gases such as the generation of carbonic acid gas and methane, greenhouse gases be by bury, (land applying) deposited in the soil or the digestion food waste produces, and without any benefit.Ideally, foodstuffs industry must adopt their refuse of effective and economic management by methods rather than discharging that flavor or tedious pollutent are arranged.

In this year, the cost that big area stores useless by product significantly increases.Along with the type of the waste product that can be supplied to agriculture livestock is restricted day by day.For example, along with in the BSE/CJD in Europe fear, many waste product are stored simply, and final suitable destiny is unknown.Obviously, another exigence is to find acceptable manner to clean to process and utilize these materials.Preferably, need to find the food-processing refuse is converted into the means of useful high value product.

Other motivating force of seeking the means of handling is combinations of the expansion of the implementation of discharge of wastewater rules and sewage surcharge.Food-processing industry must be sought cost-effective technology and provide pre-treatment or processing fully with waste water and solid (hygrometric state) refuse to them.In history, be positioned at or be close to metropolitan food processing plant and rely on local publicly owned treatment project (POTWs), waste water is handled and disposed.This selection more and more is difficult to obtain, and this is because stricter law enforcement.The pressure of dealing with the discharge of wastewater permission has increased.Mean also that to building new reduction this selection is no longer attractive with federal funds upgrading POTWs.Therefore, food-processing industry increases day by day for pressure how effectively to handle its useless product.

Permanent chemical, for example in the organism of Dioxins (dioxin) disease of accumulation and diffusion life threatening for example the potential possibility of mad cow disease (BSE) be another threat to food-processing person and food consumption person.Make this threat more obviously strengthen to farm-animals feeding food-processing residue.Food-processing person needs economic method to block this circulation.

Industrial waste, that is there is another challenge equally in the processing of shredder residues (shredder residue).Although the most of assemblies when motor vehicle, family and commercial apparatus life-span are last can be recycled, re-use or reclaim, a significantly big part remains from chopping technology and is buried.Because of the toxic substance of finding within it, for example cadmium, lead, mercury and other heavy metals cause being difficult to more dispose shredder residues.Because the obtainable space of buried applications is limited and the cost of deleterious waste treatment increases, therefore need the alternate solution.Motor vehicle is in the method that requires to invent effective with cost in ability efficient manner use shredder residues under the pressure at present with recovery industry.

In addition, these industry of city and local sewage laws and regulations requirement reduce their organic biochemical oxygen demand (BOD) (BOD), chemical oxygen demand (COD) (COD) and solid carryings (solid loading) in sewage.Because high BOD concentration finds to have high-caliber suspended solids, ammonia and protein compound in this waste water usually in the high strength food processing wastewater, food-processing industry is subjected to other supervision.Food processing plant needs effective and waste water and the solid waste of application-particular procedure (application-specific treatment) technology to manage them effectively of cost.

In other industry, produced, enlarged and strengthened similar problem by different way.For example, one of them problem is to produce the foul gas discharging relevant with refining factory, and refining factory is fat and protein with animal waste by thermal conversion.Another problem is that the soil that contains the multiple biosolids of high density pathogenic agent is deposited.

Develop the whole bag of tricks so that exhausted damaged tire (from truck and passenger vehicle) is processed into useful product, comprised the raw material of fuel, oil, carbon, combustion gas and generation tire and other rubber product.Usually, these schemes relate to heating and dissolving tire in solvent.Some scheme attempts to make the rubber for tire desulfurization, even connect to form the sulfide linkage fracture of polymkeric substance along its length.Other scheme attempts making the elastomeric material depolymerization.Depolymerization fragments into more runny short chain polymer with long chain polymer, so can more easily be used as product, for example fuel oil.Some scheme relates under the condition that is close to or higher than water stagnation point (about 3,200psi and about 370 ℃) makes water, and wherein water is that extraordinary solvent is used for and reacts with elastomeric material.Yet this scheme energy efficiency is low, because need energy to reach super critical condition.In addition, processing also needs the superalloy operating gear under super critical condition.

Excessive after deliberation amount organic materials is used to dissolve tire material to form heavy oil or desulfurization rubber product.Usually, the existing scheme of operation (less than 200psi) produces the contaminated product of heavy under temperate condition, produce better product and use than those of light naphtha, but must use the solvent of costliness or need high pressure (＞2,000psi) or the two all need.In addition, it is uneconomic using most of scheme of dissolution with solvents tire material, because in the course of processing, lost a part of solvent, and the existence cost relevant with supplementing solvent, even under the situation that can reclaim solvent and utilize again, also be like this.

In sewage work, used aerobic and anaerobic digestion person (digesters) with Treating Municipal Sewage mud (municipal sewage sludge).Have many with use the relevant problem of digestion person.The subject matter of operating them be rich in biomass materials conveyance contain in the large container that digests biomaterial.Usually, give the aerobic digestion person, and give anaerobic digestion person the Solid Conveying and Melting that suspends with the dissolved Solid Conveying and Melting.When the trophicity raw material exhausted, these bacteriums can not keep they oneself again, had therefore died.Final product between the period of digestion is the mud that contains the bacterium that dies, and must handle them in some way.A problem relevant with the gained material is that it still contains pathogenic agent.Usually, the problem relevant with whole technology is that the retention time in digestion person's container can reach 17 days, and operational condition is difficult to keep.For example, by big relatively container (general diameter is 20 to 30 feet) is remained on more than 85 °F, sometimes more than 122 °F.

Industry (particularly food-processing industry) utilizable all disposal technologies have significant restriction and shortcoming at present, and this provides the power of seeking alternative techniques.This is applicable to the technology except that using existing POTWs.Particularly, four kinds of schemes are arranged, clay treatment (undergroundly bury, composting collected manure, soil deposit), biological treatment, conventional thermal oxidative treatment (for example incineration/combustion) and pyrolysis/gasification, all these has shortcoming separately.

The shortcoming of clay treatment comprises: the potential possibility height and the regional resident of delivery or trucking costs height, leaching groundwater pollutant are exposed to high density toxic pollutant (for example depositing the pathogenic agent under the situation in the soil).Undergroundly bury generation and can cause air-polluting gas, comprise the generation greenhouse gases.

The shortcoming of biological treatment refuse comprises and is difficult to control and can not test effect, because be difficult to the air-flow that soil is immersed in fully check.If use aerobic bacteria must keep air-flow so that oxygen is provided.For example, exploitation is used for consuming the bacterium of specific compound when being placed on other enzyme system of soil meeting activation to consume the compound that obtains at first.

Burn or the shortcoming of the more ancient device of incendiary comprises that needs add the device that satisfies the stricter air pollution emission standard that government constantly requires.Burn because important group pays close attention to, with or its other technology compare, also might need the air discharge permit of longer time to obtain to burn.And processing of waste means a large amount of gaseous states of processing in exhaust, so that need very large shop equipment.Raw material also is low-calorie.Some incinerator and solid fuel or solid waste are incompatible, because these materials oxidation De Taigao in stove.On the contrary, the high water content in the raw material also is problematic because burn or combustion processes in, it is about 1 that water volatilization and removing-water volatilization needs, the process of 000Btu/lb.The great heat/energy loss of this expression system.

New class technology-pyrolysis/gasification of using-be attracting, because different with other technology of mentioning, it attempts refuse is converted into available materials, for example oil and carbon.When the optimal path of seeking to decompose waste product main what pay close attention to is that composition how to regulate the gained material makes simultaneously and decomposes required energy minimization.In the past, waste product is decomposed in the attempt of the main pyrolysis of use and evaporating method in single stage method (single step process), finds that still single stage method can not fully control the purity and the composition of the finished product.

Use cracker that organic materials is decomposed into gas, oil and tar and carbonaceous material.Cracker can heat organic materials to about 400 to 500 ℃ high temperature, but energy efficiency is low and it is not enough to form control for the gained material.Particularly, most of waste product-especially is from the product of agricultural-the contain water up to 50%.Cracker need cook off water, and this technology is starved of energy.In addition, in order to make the turnout maximum, pyrolysis chamber's general size is big.But be to use the large size pyrolysis chamber to bring the side effect that produces tangible thermograde, cause the inhomogeneous heating of waste product and cause low quality or impure tar and oil in the gained the finished product.

Used gasifier that waste product is carried out partial combustion.In fact, air, oxygen or the steam of gas-normally-with the amount that is enough to the whole combustible matls of the oxidation waste product of flowing through.Therefore, produced for example CO of some products of combustion ₂, H ₂O, CO, H ₂And light hydrocarbon, and the heat that produces is converted into oil, gas and carbonaceous material with the waste product of remnants.The gas that produces can contain some input gas (inputgas), can not store too greatly but any gas of producing all is volume, and must use or deliver to the occasion that can utilize them immediately.Gasifier also has some shortcomings identical with cracker: for example the aqueous waste product can consume big energy when the water that evaporation contains.

The product of pyrolysis and evaporating method tend to contain can not quantities received impurity.Particularly sulfur-bearing in the waste product or chloride material produce sulfocompound (for example, mercaptan) and organic chloride respectively in the gained the finished product.Usually, chlorinated hydrocarbon content is 1 to 2ppm can bear in hydrocarbon ils, but gasification or pyrolysis method all can not be guaranteed so low content with any reliability.

In addition, pyrolysis and evaporating method efficient are low, are generally about 30%.One of its reason is that product is not optimized aspect thermal content.Another reason is in single stage method, can not prepare this material in the mode that its energy is utilized in this technology again.For example, the heat energy in the solid product that is difficult to obtain to produce, and supply heat again to help the reacting by heating container.

In a word, so, the pyrolysis/gasification method is all restricted in some mode.Oil production is rich in unwanted high viscosity composition, for example tar and pitch usually.The heat transfer property of pyrolysis and gasifying process is low also therefore can not even heating.Therefore, for economic recovery, the number change of the finished product is very big, and does not have enough qualities or quality.Wet feed material needs very large energy to volatilize, and shows very large system energy loss, because water leaves with gaseous state in the raw material.Therefore, in general, the shortcoming of pyrolysis/gasification is total running cost height, and this technology is capital intensive and some by product has limited value or do not have value.

Although there are multiple version in pyrolysis and evaporating method, all these versions all have roughly similar shortcoming, and one of recent progress makes working (machining) efficiency significantly increase.For example United States Patent (USP) 5,269, and 947,5,360,553 and 5,543,061 discloses the system that replaces the single stage method of art methods with two step process.In the fs (so-called " wetting " stage), under about 200 to 250 ℃ and about 20 to 120 normal atmosphere, waste product is heated.In a preferred embodiment, waste product is subjected to about 50 atmospheric pressure.Under this condition, the multiple biopolymer of water hydrolysis in the waste materials, for example fat and protein, may there be the formation oil mixt in these biopolymers.(be also referred to as " doing " stage) in subordinate phase, to low pressure, during flash down (flash down), only about half of water is discharged system with vapor form with the mixture flash down.The continuation heated mixt finally resolves into gaseous product, oil and carbon with mixture simultaneously with the water of evaporation residue.

Compare with previous any single stage method, the main advantage of these two-step approachs is to form high-quality and more useful oil mixt.Yet the product of this method still suffers the pollution from the material of for example sulfur-bearing and chlorine-containing compound, and the needs that evaporate most water are still needed to expend lot of energy.Therefore, existing two-step approach is difficult to economically feasible ground and carries out.

Therefore, need be under acceptable fund and running cost, the method for the useful matter of processing refuse and reliable purity of low-value product production and composition.

Summary of the invention

The method of relate generally to processing refuse of the present invention and low value material.More specifically, the present invention relates under acceptable cost, and do not produce the discharging of foul smell and under high energy efficiency, refuse and low value material are changed into the method for useful products with reliable purity and composition.

Especially, method of the present invention comprises that the various feedstock conversion that will seldom have commercial value or purposes in other cases become useful matter, for example gas, oil, speciality chemical (for example lipid acid), fertilizer and carbon solid method.The present invention further comprises the device that carries out multiple process, and described multiple process changes into useful matter with refuse and comes from least a oil production of this technology.Apparatus and method of the present invention especially can be used for processing organic and inorganic wastes, tankage (offal) from poultry (for example turkey, chicken, ostrich), livestock, pig, fish, with other refuses, for example muck of shredder residues, animal, grease, vegetables oil and city sewage and sludge and tire and plastics.

In a word, the raw material that method of the present invention will prepare suitably places under heat and the pressure, and the various components in the separating obtained raw material further apply heat and pressure in these components one or more then.In the method for the invention, the various materials that produce at the difference place can be recycled and use, and are playing the part of other effects in the inventive method.

The present invention comprises the device that feedstock conversion is become at least a useful matter in addition, and this device comprises the preparation unit, puts comprising the slurry makeup, is produced the slurry of raw material by raw material; The container that is communicated with feed preparation unit is accepted the feed slurry from feed preparation unit; Extra equipment, for example pump pressurizes and heats the interchanger that slurry produces the heating slurry with being constructed to; The hydrolysis section reactor that communicates with this container, to accept the slurry of heating, wherein construct this hydrolysis section reactor, the slurry of heating is placed under temperature that increases for the first time and the pressure that increases for the first time, produce the reaction raw materials that contains at least a solid phase prod that has reacted, at least a liquid product that has reacted and water; At least one separating unit that communicates with the hydrolysis section reactor to accept at least a solid phase prod, at least a liquid product and water, is wherein constructed solid phase prod and water and at least a liquid product that has reacted that this unit separating out at least one has reacted; With the oil arrangement section reactor that communicates with separating unit, to accept at least a liquid product that has reacted, wherein construct this oil arrangement section reactor, at least a liquid product that has reacted is placed under the pressure that increases the temperature that increases for the second time and the second time of choosing wantonly, thereby at least a liquid product that has reacted is changed at least a useful matter.

The present invention further comprises the oil fuel of making by following method, and wherein this method comprises: prepare slurry by carbon raw material; In hydrolysis section, make this slurry reaction, produce the reaction raw materials that contains at least a solid phase prod that has reacted, at least a liquid product that has reacted and water; From the described raw material that has reacted, separate the described at least a solid phase prod that has reacted, described water and the described at least a liquid product that has reacted; In second reaction, the described at least a liquid product that has reacted is changed into oil fuel.

The present invention also provides the device that organic liquor is changed into hydrocarbon and carbon solid mixture, and this device comprises: heating organic liquor, thereby the well heater of the mixture of the gentle carburetion of generation liquid; The mixture of the gentle carburetion of liquid is changed into the carbon solid, and the reactor of the mixture of hydrocarbon and gas; Accept carbon solid first water cooler; Second water cooler with the mixture of accepting hydrocarbon and gas.

The present invention further comprises a kind of device, and this device comprises: the heating container with entrance and exit; Auger (auger) with first heating of entrance and exit is wherein constructed entrance and exit and selected its size, and to allow applying higher pressure in first auger, the inlet of first auger communicates with container outlet; The fluid-solid separator that communicates with the outlet of first auger, wherein this separator has first outlet and solid second outlet of liquids and gases; With second auger that is communicated with solid, this second auger provides the solid cooling.

The present invention still further comprises the method that organic liquor is changed into hydrocarbon and carbon solid mixture, and this method comprises: heating organic liquor, thereby the mixture of the gentle carburetion of generation liquid; The mixture of the gentle carburetion of liquid is changed into the carbon solid, and the mixture of hydrocarbon and gas; And the mixture that separates carbon solid and hydrocarbon and gas.

The present invention also provides the method by raw material production fuel, and this method comprises: by the feedstock production slurry; Make this slurry carry out depolymerization process, form the composition that contains at least a inorganic materials and liquid mixture; Separate described at least a inorganic materials and liquid mixture; Obtain (deriving) fuel with deriving by described liquid mixture.

The present invention further provides the method by raw material production fertilizer, this method comprises: by the feedstock production slurry; Become to contain under the temperature of at least a inorganic materials and liquid mixture and heat slurry being enough to the described raw material of depolymerization; Separate described at least a inorganic materials and liquid mixture; Obtain fertilizer with deriving by described liquid mixture.

The present invention still further provides the method by raw material production food, and this method comprises by the feedstock production slurry; Become to contain this slurry of heating under the temperature of at least a inorganic materials and liquid mixture being enough to the described raw material of depolymerization; Separate described at least a inorganic materials and liquid mixture; Obtain food with deriving by described liquid mixture.

The present invention also provides shredder residues is transformed olefiant method, and this method comprises: dissolve shredder residues in solvent; Prepare slurry by this shredder residues; This slurry and water are reacted in hydrolysis section, produce the raw material that has reacted that contains at least a solid phase prod that has reacted, at least a liquid product that has reacted; From the described raw material that has reacted, separate the described at least a solid phase prod that has reacted, described water and the described at least a liquid product that has reacted; In second reaction, the described at least a liquid product that has reacted is changed into oil.

The accompanying drawing summary

Fig. 1 shows the schema according to integrated approach of the present invention;

Fig. 2 shows employed schematic representation of apparatus in carrying out method of the present invention;

Fig. 3 shows the schema of the preparation and the hydrolysis section reaction of the inventive method;

Fig. 4 shows the schema of second segregation section of the inventive method;

Fig. 5 shows the schema of the oil arrangement section reaction of the inventive method;

Fig. 6 shows the device of the oil arrangement section of carrying out the inventive method;

Fig. 7 shows the micro-solid and the fluidic device of separate out suspended; With

Fig. 8 A and 8B show and adopt oil arrangement section reactor and the chiller/condenser of using respectively in the method for the present invention.

Fig. 9 shows the viscosity of raw material and the relation between the velocity of shear at various temperatures.

Figure 10 shows the schema that transforms the employed the inventive method of shredder residues.

Figure 11 has described the embodiment of depolymerizing reactor and separating unit.

Figure 12 has described the testing apparatus of desk-top scale used in the present invention.

Figure 13 has described the shredder residues sample.

Figure 14 has described the shredder residues fragment of various size.

Figure 15 has described the depolymerized product that is applied to the inventive method on the shredder residues.

Figure 16 has described the intermediates of the inventive method.

Figure 17 has described and has used shredder residues as oil in the middle of the hydrolysis of undressed raw material production.

Figure 18 has described various parent materials, intermediate and the finished product of the inventive method.

Figure 19 has described some distillation cracked oil products that exemplify that can use the inventive method to produce.

Figure 20 shows according to the inventive method that is applied on the shredder residues, the segmentation of the various chemical of finding in the cracking fuel gas.

Figure 21 is the hydrolysis section productive rate that shows based on 5 rounds, the chart of the productive rate consistence (run to run yield consistency) of the different rounds of the inventive method.

Figure 22 is depolymerization, hydrolysis and the oil arrangement step of following the trail of by the inventive method, and the exsiccant organism changes into the chart of various materials and gas.

Figure 23 is the chart that is applied to the material balance of the inventive method on the shredder residues.

Figure 24 has summarized water and how to have used in the method for the invention and circulate.

Figure 25 shows moving of in the device of the design according to the present invention water.

Describe in detail

Method of the present invention relates to from society or from conventional internal practice or from low value or the waste product of the generations such as commercial operation and generates one or more useful materials. Usually, method of the present invention is applied to refuse or other low value products, for example mainly contains the grease of organic material. Yet the present invention can be applied to other product (usually do not think low value) is converted into high value product.

Organic material is the material that those of ordinary skills understand usually. Particularly, for being used for the present invention, organic material is that its Constitution Elements comprises carbon and is combined with the material of one or more other elements, and other element is hydrogen, oxygen, nitrogen, sulphur and phosphorus and halogens, particularly fluorine, chlorine, bromine and iodine for example. For purpose of the present invention, organic material also comprises and contains carbon compound, this compound is combined with elements such as arsenic, selenium and silicon, and the compound of the salt of organic molecule and organic molecule and metal, metal is such as but not limited to magnesium, mercury, iron, zinc, chromium, copper, lead, aluminium and tin. Be used for many organic materials of the present invention from biogenetic derivation and comprise protein, lipid, starch, nucleic acid, carbohydrate, cellulose, lignin and chitin (chitin), and whole cell. Be used for other organic material of the present invention and have artificial or synthetic source, for example plastics, and other petroleum derivation product.

In the method for the invention, the long strand desired level with the fracture raw material applies heat and pressure. Therefore, at molecular level raw material is fractured into one or more composition materials. In the method, raw material is converted into profit or obvious cost or high value from cost or low value. Importantly, the method can be destroyed the pathogen that may be present in the raw material.

Basic skills of the present invention is designed to process potentially any refuse or low value product, comprise: the accessory substance of food production and distribution, for example turkey internal organ, Fried Fishes oil (fryer oil), cornstalk, rice husk, waste residue, (last-press) edible oil of long-term squeezing, for example rapeseed oil, soybean oil, palm oil, coconut oil, rapeseed oil, cottonseed oil, corn oil or olive oil and other oil, food processing refuse and seafood industrial waste; The accessory substance that paper and other timber industry generate, for example cellulose and xylogen by-product and paper pulp sewage; Garden refuse, for example leaf and cut careless refuse (grass clippings); Tire; Shredder residues; Plastic bottle; Sediment (harbor-dredged sediments) is fished at the harbour; Plastics and electrical equipment, for example old computer after the consumption; MSW; The oil plant residue; Industrial silt; Bagasse; Marine alga; Grind waste material; Black liquor (black liquid); The artificial coal waste material; Tar sands; Shale oil; Drilling mud; The cotton wastes material; Agricultural processing waste, for example animal wastes; The infectious medical refuse; The biopathogen body; With in addition such as the material of anthrax spores that can be used for generate biological weapons etc. Be appreciated that material listed above is not limit. In the enumerating in front, bagasse is the accessory substance of processing sugarcane, and black liquor is the accessory substance of chemical wooden oar processed, its from the dissolving wood chip, discharge lignin and remove fiber to obtain lignin and hemicellulose solution.

The refuse that the present invention uses is accessory substance or the end product of other industrial technology, commodity production and domestic or urban applications normally, and they do not have other direct purposes usually and/or it is generally thrown away. Similarly, low value products can be accessory substance or the end product of other industrial technology, commodity production and domestic or urban applications, but normally have the material of low resale value and/or its need some further processing in order to be converted into the material of used article.

When using method of the present invention, the so-called raw material of refuse and low value products or raw feed (raw feed). It is also understood that raw feed that method of the present invention is used can comprise from a large amount of sources and has dissimilar refuses and/or low value products. For example, such as fruit instant, the food processing refuse can make up with agricultural processing waste, and simultaneously processing.

Other exemplary raw feed material that the present invention uses comprises municipal sewage mud, mixed plastic (comprising polyvinyl chloride (" PVC ")), as obtaining from circulation warehouse, city, and tire.

Polyvinyl chloride (PVC) is found in vinylite baffle plate and the plastic tap water pipe road. PVC contains the chlorine of the 55wt% that has an appointment and therefore tend to produce harmful chlorine-containing compound when degraded. For example, burning PVC produces dioxin, and dioxin is some the most malicious known compounds. Be that hydrogen ion in water is combined with the chloride ion from PVC in an advantage of the early application water of the inventive method, obtain the product of solubilising, hydrochloric acid for example, a kind of relatively friendly and industrial valuable chemicals that can be used for cleaning agent and solvent.

Tire is usually available from the vehicles, for example automobile, bus, truck, aircraft and other public transport, and army and other commercial vehicles. When tire was used method of the present invention, the oil that a part generates was preferably recycled to entrance with the tire in the raw material of assist in dissolving introducing.

Shredder residues (SR) is residual material reclaim ferrous metal from the vehicle of pulverizing or remove, white articles, the consumer goods etc. after. In the situation of not utilizing advantage of the present invention, these materials are typically buried. The example of " white articles " comprises washing machine, drier, refrigerator, utensil scrubber, electric furnace, air-conditioning, water heater; This term as used herein also comprises any apparatus of processing for its metal content energy refuse. Below showing two kinds of SR sample component and the element measured by sample analysis forms.

Sample 1

Sample 2

Above-mentioned data are provided, and only are to set forth the material type that can find in given SR sample, the not application that should be construed as limiting the invention.Depend on its source, the composition of shredder residues material may change at different samples.For example, SR can comprise the fragment such as plastics, rubber, glass, fabric, paint, timber, foams, particulate, elastomerics, kish of different size shown in Figure 14.The SR of old televisor and refrigerator for example may contain heavy metal or polychlorinated biphenyls (PCB) (a kind of mixture of deleterious chlorinated cpds).Other poisonous components of finding potentially in SR comprise Polybrominated phenyl ether (PBDE), and it is usually as fire retardant with in the phthalic ester that chemically is similar to PCB and find in PVC (a kind of important component in motor vehicle is made).

The blended low value waste can be handled and process to method of the present invention and this material that do not need to classify in advance is pure logistics.In addition, the oxygen-chlorine key in the method hydrolyzable PVC of the present invention, and metal and halogenide transferred in the water.About the hydrolysis of PVC, hydrogen ion in water and halogen ion, for example Br and Cl combination produces the friendly relatively chemical that uses.In other cases, the deleterious chemical that lixiviate goes out from SR, for example PCB, PBDE are destroyed in the method, thereby produce the oil that does not contain this pollutent and other chips.The feature of two batches SR cracked oil product is provided in following table.Another advantage of the present invention is the material that it can handle and process effectively inhomogeneous size and composition.Saved the screening of particle size/reduce by depolymerization step of the present invention, its mechanism will become clearly according to following disclosure.

In the time of on method of the present invention being applied to SR, the part of the oil that is produced preferably is recycled in the inlet, dissolves SR to assist in the raw material that enters.Figure 10 has described the schema that is applied to the method on the SR.Unprocessed raw material is prepared step 110, depolymerization or " fusion step ", follows mechanical separation, so remove solid from mixture.Organism in depolymerization reduction (reduce) solid SR becomes liquid, thus make can the separating metal object with other solid organic matters and in hydrolysing step subsequently organism contact with water is improved.In a preferred embodiment of the invention, be that more preferably scope is about 700 °F-Yue 775 °F under about 690-Yue 785 temperature in scope, most preferred range is to carry out depolymerization under about 720 °F-Yue 750 °F.

The hydrolysing step that then the gained mixture is equivalent to hydrolysis section described herein 120.The organic hydrolysis of chlorination and/or bromination disconnects carbon-halogenide key in this mixture, and halogenide is transferred to aqueous phase, thereby has destroyed the compound such as PCB effectively.Hydrolysis also allows metal ion to transfer to aqueous phase, thereby makes gained oil be substantially free of pollutent.In a preferred embodiment of the invention, be about 430 °F-Yue 510 °F in scope, more preferably scope is about 440 °F-Yue 500 °F, most preferred range is to be hydrolyzed under about 450 °F-Yue 480 °F.

The raw material that has reacted that is produced experiences heat and mechanical separation step then.In being similar to the method for delayed coking, heating hydrolysis oil is to about 500 ℃.Transfer of heat is quick and isothermal to oil, and only heating " drying " organic oil arrives final temperature.Therefrom oil fuel of Huo Deing or organic liquor 500 are fed in the oil arrangement section for arrangement.Can by or produce fuel gas 146, carbon solid 142 or oil 144 on the spot or in the Refinery Coking organic liquor.Perhaps, can under the processing situation on the spot of minimum, produce the hydrocarbon ils that has with #4 diesel engine oil analogous components.

Below provide two of cracked oil product of the inventive method that is applied on the SR different batch feature.

Batch 1 batch 2

In the method for the invention, by countercurrent flow, realize high energy efficiency.Use most of energy heating liquid water; The water of flash distillation generates steam in hydrolysis, isolates described steam, and shunts the raw material that enters with preheating.As shown in the synoptic diagram of Figure 23 and Figure 25, so the water of flash distillation is circulated in the hydrolysing step process.If change the chemical constitution of unprocessed raw material, then can in different rounds, change energy efficiency.Yet, use the test under a plurality of rounds, carry out, the energy efficiency of measuring this method is about 91%, as what describe in detail in the following table.For these rounds, select 900 temperature, this is because concerning this method, it is enough, and proof even can realize high energy efficiency to high temperature following time when heated mixt.

Be applied to the method energy efficiency on the SR
	Organic calorific value :～15,000Btu/lb
Has Cp～0.75Btu/lb with 50: 50 mixture of water
	Be heated to 900 °F: 675Btu/lb mixture (1,30Btu/lb oil)
Efficient=100%-(1,350/15,000)=91%

In addition, can use commercially available parts, construct device of the present invention.Can under envrionment conditions, use the spiral conveyer and/or the chapelet of false-bottom bucket, routine, carry out the processing of initial rough stock.Can optionally use the level sieve of used by oscillating screen, to remove loose foul and chip in particulate.Powerful depolymerization step has also been saved any demand to the granule sieving of extra undressed raw material.It is apparent that according to following disclosure, the temperature and pressure of in present commercial applications, using always, for example 750 °F, 150psig is enough for the unprocessed raw material of depolymerization.Therefore when using low relatively pressure in the method for the invention, can use simple prior art, for example the jacketed reactor of intermittence or direct current is implemented the depolymerizing reactor design.The device that can obtain easily, for example vibratory screening apparatus, list and twin screw press also can be used for carrying out depolymerization with ready-made whizzer and separate.Similarly, can use commercially available apparatus and method, for example vapor recompression/distillation, roasting, fluidized-bed system and desalination and centrifugal separation unit carry out posthydrolysis processing.

The refuse and the low-value materials of embodiments of the present invention processing are converted into three kinds of useful materials usually, and all these three kinds all is valuable and itself is for environmentally friendly: high quality oils; Clean burning gas; Comprise mineral with the purifying solid and can be used as fuel, fertilizer or generate the carbon solid of raw material.In addition, the various effluents of producing in technological process of the present invention (side-streams) comprise the similar enriched material with " condensed fish soluble (fish solubles) " in some cases.Usually, useful materials thinks to have the material of the refuse, low value or the higher economic worth of other material that liken to raw material.Compare with the raw material that derives useful materials, these useful materials can have higher thermal content, perhaps can have wider application.

Method of the present invention comprises many stages, as illustrated in fig. 1 and 2.Fig. 1 shows the general introduction of the principle feature of embodiment of the present invention.Fig. 3 show implement the inventive method exemplify device 200.

Unprocessed raw material 100 shown in Figure 1 can be the organic and/or inorganic logistics of any refuse or low value potentially.Preferably, unprocessed raw material contains the carbonaceous material of significant quantity.

Unprocessed raw material 100 is placed preparation section 110.An aspect of preparation section is to use slurrying and other crushing technologies, and the size that reduces unprocessed raw material is to the size that is suitable for pumping.The preparation section can comprise one or more step, and can comprise the interpolation material or drive away material from unprocessed raw material, and causes flowing through the slurry 112 of hydrolysis section 120.Slurryization can involve interpolation water (or other suitable fluids), and in unprocessed raw material 100, this depends on its initial water content.It is useful using slurry, be because the wet pulverization in preparation section 110 can reduce friction and energy consumption, and because slurry can easily be transferred to another container from a container by pump.Suitable slurry makeup is put and is comprised: pulping engine, online pulverizer or maserator.From preparation section 110, discharge the mixture 121 of steam and gas.

Bone and other inorganic minerals are complete parts of animal and animal waste.The organic substance of protein, fat and carbohydrate form by physics and chemical fixation to this inorganic mineral, thereby make this organism be difficult to be processed into value product, unless separate the two.Therefore, in step 114, slurry experience depolymerization step, it is heated to 275 °F to 380 °F at this, preferred 275 °F to 325 °F and even more preferably 300 to 325 temperature, so that the separation inorganic substance, for example bone and other solid matters are with organic composition.Persons skilled in the art will recognize that inorganic composition with organic substance is different for different batches, this depends on employed raw material properties.Bone material 116 only plans to be used for setting forth the type of the inorganic substance that provide in some embodiments of the present invention.For example shredder residues, tire, plastics or rubber constitute under the situation of unprocessed raw material therein, and inorganic substance can not comprise the bone material.

Depolymerization step (being also referred to as heating steps 114) was carried out 15 minutes and preferred 45 minutes at least.Depend on temperature heat-up time, requirement is lacked to 15 minutes and is required greater than 1 hour in lower temperature range under higher temperature.Be heated to total viscosity of reducing slurry under this temperature sharp and to be hydrolyzed into amino acid structure unit (or two-and three-peptide) consistent with raw material internal protein material, physics between result and the inorganic substance and chemical bond rupture.The decline of this viscosity allows to separate the fixed insoluble solid, for example contains bone material 116 and the slurry of not wanting mineral substance and broken bone, thereby is entered the liquid mixture 118 of hydrolysis section subsequently.

Isolated mineral substance mainly comprises efflorescence and granulous bone material and from the mineral of the certain content in the sand in incoming stock, soil or other pollutents in this stage.Can realize separating of mineral substance and all the other materials by gravity separation, perhaps can utilize other tripping devices that those skilled in the art are afamiliar with, for example liquid/solid whizzer, sieve or strainer.Isolating mineral substance like this can be used as mineral manure.By separating technology, isolating mineral substance does not preferably contain organism, but in practice, has the organism of trace.

Coming from isolating liquid mixture 118 typically comprises and contains fat and the oil phase of carbohydrate and by the amino acid of protein degradation acquisition and little peptide dissolved water within it.Liquid mixture can comprise some insolubless in addition, and described insolubles comprises some mineral and some peptides that do not decompose.In view of the foregoing, the composition of liquid mixture makes it also directly or with conc forms to be used as food, fertilizer, fuel or other products from hydrolysis 120 paths shuntings (divert).In some embodiments of the present invention, spissated liquid mixture can be used as boiler or motor spirit uses, and perhaps can for example further process in refinery.Use the alkyl raw material in the present invention, for example plastic waste, rubber, used in some embodiments of tire etc., can be in conjunction with organic solvent and unprocessed raw material 100, with the organic functions of maximization raw material and and then improve the productive rate of useful liquid mixture.

As skilled person understands that depolymerization step 114 also may be used on other technologies, the animal waste that for example wherein contains bone and mineral substance is decomposed to form in refinement and the processing of animal of other useful matteies.Usually, compare, apply 275 °F to 380 °F with possible up to now method, preferred 275 °F to 325 °F, with in addition more preferably 300 to 325 heat will carry out organic substance to this raw material and more effectively separate with mineral with bone.So this method helps to separate bone and mineral substance and remaining raw material, and causes purer organic moiety, and reduce the organic content that becomes useless on the useless mineral substance because of being fixed to.

Therefore, the present invention comprises that further refining and process (rendering) contains the method that organic substance is fixed to the animal body part on the insoluble solids, and this method comprises, partly prepares slurry by animal body; Heat this slurry to 275 to 380 °F, preferred 275 °F to 325 °F and even more preferably 300 °F to 325 °F, to produce liquid mixture and insolubles; With remove the bone material.Existing animal is refined the temperature that does not typically have heating raw to arrive under this high temperature with working method and mostly just be heated to 212 (100 ℃) before noting.In addition, prior existing animal is refined with working method and typically produces two batches product: meat in one batch and bone meal and the fat in the second batch.On the contrary, two batches of method generation heterogeneity of the present invention: mainly contain bone, that is separate and can be used as for example solid matter of mineral manure fully; With the liquid portion that itself comprises separating oil part, what described separating oil partly can be used for generating lipid acid and can be used as the animal-derived food product feed contains water section (it contains dissolved amino acid in water).

In hydrolysis section 120, slurry is placed under the pressure of heating and increase, wherein slurry experience hydrolysing step is also referred to as the hydrolysis section reaction.This heating and pressure condition cause the cellularstructure of biological components in the slurry to be decomposed, and discharge the formation molecule such as protein, fat, nucleic acid and carbohydrate.In addition, by the water in slurry, the many polymer organic materials of hydrolysis become the mixture of fairly simple organic products.Especially, fat can partly decompose, and obtains the organic substance that can float, for example lipid acid (it contains the carboxylic acid group) and water-soluble glycerine (molecule that promptly contains 3 hydroxyls).Protein typically resolves into fairly simple polypeptide, peptide and composition amino acid.The carbohydrate great majority resolve into fairly simple water soluble saccharide.Oxygen such as PET and PVC in the plastics and chlorine key also rupture in hydrolysis section.Have the water particularly advantageous in hydrolysis section, this is because its assists transmission heat to raw material.

Be appreciated that when the term anti of using in conjunction with embodiment of the present invention should (react, reacting reaction) can comprise many dissimilar chemical transformation.Especially, term anti should comprise combination or the associating chemical transformation that comes from two or more materials, described chemical transformation will obtain one or more products, with decomposition that can comprise other types or conversion, described decomposition or conversion involve by temperature, pressure condition induces or the decomposition or the conversion of the simple species of electromagnetic radiation, and can further comprise the conversion that involves solvent, for example hydrolysis.When further being appreciated that section in using term " reaction " description process or process herein, can carry out simultaneously greater than a chemical transformation.Therefore, reaction can involve for example hydrolysis and decomposition simultaneously.

Typically in hydrolysis section 120, the mixture 126 of released vapour and gas products from slurry.The raw material that has reacted 122 that comes from hydrolysis section typically is made up of the mixture of the mixture of the solid phase prod that has reacted and the liquid product that reacted.These various products typically are characterised in that oil phase, water and wet mineral facies.Water and oil phase typically contain various lysed organic substances.Preferably be separated in the steam of generation in the hydrolysis section 120 and the mixture 126 of gas by condenser, and the slurry that uses steam preheating to enter.

The raw material 1222 that will react then places segregation section 130, drives away the further mixture 132 of steam and gas at this, and isolates mixture 134 or other solid matters of mineral.Preferably, the solid matter that obtains in this section does not comprise the carbon solid, unless the carbon solid is present in the raw material of input.Segregation section 130 can comprise greater than an independent separation.In some embodiments of the present invention, solid matter can experience further processing in the roasting device, makes from any residual organic wherein and burns and roasting.Other materials of generating of each some place of described method herein, for example spissated uncondensable gas, solid inorganic thing 116 and aqueous enriched fuel can be fed in the roasting device equally for further processing.In some embodiments of the present invention, the solid of production roasting and produce deep fat and/or steam when in various application, using, the roasting device plays dual function.For example, hot steam can for example be used to supply steam turbine in power station or other industry and production.

Residual substances from segregation section 130 is made up of the mixture of liquid product and organic liquor 500, and described liquid product comprises the water 138 (water with solvend) that is produced.Organic liquor 500 typically is the mixture that contains carbon species, for example comes from the liquid of the liquid product that has reacted in the hydrolysis section.Preferably, separate most of water that produce 138, and with liquid product, for example organic liquor 500 directs in the oil arrangement section 140.Therefore, organic liquor preferably includes and aqueous phase separation and the liquid product that has reacted that in most of the cases also is separated with the solid phase prod that has reacted.The water 138 that is produced contains chemical compound lot, comprising sulfur-bearing and chloride material and preferred the shunting for concentrating 139.Wish to isolate these compounds, in preferred embodiments, concentrate and obtain condensation product 151 (it is main waste water (municipal-strength waste water) that its purity is better than the city usually), with enriched material 153 (in many cases, it can be used as organic-fuel or is similar to the liquid fertilizer of extract).

Some organic liquor 500 can be diverted in the optional separation 137, for example by the fractionation of organic liquor, form special organic chemicals 143, for example lipid acid or amino acid.Residual cut, the liquid fractionation 145 (it can comprise can not as the cut of speciality chemical) that usually is called " heavy mother liquor " can direct in the oil arrangement section 140 again.

When raw material was city sewage and sludge, the raw material that has reacted 122 that reacts from hydrolysis section typically comprised the water that is produced, organic and the solid matrix of inorganic substance and the organic liquor of a small amount of.The water that is produced from municipal effluent mud is shunted then for concentrating, and forms the product that can be used as fertilizer.

Put in order in the section 140 at the oil that also is called " oil arrangement ", organic liquor 500 is placed in one, and its experiences under the condition of second reaction.Second reaction can involve one or more process known in the art, for example simply dehydration, distilled fatty acid, thermally splitting, catalytic cracking, removes mud etc.Also possible situation is that organic liquor contains a certain amount of solid phase prod that has reacted that also flow in the oil arrangement section.Organic liquor and the solid phase prod that has reacted can be called as solid matrix together.In second reaction, organic liquor changes into the mixture of the useful matter that generally includes carbon solid 142 and the mixture of the hydrocarbon that typically discharges with hydrocarbon vapour and gas 148 forms.This conversion can involve one or more materials that decompose in the organic liquor.Appropriate condition in the oil arrangement section is typically used the temperature that raises with respect to hydrolysis section and is used the pressure that descends with respect to hydrolysis section.Oil arrangement section does not typically involve uses the water that adds.Can use many different devices to carry out oil arrangement section, further describe as the present invention.

Carbon solid 142 typically is similar to coke, promptly is generally suitable for the hard carbonaceous material with high caloric value as fuel.Carbon solid 142 preferably contains seldom (if any) non-flammable mineral, and described non-flammable mineral typically come from the anoxic atmosphere and burn carbonaceous material.Mineral content in the carbon solid 142 is more preferably less than 5wt% preferably less than 10wt%, still is more preferably less than 2wt%.Most preferably less than 1wt%.Contain at carbon solid 142 under the situation of mineral, they are also referred to as carbon-mineral substrate.

When biomaterial was the raw material of the inventive method, hydrocarbon vapour and gas 148 were called as " biologically-derived hydrocarbon ".If unprocessed raw material comprises tire, rubber or plastics respectively, then hydrocarbon vapour and gas can be called " tire is derived ", " rubber is derived " or " plastics are derived " with changing.Hydrocarbon vapour and gas 148 typically comprise the appropriate hydrocarbon gas and the non-hydrocarbon gas impurity of some traces possibly.Appropriate hydrocarbon gas comprises the gas such as fuel gas 146; Hydrocarbon vapour can be condensed into liquid or oil 144 easily, for example light composition of #2 diesel engine oil.Person of skill in the art will appreciate that the #2 diesel engine oil is the oil with relative low viscosity or density.

When raw material is city sewage and sludge, typically comprise the mixture of hydrocarbon ils, fuel gas and mineral and carbon mixture with solid form from the solid phase prod of oil arrangement section.

Be appreciated that the operating parameters that to reduce the method for abridged edition invention in one or more situations, to adapt to dissimilar unprocessed raw materials.For example, at unprocessed raw material, for example under the situation of turkey tankage, main component is animal tallow, protein, carbohydrate and mineral.Therefore, the surplus of main ingredient can determine some aspects of operational condition of the present invention.In addition, the temperature range of may command first and oil arrangement section reactor produces specific product, thus the economic worth that maximization can be obtained by the production of various products.

Fig. 2 shows the device 200 of implementing the inventive method.Based on instruction of the present invention, in the limit of power of the those of ordinary skill that is assembled in process engineering or field of chemical engineering of each assembly of device 200.Therefore, the details of this technology those skilled in the art are afamiliar with, and therefore saves from description of the invention.In addition, just as described here, those skilled in the art can substitute single workpiece shown in Figure 2 with each workpiece of device, and implements method of the present invention.

Can in feedstock production device 210, carry out feedstock production and slurryization.After feedstock production and feed slurryization, slurry flows is in the container 220 of the lp venting that is called raw material storage tank.Preferably, in raw material storage tank or before raw material is heated, produce the slurry of heating, optional the pressurizeing of slurry to described heating enters in the hydrolysis section reactor afterwards.Typically comprise the container that keeps slurry, carrying out this heating and pressurization in the equipment of the pump of increase slurry pressure and the interchanger of heating slurry.Typically use the condition of about 140 and 1PSI, so that to keep slurry be liquid state and limit biological activity.In preferred embodiments, the heating first jar to about 140 °F (about 60 ℃) temperature and place under the pressure of about 1p.s.i..This condition in first jar causes that effectively biological activity stops.In the embodiment that exemplifies, first jar capacity can be about 1,000, the 000U.S. gallon; Therefore for the circulation of 100-150 gallon per minute, the effective residence time in this jar is about 700 minutes.In this embodiment second jar can maintain under about 300 temperature and content is placed under the pressure of maximum about 100p.s.i..Pressure is usually a little more than at the saturation pressure to mixture under the fixed temperature.For example, the saturation pressure of mixture is 66p.s.i down at about 300 °F (about 150 ℃).Condition in second jar is typically enough harsh to decompose the proteinaceous material in the slurry, makes slurry loose and drive away ammonia.Second jar capacity is typically less than first jar with can be as small as the 2500U.S. gallon.Therefore, in one embodiment, the flow velocity of about 40 gallon per minute obtains about 1 hour residence time in second jar.Under lower flow velocity, can realize for specific raw material the long preferred residence time, for example a few hours in second jar.

Carry out hydrolysis section of the present invention in hydrolysis section reactor 230, described hydrolysis section reactor 230 preferably includes multi-chamber container, so that there is the narrow distribution of each component substances residence time of slurry.In an alternative embodiment, the hydrolysis section reactor also can be a helical reactors.Preferably, this container is furnished with baffle plate and can stirs the agitator of electronic a plurality of blades of slurry simultaneously in each chamber.In preferred embodiments, in this container at four chambers.In another embodiment preferred, carry out the heating of slurry in several sections before this container.

Can in the flash chamber 240 with ventilation opening (" second section separator "), be implemented in the flash distillation of the raw material that has reacted after the hydrolysis section.Preferably, the pressure in flash chamber 240 significantly is lower than hydrolysis section reactor 230.In one embodiment, the pressure in flash chamber is about 300psi, and wherein the pressure in the hydrolysis section reactor is about 600psi.

Can use various device to realize various second section separation of effusive raw material from hydrolysis section reactor 230.Preferably, this separation provides steam and gas 132, organic liquor 500, mineral 134 and the mixture of the water with solvend 138 that produced.Steam and gas flow back in the preparation section for 132 preferred branches, heat with auxiliary material.

Can adopt centrifugal, cyclonic separator or adopt static jar (static tank), realize separating of mineral and organic liquor and water.Can adopt for example drying oven or other mineral moisture eliminators, " annular " moisture eliminator (not shown among Fig. 2) is for example realized the drying of mineral 134.(in an alternative embodiment, can make emulsion breaking by adding chemical, thereby promote to separate.)

The water with solvend 138 that is produced (it comes from separating of organic liquor and water) can concentrate in industrial typically obtainable vaporizer 250.Can be included in the organic liquor storage vessel 252 with the organic liquor 500 of mineral and aqueous phase separation, transfer to afterwards in the oil arrangement section reactor 260.This storage vessel can be the common storage vessel that typically uses industrial.

Exemplify in the embodiment of the present invention, the organic liquor 500 of some or all can be shunted, to obtain one or more speciality chemicals.Typically, this involves organic liquor is carried out fractionation.Typically fractionated organic liquor was carried out in distillation in distillation tower 254.Before in flowing into distillation tower, can carry out pickling, to isolate the amino acid of trace to organic liquor.From most of volatile matter of organic liquor, for example lipid acid is distilled out and is collected.Any heavy material of finding in the distillation tower bottom, for example nonvolatile fat and fat derivant are transported in the oil arrangement section reactor 260.

Exemplify in the embodiment at of the present invention other, can shunt the organic liquor 500 of some or all, to obtain carboxylic acid oil (carboxylic oil).Carboxylic acid oil can be directly as spendable fuel source in boiler, well heater or engine.In some embodiments of the present invention, for example in refinery, carboxylic acid oil is further processed.Perhaps, can before using,, further process or purification of carboxylic acids oil by filtration and/or centrifugal.For example, carboxylic acid oil can experience hydrotreatment (method of using always in the refinery), removes denitrification and sulphur from thick oil, obtains the clearer burnt fuel, because the existence of nitrogen and sulphur can cause forming Nox and SOx in combustion processes.Described as the embodiment part, low by the sulphur content of carboxylic acid oil provided by the invention, typically＜0.2%, therefore require very a spot of hydrogen for the hydrotreatment purpose.The easy degree that the grade of carboxylic acid oil promotes is also owing to low nitrogen content, and most of nitrogen exist with the amine form rather than with heterocycle.

Can use various raw materials to generate useful carboxylic acid oil at this point place of the inventive method.Preferably fatty/greasy raw material, for example animal tallow, oily seed-soybean, rapeseed oil (canola), trap grease and protein source are to maximize the productive rate of useful carboxylic acid oil.The material that is suitable for this purpose does not comprise animal waste, plant waste, refuse and from the logistics (DDG) of the low value of ethanol production facilities with getting rid of.

Coming from second section isolating organic liquor also can flow in the oil arrangement section reactor 260.Wherein carry out organic liquor within it and change into one or more useful matteies, for example second of oil and carbon solid 142 reaction.Effusive oil can further separate in separator 270 from oil arrangement section reactor, to produce oil 144 and fuel gas 146.Separation can be included in cold oil in each step, and it is diverted to oil in reserve 280 in the storage vessel.Cooling comes from the carbon solid 142 of oil arrangement section reactor and also can store, and perhaps further heats according to method known to those skilled in the art, handles then, to activate them.For example, can be at extra reactor internal heating carbon solid, and activate by injecting superheated vapour.

As mentioned above, the unprocessed raw material that exemplifies comprises the refuse from agricultural and food-processing industry.This refuse can comprise the part of animal, for example wing, bone, feather, organ, skin, head, blood and neck, soft tissue, claw and hair.Typical animal part is those of finding in the turkey tankage and the corpse resistates that comes from the slaughterhouse.Be suitable for adopting other refuses of the inventive method processing to comprise, for example hamburger commission agent's useless grease and such as the material from dissolved air floatation (" the DAF ") mud of food processing plant from fast food enterprise from food-processing industry.Agricultural waste can comprise the muck of animal muck or sheep, pig and milk cow, and such as foreign material (chickenlitter) of chicken and the other materials the residue of crops, exemplifying in the embodiment shown in Fig. 3-5, unprocessed raw material 100 is byproducts of food-processing, for example the turkey tankage.

As shown in Figure 3, unprocessed raw material 100 is prepared and slurryization 110 at first, produces feed slurry 112 and is attended by steam and gas 121.Slurry 112 can be in interchanger 114 be transferred to raw material storage tank (" FST " or homogenizer) raw material storage 320, other hard main parts are decomposed in described interchanger 114 internal heating raw materials make the proteinaceous material that is fixed on the bone and mixture.For the raw material such as food-processing refuse or city sewage and sludge, the heating that is used for this purpose is to reach 275 to 380 temperature, preferred 275 °F to 325 °F and even more preferably 300 °F to 325 °F.In scope is that 300-325 internal heating should preferably continue about 1 hour.The result of this heating reduces the viscosity of slurry, makes the content bioinactivation, and produces mineral mixture (comprising efflorescence and granulous bone) and liquid mixture.In step 310, for example by gravity separation or centrifugal by liquid/solid, perhaps screen cloth or strainer separate the insoluble solid and the liquid mixture 118 that contain mineral and bone material 116.Make the liquid mixture cooling of the mixture that comprises water and water-insoluble organic constituent and some trace mineral and direct in the raw material storage tanks 320 (" FST " or homogenizer).Arrive about 275-280 °F at FST internal heating content, and place under the pressure of about 50p.s.i., so that produce the raw material of regulating 322, a kind of raw material relatively uniformly that is suitable for flowing in the hydrolysis section reactor.In the raw material storage process, steam and gaseous impurities 338 are preferably by emptying 336.

Therefore, an advantage of the invention is in FST to outgas, remove undesired gaseous impurities in early days in universal method of the present invention.Feed slurry 112 can remain on 320 any times easily of raw material storage, is further processed by method of the present invention up to it.Preferably, FST supply constant feed stream makes the raw material pressurization and is transported in the hydrolysis section reactor in the high pressure shurry pump.In preferred embodiments, feed slurry 112 can remain on any time easily in the big storage tank, is further processed by method of the present invention up to it.

For containing significant quantity ammonia (NH ₃) unprocessed raw material, turkey tankage for example, advantageously or in preparation section 110 (in this case, it is a kind of component of steam and gas 121) or in canned paragraphs 320 (it is with steam and gaseous impurities 338 emptying at this), remove free ammonia.A source of ammonia is the uricolysis of finding in the urine of residual quantity, and described urine usually is present in the aggregate (aggregate) of animal body part.The method of removing ammonia was separated the urine content with including, but not limited to before slurryization in those skilled in the art's ken, use enzyme liberating and apply heat.In addition, can transform the ammonia salify by acidifying, for example ammonium sulfate or ammonium phosphate.In preferred embodiments, FST comprises two containers that maintain under the different condition.First such container plays the effect of storage, and second container carries out proteinic decomposition and discharge ammonia.

The feed slurry 322 of effusive adjusting from raw material storage tank 320 places hydrolysis section 330, and wherein the water-content in the feed slurry 322 of regulating influences the hydrolysis of existing many biological polymers.Provide competent stirring (providing), so that solid keeps suspending by mixing tank and/or circulation device.Hydrolysis section typically spent about 5-about 60 minutes.Output from hydrolysis section is the raw material 122 that has reacted.Typically steam and gas 339 also discharge from hydrolysis section.

In hydrolysis section 330, carry out certain degassing, wherein carry out the part of nitrogen and sulphur compound and remove, and can carry out wherein that remarkable amounts of protein also is dissociated into product such as ammonia and potential carbonic acid gas take off amine and decarboxylic reaction.In practice, for method of the present invention, decarboxylic reaction is undesired, because the product except carbonic acid gas is an amine, amine tends to have water-soluble and volatilization.Therefore, take off generally that amine reaction is better than decarboxylic reaction and when raw material comprises material such as protein and fat, typically comprise carboxylic acid by the liquid product that has reacted of hydrolysis section acquisition.Therefore, because decarboxylic reaction typically carrying out than taking off under the high temperature of amine reaction, hydrolysis section is preferably moved under the possible minimum temperature when fat mols decomposes.Scheme can change the interior pH of hydrolysis section by adding acid, thereby stop decarboxylic reaction as an alternative.

If allow oil arrangement section reactor processing by some type, then in the preheating section of this section and front, remove denitrification and sulphur compound, to prevent to form organic nitrogen compound, ammonia and various sulphur compound, these may be non-required components in the biologically-derived hydrocarbon of gained.

The representative condition of the section of being hydrolyzed is 150 ℃-330 ℃ in this example, but pressure or the about 600psi of preferred about 250 ℃ and about 50atm, such as obtainable in the hydrolysis section reactor.Usually, the pressure range in the hydrolysis section reactor is 20-120atm.Total preheating and hydrolysis section are about 120 minutes at most heat-up time.Change this condition according to employed raw material.In one aspect of the invention, on being applied to the raw material that contains PVC, the service temperature in the hydrolysis section is enough high and then carry out washing step, so that remove chlorinated products.

Usually, be the section of being hydrolyzed under the about 150 ℃-Yue 330 ℃ temperature in scope, so that can realize in following three conversions at least one.The first, protein degradation becomes independent amino-acid residue, and described protein is made up of these amino-acid residues.This can be by each is realized the peptide amide bond between the amino-acid residue in for protein hydrolysate main chain under about 150-220 ℃ the temperature in scope.The second, fat mols can resolve into fatty acid molecule, and a kind of can be the process of carrying out in 200-290 ℃ in scope.Fat is hydrolyzed, and triglyceride level is decomposed, and forms free fatty acids and glycerine.The 3rd, can in hydrolysis section, carry out amino acid whose take off amine and decarboxylation.If allow to carry out oil arrangement section reactor reaction, the carboxylic acid group who then still is fixed on their amino acid moieties separately will all change into hydrocarbon under gentle relatively operational condition.In addition, can exist and take off more aminating amino acid, described to take off amine reaction be the process of typically carrying out in 210-320 ℃ temperature range.Therefore, in independent hydrolysis section, all proteins basically that is present in the slurry changes into amino acid under low relatively hydrolysis section service temperature.In addition, can control the amino acid whose amine degree of taking off by the service temperature of selecting hydrolysis section suitably.

Change with employed raw material as the physical condition that skilled person understands that the operation of hydrolysis section reactor.For example, the tankage of animal typically use range be about 200 ℃-Yue 250 ℃ hydrolysis section temperature.City sewage and sludge typically use range is about 170 ℃-Yue 250 ℃ hydrolysis section temperature.Contain mix plastics raw material typically use range be about 200 ℃-Yue 250 ℃ hydrolysis section temperature.Tire typically use range is about 250 ℃-Yue 400 ℃ hydrolysis section temperature.In the hydrolysis section reactor of the inventive method, be used for tire processing typical operation conditions be under 275 ℃ and 300psi, and solvent and tire is 1: 1 or lower than by weight.For giving fixed temperature, therefore this tonnage is both economical far below the pressure of reporting in other tire working method.

The hydrolysis section of tire processing also can involve water to remove the material that contains such as the dvielement of chlorine.Preferably, under normal operational condition, this material almost completely is removed.For hydrolysis section, can be mixed together tire material, solvent and water, solvent and water are continued contact tire.

Typically select under the service temperature that the pressure in the hydrolysis section reactor approaches to be discussed water saturation to press.Saturation pressure is to need applied pressure when keeping water to avoid seething with excitement under given temperature, and also depends on the existence and the amount of other gases in the feed slurry of purifying.Total pressure in the reactor is greater than the vapour pressure of water in the slurry mixture, so that water does not seethe with excitement.Pressure range is preferably 45-55atm, can be in the 40-60atm scope and also can be in the 30-70atm scope.Typically, by more than the saturation pressure at most 0-100psi and the quantity in the 0-100psi scope regulate pressure so that can be from feedstock production, raw material storage or hydrolysis section reactor the undesired gas 336 of emptying.

An advantage of the invention is that emptying allows to remove gaseous impurities in feedstock production 110, raw material storage 320 and hydrolysis section process, for example ammonia, carbonic acid gas and sulfurous gas.Typically, hydrolysis section 330 generations come from the interior sulfur-bearing of various biomaterials and partly decompose the sulfurous gas that obtains.The main source of sulphur is a protein molecule, and numerous protein has the sulphur bridge between cysteine residues.Sulfurous gas is hydrogen sulfide (H typically ₂S) and mercaptan (alkyl sulfur compound), for example methyl mercaptan.In addition, can produce some salt, sulfurated lime (CaS) for example and separates these salt usually during the stage of back.

After hydrolysis section, typically flash distillation 340 comprises that the raw material that has reacted 122 of at least a liquid product that has reacted and at least a solid phase prod that has reacted and water arrives lower pressure, and allows the excessive heat of release to turn back in the hydrolysis section heating zone before.Typically, preferably in two or three stages, descend by pressure repeatedly and to realize flash distillation.The effect of flash distillation is emptying residual steam and the gas 132 relevant with the raw material that has reacted.By decompression dehydration is effectively, because driven away water under the situation of not using heat.Effectively utilize the further progress that excessive heat is called as heat recuperation and represents the inventive method.Hydrolysis section makes the fact of water (it can with vapor form emptying) and other gases 339 make recovered energy effectively together.Water and steam are effectively in heat exchange, and can use one or more condenser, direct in the hydrolysis section heating zone before again.Condenser is quite compact and helps efficient.Therefore, also preferably use the steam of discharging from the raw material 122 that has reacted and raw material that gas 132 boosting flow into and the temperature of keeping hydrolysis section, thereby reduce the power loss of the inventive method.Steam and gas 339 also can flow in one or more interchanger of placing before or after the raw material storage 320.In some cases, steam also can directly be annotated and get back in the raw material 100 that enters.Preferably, in conjunction with from the steam of hydrolysis section 330 and gas 339 with in flowing to interchanger 114 before steam and gas 132.

In interchanger 114, steam and gas are separated from one another.Most of vapor condensations obtain condensation product 151.Preferably, guide this condensation product again and combine, just as described further below with the later stage that comes from the inventive method " water that is produced ".Residual small amount of steam is with gas emptying 116.Preferably, the gas of these emptying combines with other gases that the later stage of the inventive method produces, and obtains fuel gas.

At raw material that flash distillation 340 has been reacted and after reclaiming heat, intermediate raw material 400 typically comprises at least a liquid product that has reacted, at least a solid phase prod that has reacted and water.At least a liquid product that has reacted typically is the organic liquor composition; At least a solid phase prod that has reacted typically comprises mineral.Intermediate raw material preferably is substantially free of gas products.

Fig. 4 shows the separation sequence that is applied on the intermediate raw material.Another advantage of the inventive method is that the intermediate raw material that will come from hydrolysis section places under one or more segregation section, removes mineral and water, afterwards processing in the reaction of oil arrangement section.Segregation section uses separating device, for example whizzer, cyclonic separator, distillation tower, filtration unit and sieve, and also can use distillation, from middle raw material 400, remove very fine carbon solid.Usually, further pressure drop will be reclaimed more steam, and promote solid/liquid separation to reclaim mineral and other solids.

The intermediate raw material 400 that typically comprises organic liquor, water and mineral preferably places first to separate 410 times, and described first separation 410 will be removed most of mineral 412 and be produced the mixture 414 of low organic liquor of ash content and water.This separation is characterized by solid/liquid separation, and can adopt first whizzer or by solid/liquid separation apparatus, for example machinery or non-mechanical method, and for example gravity settling is realized.Isolated mineral 412 are moistening typically, therefore place dryer section 420, are transported to the exsiccant mineral afterwards and store 430.Dryer section is typically carried out under condition of normal pressure.Gained exsiccant mineral can have sizable commercial applications as soil improvement agent or other industrial precursors.

Place second to separate 440 organic liquor/water mixture 414, to drive away water and to stay organic liquor 500.Can use the second liquid/liquid whizzer (or other tripping devices) to realize the second such separation.Gravitational difference allows water and the organic liquor that centrifugation produced.The water of being driven away that is produced 138 contains the dissolved organic molecule of significant quantity, for example glycerine and be derived from more proteolytic water-soluble amino acids.The water that is produced typically comprises chloride impurity.Before the reaction of oil arrangement section, isolate this impurity and represent the extra advantage of the present invention, because can therefore not pollute product subsequently.

The water 138 that is produced can for example concentrate 139 by evaporation, can and be transported to enriched material in the water condensate 151 of method internal recycle of the present invention and stores 460 enriched material 153 thereby produce.Typically realize evaporation by applying slight vacuum.Mainly comprise amino acid, glycerine and potential ammonium salt, for example the enriched material of the slurry of ammonium sulfate or ammonium phosphate typically has commercial value, for example the fertilizer of selling in shop, family garden that is called " extract ".

Be appreciated that the segregation section that the invention is not restricted to comprise two steps.The present invention also is not limited to carry out the order of any separating step.Therefore, consistent with the present invention is that the product that intermediate raw material 400 is separated into such as organic liquor, mineral and water carries out in one step or in greater than two steps.In addition, in some cases, mineral can remain in the organic raw material by design, therefore do not need to separate them in oil arrangement section first being processed.

When adopting embodiment of the present invention processing tire, a part of organic liquor can be used as the finished product, and described the finished product are the desulfurization tire raw materials that are used to make rubber product.

Fig. 5 shows the stage of the inventive method, and the organic liquor 500 that wherein comes from the segregation section of Fig. 4 places oil arrangement section 140 times, produces one or more useful products.Organic liquor 500 enters storage vessel usually, afterwards further processing.It will be understood by those skilled in the art that the products that obtain by oil arrangement section 140 really cutting cloth change with employed condition in the oil arrangement section, comprising the type of employed device.For example, in some oil arrangement section reactions, main product is hydrocarbon vapour and gas 148, exists seldom or does not have a carbon solid.

Can randomly guide a part or all organic liquor 500 for processing before oil arrangement section 140, obtain one or more speciality chemicals 143.According to this optional method, some required organic liquor parts 500 typically place separating technology, for example in the fractionation 510 or with compound reaction such as alcohol, form another compound, just as understood by those skilled in the art.This separating technology produces speciality chemical 143, and usually stays the fractionation mother liquor 145 that is called " heavy mother liquor ", and described fractionation mother liquor 145 comprises the organic molecule of higher molecular weight, for example triglyceride oil.Fractionation mother liquor 145 can direct in the oil arrangement section 140 for being worked in the organic liquor 500 with similar mode again.

Speciality chemical 143 typically is organic compound, for example the amino acid of lipid acid, fatty acid ester, fatty amide or a certain scope.Preferably, speciality chemical 143 is a lipid acid.More preferably, speciality chemical 143 is that scope is C _12-20Lipid acid.Even more preferably, speciality chemical 143 is that scope is C _16-20Lipid acid.When speciality chemical 143 was fatty amide and fatty acid ester, they were typically by forming with fatty acid response.The speciality chemical 143 that comes from raw material such as the turkey tankage can be used as lubricant and coating and paint.

In oil arrangement section 140, the water-content of organic liquor 500 is almost 0, and is main by adopting high temperature rather than by excessive water or steam or interpolation water or steam hydrolysis so that the condition of oil arrangement section makes, thereby decomposes residual organic molecule.The representative condition that carries out oil arrangement section is about 400 ℃.As obtainable in oil arrangement section reactor or other containers.Best temperature changes according to total reaction conditions.Oil arrangement section is about 120 minutes of the about 5-of cost typically, but precise time changes according to the type of employed reactor.In practice, each of mother liquor various time quantums of cost in oil arrangement section reactor.For example.Vapor phase is to the time of passing fast and the liquid cost is long.Comprise the mixture of hydrocarbon vapour and gas 148 independently from the ejecta of oil arrangement section, wherein non-hydrocarbon gas can comprise carbonic acid gas, CO and nitrogen and sulfocompound and carbon solid 142.Carbon solid 142 preferred class are similar to high-quality coke.The mixture 148 of hydrocarbon vapour and gas typically contains oil vapour.Preferred selection oil is put the condition of section in order, optimizes the purity of carbon solid 142, and the mixture 148 of hydrocarbon vapour and gas.After oil arrangement section, fast quench hot steam, for example mixture 148 termination reactions of hydrocarbon vapour and gas and minimize the formation coke.In preferred embodiments, can perhaps use hot-fluid and heat-eliminating medium,, realize the fast quench of steam by quench step repeatedly by steam being directed in the water-filled rotary drum.Use therein under the situation of this repeatedly quench step, advantageously from oil, obtain multistage cut (diesel oil, gasoline etc.), so that can shunt various cuts, to separate commercial applications.Perhaps, in another embodiment, can be in the presence of the organic liquor that enters, the quenching oil steam, thus also promote the recovery of energy.

Usually, be to carry out oil arrangement section under the about 310 ℃-Yue 510 ℃ temperature in scope, so that can realize in following two conversions at least one.The first, lipid acid resolves into hydrocarbon.This can be by realizing for remove decarboxylate under about 316-400 ℃ the temperature from each fatty acid separation in scope.The second, hydrocarbon molecule itself " cracking " forms the distribution of the molecule of lower molecular weight, and this process can be carried out in about 450-510 ℃ scope.Yet, typically, under the temperature more than 480 ℃, carry out the cracking of hydrocarbon.Preferably, under the temperature higher, carry out oil arrangement section than hydrolysis section.Be not appreciated that having significantly to break away under the situation of the principle of the invention, can change the temperature that may be used on the oil arrangement section described herein.For example, can be under about 300-525 ℃ the temperature in scope, and in 400-600 ℃ scope, carry out oil arrangement section.In some embodiments, the temperature of oil arrangement section reactor is about 400 ℃ to about 510 ℃.

In addition, at least one embodiment, oil arrangement section reactor slightly is pressurized to the pressure of about 15psig to about 70psig, and promptly the above about 15psi of normal atmosphere is to about 70psi more than the normal atmosphere.Preferably, the pressure in oil arrangement section reactor is lower than the hydrolysis section reactor.

Any carbon solid 142 that is generated by oil arrangement section typically at first is transported in the carbon solid cooling device 630, wherein allows its afterheat of carbon loss.After cooling, carbon solid 142 is transported to carbon and stores 540 places, and can sell and be used for many useful application.For example, sell carbon for using with " soil improvement agent " form in home gardening, this is because the many bacteriums in the soil need carbon source.Especially, the carbon that is produced has the quality that is similar to many forms " gac ", therefore also can be used as the material of the discharge of steam thing of absorption machine motor-car, perhaps uses in domestic filter.In addition, because its purity causes that carbon is the same with coal to can be used as solid fuel, but do not have following shortcoming: produce and come from burning toxic discharge of causing of the pollutent of discovery typically in product of coal.In addition, can for example come from the carbon solid of the inventive method by using carbonaceous additive, in and in the soil matrix many environment toxic substances.

Except or alternative carbon solid 142, the useful product that generates by the inventive method can be the coal of cleaning.When unprocessed raw material is unprocessed coal, generate the coal of cleaning.Find that with obtainable unprocessed coal facies ratio typically, the coal particulate that the inventive method produced does not advantageously have sulfur-bearing and chloride pollutent.These performances of the coal that generates by the inventive method make them especially attractive as the fuel source of clean burning.

Typically direct in the chiller/condenser 850 by the hydrocarbon vapour of oil arrangement section reactor generation and the mixture 148 of gas, become fuel gas 146 and hydrocarbon ils 144 at this separating mixture.Fuel gas 146 has caloric value and itself can be in inside be redistributed to method of the present invention, in order that heat energy was provided in each stage or can be used for generating or produce other forms of energy using for outside or inner.Oil 144 comprises that typically its carbochain has the hydrocarbon that is less than or equal to 20 carbon atoms.In this one side, this mixture is similar to oil fuel, for example the light component in the diesel engine oil of #2 grade.This product also can be sold commercial.Yet, be appreciated that the accurate composition of oil 144 depends on raw material, and the reaction conditions that also depends on oil arrangement section.Therefore oil can comprise paraffins, alpha-olefin and aromatic hydrocarbons, and saturated aliphatic hydrocarbon.For example, when raw material was made up of tire, the gained oil composition was different from the composition of gained when raw material is the turkey tankage.Find, come from oil and be rich in alkene and diolefine with the high raw material of lipid content.But do not expect, can from oil, remove this alkene by saturated or various separation methods again by those skilled in the art are afamiliar with.

When unprocessed raw material is tire, found with this area in other solvent phase ratios of using at present, the oil of the terminal stage that from hydrocarbon ils 144, obtains, tire deutero-hydrocarbon is the excellent solvent that is used for tire in the case.According to the General Principle of " similar mixing " in the chemistry, because the oil of terminal stage finally comes from tire, so its chemical property is similar to initial tire, so it is the good solvent of tire.When the unprocessed raw material that uses with the inventive method is tire, before slurry preparation or among, at least some tire deutero-hydrocarbon are directed in the undressed raw material of input again, with assist in dissolving it.Typically, the boiling range of tire deutero-hydrocarbon is about 100 ℃-Yue 350 ℃.In preferred embodiments, before being applied on the tire, heating tire deutero-hydrocarbon.In another embodiment, tire deutero-hydrocarbon is applied on the tire and heats this mixture to about 200 ℃ to 350 ℃ temperature.Use the oil production of terminal stage to save circulation (recurring) cost of other solvents and replenished (make-up) consumption.

In various embodiments of the present invention, use the composition of four corner of the oil of terminal stage, the perhaps only part in these compositions is with the dissolving tire.Preferably, all tire deutero-hydrocarbon is directed in the unprocessed raw material of input again.In another embodiment, the only heavy oil product of terminal stage guiding more in such a way.If use the composition of a part, then can or the course of processing of terminal stage or first section in solvent is divided into a plurality of parts.Use final oil production as solvent make method of the present invention than additive method economy many.Because first batch tire for processing in any given moment can not get this oil usually, therefore can use the initial decomposition of the auxiliary tire of another solvent in addition.This solvent is a toluene, and other are known to those skilled in the art.

When unprocessed raw material is city sewage and sludge, preferably promote separating of organism and inorganic substance.Therefore, in preferred embodiments, some hydrocarbon ils 144, biologically-derived in this case hydrocarbon is directed in the product of unprocessed raw material or hydrolysis section again, so that auxiliary this material that floats.In other embodiments, can use the material such as trap grease, they for example obtain from the snack food product outlet.The principle that material is floated is that the material lighter than water is incorporated in the unprocessed raw material, perhaps in the product of hydrolysis section, floats with the auxiliary organic substance heavier than water, thereby helps separation of organic substances and inorganic substance.The result is than being more prone to centrifugal mud in other cases.

The further advantage of the inventive method is that all products are DNA and do not contain pathogenic former.That is to say that they do not have the pathogenic former material that is derived from zooblast, bacterium, virus or Protein virus.This material is not intactly survived in the method for the invention.This is important result, does not have the danger of using any product of the inventive method in the agricultural application that this molecule may enter the danger in the food cycle again because have therein.

The liquid product that has reacted of the self-separation that is converted section, for example to become the device of hydrocarbon and carbon solid mixture be a suitable oil arrangement section reactor that uses with the inventive method to organic liquor.As shown in Figure 6, preferred oil arrangement section reactor 600 according to an embodiment of the invention comprises well heater 610 heating organic liquor, thereby produces the mixture of the gentle carburetion of liquid; Reactor 620, the mixture of the gentle carburetion of invert liquid become the mixture 148 of carbon solid 142 and hydrocarbon vapour and gas; First water cooler 630 is accepted carbon solid 142; With second water cooler 640, accept hydrocarbon vapour and gas.Oil arrangement section reactor 600 can comprise in addition and communicating with reactor 620 for separate hydrocarbons steam and the gas 148 fluid-solid separator 624 with carbon solid 142.

Well heater 610 is preferred efficient and compact, comprises a large amount of internal pipelines, and described internal pipeline produces big heat interchanging area.Well heater 610 typically is " fired heater ".The outlet of organic liquor/vapour mixture that well heater 610 typically has the inlet of organic liquor accepted and steam 602 and a guiding heating in the reactor 620.Content when the steam 602 of about 2-5wt% is in entering well heater 610 and organic liquor accompany.The auxiliary even heating of the steam of this consumption also prevents that residue is accumulated in the well heater inboard.In preferred embodiments, use one or more preheaters heating organic liquor 500, mix it and steam afterwards and/or shift it in well heater 610.By giving oil arrangement section pressure in the pump housing system that stores after 500.

Reactor 620 preferably includes the spiral propeller of at least one heating, and have respectively acceptance from the mixture of the mixture of the heating of the gentle carburetion of liquid of well heater 610 and guiding carbon solid and hydrocarbon and gas in the fluid-solid separator and the entrance and exit of constructing.The mixture of the heating of the gentle carburetion of liquid and steam flow in the reactor 620, and it resolves into the carbon solid and preferably contains the mixture of the oil and the appropriate hydrocarbon gas of fuel gas composition at this.Typically, carbon solid generation is about 10wt% of the gentle carburetion mixture weight of liquid.In other embodiments, depend on the composition of unprocessed raw material, the carbon solid that is produced is about 5% to about 20% of the gentle carburetion mixture weight of liquid.In some embodiments of the present invention, in reactor 620, accumulate, regulate the material quantity of being processed for fear of excessive carbon solid.

Spiral propeller is suitable for producing the mixture of carbon solid and various hydrocarbon, and this is because its allows the residence time and the temperature of the organic liquor that control enters, with because its allows carbon solid effectively to separate with volatile products.Preferably, select the size of spiral propeller, so that optimize gained hydrocarbon mixture and carbon solid purity.For example, the diameter of section major decision of spiral propeller vapour stream cross wherein speed.Preferably, flow velocity is not so high as to ash content and is carried with steam, produces impure hydrocarbon mixture.The residence time of the mixture of the heating of organic liquor, steam and water vapour, when reaction, also determined the size of spiral propeller.Preferably, oil arrangement section reactor can be processed at least 1000 tons of organic liquor/skies.

Preferably, oil arrangement section reactor 600 comprises the fluid-solid separator that communicates with the outlet of reactor 620.The fluid-solid separator preferably has first outlet and second outlet of carbon solid of hydrocarbon and gas.Preferably guide back well heater 610 and burning again from some fuel gas of hydrocarbon and gaseous mixture,, thereby help the overall efficiency of the inventive method with the auxiliary temperature of keeping in the well heater.

Temperature usually is guided first water cooler, is in the carbon solid cooling device 630 up to about 500 ℃ carbon solid, the refrigerative spiral propeller that described carbon solid cooling device 630 preferably is communicated with by air lock arrangement and reactor or optional fluid-solid separator.In some embodiments of the present invention, can use more than a cooling spiral thruster 630.The preferred water of introducing is in carbon solid cooling device 630, with auxiliary process of cooling.With the carbon solid optional by other e Foerderanlage of conveyor screw or some, for example chapelet 654 is transferred in the final product stock system 650, perhaps transfers in another well heater/reactor, with the activated carbon solid.

Second water cooler 640 that receives the mixture of hydrocarbon vapour and gas preferably includes the carbon granules separator in order to isolate any residual carbon solid and it is turned back in the reactor 620.

Preferred oil arrangement section reactor among Fig. 6 is favourable, because spiral propeller allows the organic liquor of heating to carry out the hydrocarbon thermally splitting continuously and do not have the carbon solid additional accumulation relevant with cracking usually.Known other devices of those skilled in the art, " delay coking device " that for example uses in factory of petrochemical refining realized the thermally splitting of hydrocarbon and realize cracking under than the sweeping condition of the reactor of Fig. 6, but follow cracking carbon solid to be accumulated on the reactor wall inboard.Need periodically remove this accumulation, thereby require or significantly big stoppage time or even replacing reactor vessel.However, can think that this device realizes that oil arrangement section of the present invention reaction is feasible, this depends on and accounts for leading economic situation.Delay coking device produces and different distributions from the product of Fig. 6 reactor.For example, delay coking device makes the fatty acid molecule decarboxylation at first, obtains hydrocarbon, and the further then described hydrocarbon of cracking obtains short hydrocarbon.

Except the delayed coking apparatus, also can adopt other devices of fit for service, realize oil arrangement section of the present invention reaction.Can be at Chemistry of Petrochemical Processes, the 2nd edition, S.Matar and L.F.Hatch (Gulf Professional Publishing, 2001) especially find the example and the method for suitable device in the 3rd chapter.Suitable method typically is two classes, the hot method that for example adopts hydrotreater to realize, the catalysis method that perhaps for example adopts the fluid catalytic cracking device to realize.

The thermal transition method typically comprises pyrogenic process, viscosity breaking and steam cracking.Pyrogenic process typically is applied to heavy ends, for example has those of high asphalt content.Pyrogenic process produces appropriate hydrocarbon gas, mainly is the appropriate hydrocarbon gas of high degree of unsaturation character, pressure naphtha, intermediate distillate and coke.Typically gas and liquid ingredient are carried out hydrotreatment, make the saturated and desulfurization of various products.The homolysis that the primitive reaction of excessive thermally splitting is based on carbon-carbon bond produces paired alkyl diradical.Each alkyl diradical tends to or further cracking, thereby obtains alkene, perhaps captures hydrogen atom from another hydrocarbon, thereby produces another alkyl diradical.The reaction product general inclination is not in being branched hydrocarbon, and this mainly is because alkyl itself does not have isomerization.

There are two main class cracking technologies: delayed coking and fluid coking.In delayed coking, reactor system has the well heater of the short contacting time that communicates with big rotary drum, and described rotary drum soaks multiple batches of preheating material.From the steam diversion at rotary drum top in the fractionator for being separated into gas, petroleum naphtha, kerosene and gas oil.Operational condition typically is at 480-500 ℃ of following 25-30psi.Can for example operate the improved productive rate that obtains product liquid under the 15psi by at lower pressure.Hot conditions produces more coke and gas, but less liquid product.Although the quality of coke is finally decided by the quality of raw material, also can be owing to drum size, rate of heating, soak time, pressure and final temperature of reaction change.When rotary drum is filled coke, shunt a collection of former second rotary drum of expecting, so that can turn first rotary drum or make it " decoking ".Typically, can adopt hydrojet nozzle, the water of guiding 3000psi pressure is at least realized the rotary drum decoking in coke.Those skilled in the art can implement the delayed coking apparatus for carrying out oil arrangement section of the present invention reaction.

In fluid coking, use the coke supply cracking reaction fuel that is produced.By in fluidized-bed reactor, on the coke granule that forms in advance, spray hot charge, produce the fluid coke.Temperature of reactor typically is 520 ℃.The main drawback of this method is that it does not reduce the sulphur content in the coke.The fluid coking work-around solution that preferably is called " flexicoking " is because it uses coke gasification and combined stream coking.The two is in one skilled in the relevant art's the ability for carrying out oil arrangement section of the present invention reaction to implement fluid coking and flexicoker.

Viscosity breaking is to be applied to the highly viscous raw material of thermally splitting, for example contains those of waxy substance, forms not the gentle method of heavy-gravity product mixture so.Typically, 450 ℃ temperature and short heat-up time used in viscosity breaking.From under the organic liquor of segregation section especially those situations of heavy-gravity, it usefully is used for the present invention therein.

The catalysis process of the mixture of convert hydrocarbons comprises the many diverse ways that those skilled in the art are afamiliar with.Example comprises catalytic reforming (particularly being applied on the petroleum naphtha), catalytic cracking, hydrocracking, hydrodealkylation, isomerization, alkanisation and polymerization.Some hydroprocessing processs of herein also mentioning use one or more catalyzer.Those of ordinary skill in the art can use each in these catalysis process and install, and realizes oil arrangement section of the present invention reaction.

Catalytic reforming is particularly suitable for carrying out oil arrangement section of the present invention reaction.Catalytic cracking makes the raw material cracking of lesser value produce lightweight and the medium distillate and the light hydrocarbon gas of higher-value.Employed typical catalyst is synthetic soft silica-aluminum oxide in catalytic cracking, has or do not exist zeolite.Because these catalyzer promote isomerization reaction to form carbon ion in reaction process, and because carbon ion tends to quick spontaneous rearrangement, but the life-span is longer, with therefore its reaction preference is bigger, therefore compare with the product that thermally splitting obtains, this products distribution tends to have more branched-chain hydrocarbon and unsaturated product still less.This is favourable, because the side chain product tends to improve the octane value of the hydrocarbon mixture that is produced and because saturated product tends to more stable than its undersaturated counterpart.

Fluidized-bed is typically used in catalytic cracking, perhaps so uncommon moving-bed.In fluidized-bed process, the raw material of preheating follows hot regenerated catalyst to enter reactor.Catalyzer is as highly porous powder.It is about 10-20psig that condition in the reactor typically is 450-520 ℃ and pressure.The fluid catalytic cracking device typically produces lightweight (C ₃-C ₅) unsaturated hydrocarbons, have high-octane gasoline, gas oil and tar.Recently improve gas and gasoline yield by what adopt higher temperature, long residence time and higher catalyst/oil.Also consistent with the present invention is to adopt " degree of depth catalysis fluidisation " to realize oil arrangement section.This method is favourable, because it produces the lightweight unsaturated hydrocarbons of high yield.

In moving bed process, catalyzer is by the hot bead form of gravity in raw material enters catalyst regeneration zones.This method produces saturated and unsaturated light hydrocarbon gas and is rich in the mixture of the gasoline products of aromatic hydrocarbons and side chain paraffins.

In addition, oil arrangement section of the present invention reaction can be used hydrocracking process, and this technology is the catalytic cracking in the presence of hydrogen basically.This technology mainly obtains the stable hydrocarbon product.

At " Liquid hydrocarbon fuels from biomass (from the liquid hydrocarbon fuel of biological substance) ", D.C.Elliott and G.F.Schiefelbein, Amer.Chem.Div.Fuel.Chem.Preprints, 34, the additive method of realizing oil arrangement section of the present invention reaction is disclosed among the 11160-1166 (1989).

The modification variant injection water steam that can use the inventive method is light oil at ground place's refining settling then, thereby makes this abundant inaccessible resource to obtain far away in subterranean burnt sand settling.Experiment shows that also method of the present invention can extract sulphur, mercury, petroleum naphtha and alkene from coal, and all these are vendible commodity, thereby makes the more red-hot and cleaning of burning of coal.Make also that by method pre-treatment of the present invention some coals are more crisp, the result needed less energy to pulverize them before the power station internal combustion.

For some raw material, method use separate out suspended fine-particle solid of the present invention and fluidic device are as the part of feedstock production section.In addition, many other industry and commercial applications require solid with the isolating suspension of liquid phase.Fig. 7 shows the tripping device 700 according to the preferred embodiment of the invention, and it can be used for this separation.Requiring another example of the application of separate solid suspension is separate red hemocyte and white cell from whole blood.When the size of the solid particulate that suspends was big, when perhaps its density significantly was different from fluid, existence can separate their many dissimilar device.For example, under stress, there not being the significantly solid material of distortion, can use to have the strainer of opening less than many different structures of suspended solids.When there are significantly big density difference in solid particulate and fluid, can use settler, sedimentation chamber and simple cyclonic separator effectively.When size or density difference hour, it can be effective using the active device of centrifugal force.Yet for having density only somewhat different than the very little granularity of the deformable material of suspension, the efficient of all these tripping devices sharply descends.

About the preferred method of the present invention, wherein little, the deformable of suspended solids size and a kind of application with little density difference are city sewage and sludge (MSS).The material of the suspension in MSS is mainly by from bacterium with size typically is about 1 micron cellular material and the abscess chip is formed.This material deformable and having at water in suspension Media density 10% with interior effective density.In the raw material of preparation MSS as the inventive method, separating this solid material and water is preferred step.Can realize this separation by using whizzer, yet in preferred embodiments, use tripping device 700.

According to the preferred embodiments of the invention, the solid and the liquid ingredient that preferably use tripping device shown in Figure 7 700 to separate in the unprocessed raw material, for example MSS further processes by method of the present invention afterwards.This device also may be used on wherein solid particulate deformable or its effective density liquid phase 10% with interior other industry or commercial wastewater sludge on.

Device 700 preferably includes shell 702, and described shell 702 contains the rotary components 704 that is installed in the internal chamber 706 with frusto-conical.The shape of internal chamber 706 typically comprises frustum of a cone cross section with cone angle and in the bottom of the rescinded angle cone of the miscellaneous part that holds rotary components 704 and/or the extra cross section at place, top.Shell 702 preferably include communicate with each other and the turner shell of airtight rotary components 704 at the bottom of (spinner case bottom) 714 and turner shell top (spinner casetop) 716.Tripping device 700 further comprises inlet 710 and first outlet, 730 and second outlet 750 that is communicated with internal chamber.Inlet 710 allows to introduce the hydrocarbon that contains suspended solids and arrives in the static inwall 720 and the annular space 712 between the rotary components of internal chamber.

Rotary components comprises the right cylinder of the frusto-conical with hollow inside, and described right cylinder is preferably made by the turner bottom 722 that communicates with tapered cylinder body wall 724, and described tapered cylinder body wall 724 itself communicates with turner top 718.During rotary components is installed in one heart on the major axis 736 of bare spindle 726, described major axis is typically about 50 for about 1000r.p.m.-in scope, rotates under the speed of 000r.p.m..In separating the preferred embodiment of MSS, speed of rotation is about 10,000r.p.m..Preferred selection speed of rotation is so that minimize unordered flowing.Rotary components reduces gradually, so that along with narrowed width, effectively section area descends.Typically cone angle is about 1 ° to about 10 °.In preferred embodiments, cone angle is about 2 ° to about 2.5 ° and even more preferably from about 2.25 °.The hollow of rotary components is inner to be communicated with second outlet 750.

Preferably, between the inlet 710 of separator 700 and inside, there is pressure reduction.Typically, this pressure reduction is controlled for about 3-150p.s.i. and by two pumps (not shown among Fig. 7).

The flow velocity of the separator of different size and the surface-area of rotating cylindrical body change in proportion.Preferably, structure inlet and circular clearance provide about 1 flow velocity to about 200 gallon per minute.More preferably flow velocity is about 1 to about 20 gallon per minute, even more preferably in order to handle MSS, flow velocity is about 10 gallon per minute.

Give wall 724 perforation of rotary components.Hole dimension in the wall 724 typically is about 1 to about 200 microns.Preferably, hole dimension is about 50 microns.Wall 724 is preferably by plastic material, and for example HDPE or nonhygroscopic any other material are made, to avoid in operating process mesoporosity closure.

The material of fluid and suspension flows on usually axially along circular channel 712, and the flow through rotation wall 724 of perforation of a part of fluid enters in the cylindrical hollow inside 728 simultaneously.Hollow inner 728 is communicated with through spindle inlet 732 with the spindle 724 of hollow.Most of particles suspended prevent that fluid from flowing through the right cylinder of perforation, and this is because due to the shearing and centrifugal force of the surface of rotating cylindrical body.Therefore cylindrical speed of rotation is set in shearing and the centrifugal force on the suspended particle effectively, can use it to control and can prevent the fluid hole circle cylinder mobile particulate minimum size that wears long.Flow into the water of right cylinder 728 inside and particle flow through subsequently spindle inlet 732 enter in the center of bare spindle 726, and flow to spindle outlet 734, afterwards by second outlet, 750 dischargings.

As replying that rotating cylindrical body moves, the material in the circular channel 712 is followed helical flow path closely.Preferably, the thickness of circular channel 712 is constant along its length direction.Use for some, this annular space can change from the top to the bottom.Variation in the annular space can influence the flow condition of perforation turner near surface.At circular channel end, provide first outlet 730, the existing spissated fluid stream of discharging away from inlet.

The operation of the device of Fig. 7 does not preferably rely on orientation.In preferred embodiments, the cylinder axis of awl change is vertical orientated in the bottom and first outlet 730.

Compare with known other tripping devices of prior art, the advantage of the device of Fig. 7 is, it can process the mud with broad range particle characteristic, wherein especially comprise have size range be lower than 1 micron those or density of deformable suspended particle at suspension 10% with interior those.In preferred embodiments, be configured in circular clearance and hole dimension in the wall 724, separate the suspension of city sewage and sludge.In some embodiments of the inventive method, use many these separators abreast, realize that the high throughput of undressed raw material separates.

Be appreciated that separator shown in Figure 7 700 does not accurately draw in proportion, but various element is approximated to ratio each other.Therefore, can be according to the known general principle structure of the those of ordinary skill of mechanical engineering and design field separator 700.

In preferred embodiments, the external diameter of turner bottom 722 is about 2.2`` for the external diameter at about 2`` and turner top 718.714 preferred length is that about 7`` is to about 8`` at the bottom of the turner shell.The preferred length of rotation wall 724 for about 4`` to about 6`` and its preferred thickness preferably along its consistent length and be about 1.5``.The preferred diameter of the outlet of relevant with this turner (conjunction) is that the external diameter at the bottom of about 0.8`` and the turner shell is preferably about 3``.The external diameter on turner shell top then is preferably about 4``.Spindle 726 is that internal diameter hollow and preferred is about 0.25``.The external diameter of spindle 726 can and can be about 0.5`` to about 0.75`` along its length direction variation.In this embodiment, the distance between spindle inlet 732 and the spindle outlet 734 can be about 6``.The thickness of circular channel 712 is preferably about 0.50 inch of about 0.05-.

The preferred size of herein listing only is one and exemplifies and according to design alternative and required circulation, is familiar with each size of component that the mechanical engineer of this area can amplify or dwindle separator 700 in proportion, so that realize operation efficiency.

Preferably, realize carrying out the whole device of the inventive method by comprising the computer-controlled system of simple valve positioner, pump and temperature.Develop this system in the skill of the those of ordinary skill in computer art control engineering field.

Device of the present invention can optionally amplify in proportion.For example can predict, handle the factory in thousands of tons of refuse/sky, also can build simultaneously can be in transportation of flat bed truck back and the midget plant that can only handle one ton of refuse/sky.

Provide following examples to set forth method of the present invention and material, but the not invention of requirement for restriction protection.

Embodiment

Embodiment 1: pilot plant-shredder residues processing

Use apparatus and method of the present invention to build testing installation.

According to an exemplary application of pilot plant, experimental raw is a shredder residues.In the SR material of the 3000lbs that this pilot scale round is received, remove 1072lbs foul/particulate and use hot wash, process the SR that 715.5lbs does not contain particulate, and reservation 1212.5lbs does not contain the SR of particulate for test in the future by the depolymerization unit.Do not contain the SR of particulate and tire and the about 1741lbs exhausted machine oil that 79.5lbs pulverizes by the processing of depolymerization unit.The sample that transfers out various products is measured heavy metal and pollutent, for example net result of PCB and chlorine for analysis.

Based on the result that comparative sample is analyzed, find order of magnitude of PCB decline, drop to less than 2ppm from 35-65ppm.

Carry out the thermally splitting of this hydrolysing oil in laboratory-scale reactors, the typical refinery technology of transport fuel is made in simulation.The hydrolysing oil of producing by the inventive method cracking under near 500 ℃ temperature is similar to the temperature of using in the delay coking device in refinery.The product that is produced is hydrocarbon fuel, fuel gas and solid carbon product.Fuel/air/carbon fraction is respectively 84%, 10% and 6%.This cracking produces the hydrocarbon ils of gasoline, diesel oil and residual weight.Be distributed as gasoline (12%), kerosene (38%), diesel oil (32%), heavy oil (15%) and gas (3%) from the cracked product.

From the SR material of initial 3000lbs., take out sample for initial test.In order to improve the material processing of SR, by all the other SR of bolting of 1/16``, remove foul and particulate then.The SR material contains foul and the particulate of the 1072lbs. that has an appointment, this account for whole samples about 36% and according to 1.5 times of amounts of initial sample analysis expection.

Foul and the particulate of removing by screening with hot wash also carried and analyzed for PCB.The residual material that does not contain particulate of a part passes through the depolymerization unit processing of pilot scale.Another part stores for test in the future.Amount is put in the depolymerization unit for the SR material that does not contain particulate of 715.5lbs..

Depolymerization

The depolymerization test is made up of the SR that 715.5lbs. does not contain particulate with raw material, and the described SR that does not contain particulate processes altogether with the damaged tire of 79.5lbs. and the low value oil of 1741lbs..Use is by being processed into gel and heavy oil/solid matrix in the temperature of maximum 340 ℃ (650) and the depolymerization unit formed of 75 gallons container operating down of the pressure of 100psig at most.For the restriction of the service temperature of the maximum operating temp that offsets 300 ℃ (572) that employed particular device structure in pilot plant test is reached and deep fat system, the residence time that increases each round is in 8 hours skies.Under comparatively high temps, depolymerization process is typically carried out less than 1 hour.

Use diesel-fuel conduct solvent easily, wash heavy oil/solid matrix, thereby obtain the extracted gel and the unconverted solid matter of 55: 45 ratio.In conjunction with this extractible gel and the gel from the depolymerization unit, removed easily, and as the raw material of hydrolysing step.SR-tire-oily raw material of processing 2536lbs. changes into low-ash gel with 1925lbs in the depolymerization unit.Those of ordinary skill in the art will recognize that the gel content that is generated by described method changes according to many factors, for example duration of test runs and in unprocessed raw material the content etc. of inorganics.There are the overhead vapours of about 113lbs and the solid that can not transform of about 343lbs.

As previously mentioned, the low value oil of 1741lbs. also cycles through the SR/ tire raw material that enters in the depolymerization unit, so that significantly increase the heat transfer rate that arrives the SR/ tire and accelerate heat-processed.Although use useless machine oil in this embodiment, any oil that steam forces down can be used for same purpose comprising the turning oil that is generated by the inventive method.For organism fraction in the further raising raw material and final oily productive rate, damaged tire is joined in the SR sample, so that its organic content height.

Last in depolymerization process, flash distillation from this unitary water and gas to normal atmosphere.Cool off this unit to 200, the SR that shifts depolymerization afterwards is in storage tank.After expel liquid, remove the solid metal and the inorganics that are retained in the depolymerization unit.

Hydrolysis

Use portable jar and low mobile high temperature positive-displacement pump, the SR of depolymerization is fed in two hydrolysis reactors.Pressure by existing pilot plant reduces control valve, connects this reactor and receiving tank.From the water vapor condensation of hydrolysis reactor and be transported in the drainer.The hydrolysis round is processed a part of depolymerized product.The depolymerization SR/ tire/oil of about 800lbs and the used oil of 800lbs increase the mobility of cold depolymerized product, and by the water of hydrolysing step with the speed processing 900lbs of 3lb/min.It is under the temperature in about 440-Yue 500 scopes that mixture is placed scope.After hydrolysis, flash distillation from shredder residues oil and be stored in the flash tank.The hydrolysis post-treatment comprises solid/liquid separation, and to remove residual solid objects, for example wood shavings and liquid/liquid segregation are removed from water and deoiled.Separate the use whizzer for these.

Illustrated in the following table in hydrolysis and from SR/ tire raw material, almost completely removed muriate, bromide and PCB.This shows the oil that produced and is substantially free of non-required PCB, muriate or other halogenide from any refined product of this oil.

Heavy metal	The SR raw material	Separate coagel	Hydrolysing oil *
				The plumbous mercury nickel of arsenic (total) barium cadmium (total) chromium-copper iron selenium silver zinc	13 370 13 94 4167 - 740 1.23 - ND ND 5233	ND 58 5.5 4.5 58 1000 58 0.21 ND ND ND 850	ND/ND 13/4.7 2.7/ND ND/6.1 36/36 560/1200 13/29 0.16/ND ND/ND ND/ND ND/ND 870/760

Separate

For the separating step after the hydrolysis, use decanting vessel and liquid-liquid centrifuge.

Thermally splitting

In laboratory-scale reactors, under the temperature near 500 ℃ (932), the about 10 liters of hydrolysing oils from SR of thermally splitting in 6 rounds produce hydrocarbon ils, fuel gas and solid carbon product.Figure 12 shows the unitary picture of laboratory scale thermally splitting.Emptying gas and oil vapour in reaction process are so that keep goal pressure.Stop test when stopping the emptying of gas, this proves by the constant gaseous tension.Come the distribution of the oil/gas/carbon fraction of autothermic cracking device to be respectively 84%, 10% and 6%.The distillation of TCP cracked oil obtains that 12% lightweight distillates fuel, 38% medium distillate, 32% diesel oil and 15% heavy fuel oil (HFO) and 3% be as the raw material of condensable gases not.

Distillation fraction	Industrial use	Temperature range
			The lightweight distillate	Gasoline, motor spirit	122-302°F
Medium distillate	Kerosene, jet fuel	302-482°F
			Diesel oil	Diesel-fuel; Heated oil	482-644°F
Heavy fuel oil (HFO)	Industrial fuel	644-676°F

The TCP liquid fuel

The chemistry and the physical features of TCP hydrolysing oil have been listed in the following table 1.TCP cracked oil product is the reproducible diesel oil that is similar to conventional diesel-fuel.This reproducible diesel oil can be used for various purposes, for example as the direct substitute of diesel-fuel or as the blend components of diesel-fuel.The TCP cracked oil can further be distilled into gasoline and other cuts.The chemistry and the physical features of TCP cracked oil have been listed in the table 2.

Table 1-is from the TCP hydrolysing oil feature of SR raw material

Table 2-is from the TCP renewable diesel feature of SR raw material

Embodiment 2: testing installation-turkey processing

Use apparatus and method of the present invention to build pilot plant.Pilot plant can be handled 7 tons of refuse/skies.

According to a kind of exemplary application of pilot plant, experimental raw is a turkey processing space refuse: feather, bone, skin, blood, fat, internal organ.This quantity of material of 10,044 pounds is put into the hydrolysis section of device: 350 horsepowers pulverizer, pulverizer are the slurry of taupe brown with this material transition.Material flow in a series of jar and pipeline of heating and reformate mixture thus.

After 2 hours, produce the light brown logistics of the thin oil (fine oil) of steam treatment.The oil of producing by this method is very light.The longest carbochain is C ₂₀The oils that is produced is similar to the mixture of half oil fuel, half gasoline.

For the complicated raw material such as the turkey tankage, prove the Energy Efficient of method 85% of the present invention.This means for every 100B.t.u. (Btu) in the raw material that enters in the workshop, only use 15B.t.u this method that turns round.For the material of relatively dry, carbon-heavy or moisture-light-weight rough stock for example, plastics for example, efficient even better.

The hydrolysis section reactor comprises installs also about 20 feet high, 3 feet wide jars of electricity consumption heater coil parcel securely.In the hydrolysis section reactor, by heat and pressure hydrolysis material.The two does not produce very extreme or intensive energy temperature and pressure, and this is because water assists the transmission heat in raw material.Mostly just spend about 15 minutes and in pilot plant, carry out this technology.

At the heating organic materials and after reactor vessel is divided depolymerization, begin second section.In this stage, reduce slurry to lower pressure.Decompress(ion) will discharge the slurry free-water of half approximately immediately fast.More effective out and away by decompression dehydration than the heating and the water that seethes with excitement, especially because there is not wasted heat.The water that " flash distillation " fallen is transported in the pipeline, and described pipeline is guided back this method section of beginning, the process-stream that enters with heating.

In second section, the mineral sedimentation, and by-pass flow is in storage tank.In the turkey refuse, these mineral great majority are from bone.Mineral are as the exsiccant brown ceramic powder form output of being rich in calcium and phosphorus.It can be used as fertilizer, because its microcosmic nutrition (micro-nutrient) is well balanced.Especially, it has microcosmic-and macroscopical nutraceutical useful range.These mineral contain the health plant growth and form the element of desired appropriate amount, for example calcium and phosphorus.

In pilot plant, all the other spissated organism flow in the oil arrangement section reactor and carry out the processing of oil arrangement section, and are just as described above.The gas that comes from this processing uses in the workshop on the spot, to heat method of the present invention.Oil and carbon flow in the storage tank as the product of useful higher-value.

Depend on raw material and first and process period of oil arrangement section, method of the present invention can be manufactured on other speciality chemicals that extract in the each several part of this technology.The turkey tankage for example can be made lipid acid for using in soap, tire, paint and lubricant.

Embodiment 3: operating gear

Adopt the extra equipment in the exploitation, construct full-scale commercial-scale erecting device.Under peaking capacity, design this device and obtain surpassing 500 barrels of oil/skies, some in them can turn back in this system, produce heat to supply with maximum system energy.The oil that is produced is the oil of high quality with #2 heated oil same levels.This device produces about 21,000 gallons water, and described water clean enough so that be discharged in the municipal effluent system, and does not also contain the former vehicle of causing a disease.This device is also made about 25 tons of mineral, enriched material and carbon.

Embodiment 4: waste materials exemplify conversion

Table 1 shows each the following waste materials for 100lbs, when using method of the present invention that they are changed into useful materials, and final product and ratio thereof.

Municipal effluent refuse (comprise 75% sewage sludge and 25% grease catch refuse); Tire; Poultry processing refuse (comprising organ, bone, blood, feather and fat); Plastic Bottle (comprising the blend of making the employed polyethylene terephthalate of soda bottle (PET) and making the employed high density polyethylene(HDPE) of milk jug (HDPE)); Paper; Clinical waste (mainly come from hospital and comprise plastic injector, infusion bag, gauze, paper wrapper and wet refuse); And heavy oil (for example vacuum residue of refinery and Tar sands).The content of table 1 is unit with the pound.

Table 1

Raw material	Oil	Gas	Solid and enriched material	Water
					City sewage and sludge tire poultry processing refuse Plastic Bottle paper **Clinical waste heavy oil	26 44 39 70 8 65 74	9 10 6 16 48 10 17	8 (carbon and mineral solids) *42 (carbon and metal solids) 5 (carbon and mineral solids), 6 (carbon solids) 24 (carbon solid), 5 (carbon and metal solids) 9 (carbon solid)	57 4 50 8 20 20 -

^*For paper, this chart is based on pure cellulose; Estimate the certain paper raw material, for example the productive rate of newsprinting paper or wastepaper these charts 10% in.

^*Solid product from city sewage and sludge also can contain heavy metal.

It should be noted that the productive rate of ox and pork processing refuse is similar to the productive rate of poultry processing refuse.

Embodiment 5: remove pollutent from coal particulate and high sulphur coal

Hanging down the analysis of detection mercury on the unprocessed particulate high sulphur coal and on each product of application the inventive method.Under each situation, limit of detection is 0.01ppm.According to the undressed raw material of coal particulate, the content of mercury is 0.12ppm, does not have detectable mercury on finished carbon.

According to the unprocessed raw material of high sulphur coal, the content of mercury is 0.02ppm; On finished carbon, there is not detectable mercury.

Embodiment 6: remove amounts of sulphur contaminants from the coal particulate

Unprocessed particulate contains 1.71% sulphur.Composite carbon contains 1.58% sulphur, descends 7.6% with respect to unprocessed particulate.Contain 1.51% sulphur by the carbon of using the inventive method production, descend 11.6% with respect to unprocessed raw material.

Embodiment 7: remove amounts of sulphur contaminants from high sulphur coal

Unprocessed high sulphur coal contains the sulphur of 2.34wt%.After using method of the present invention, the gained solid phase prod contains the sulphur of 2.11wt%.

Embodiment 8: remove pollutent from low sulphur coal

Unprocessed coal contains 1.08% sulphur; The carbon that obtains according to the inventive method contains 0.49% sulphur, descends 54.6%.In the water of producing, also detect the very sulphur of lower concentration (45ppm).

In the Another Application of the inventive method that is applied to same sample, carbon contains 0.57% sulphur, descends 47.2%.Contain the sulphur of 0.9wt% from the gas (gas that from this technology, discharges) that this application produced, thereby show that sulphur is driven away, finally mainly in gas products.

Importantly when initial sulphur content is very low, can remove the sulfurous pollutants of half approximately.

Method of the present invention is also removed mercury effectively.When detection level may reach about 10ppb, mercury was not present in the carbon of the inventive method production basically.Detect the mercury of 30ppb (0.028ppm) in the water of being produced, thereby show removed mercury from coal, it is transferred in the water.When mercury was in water, it was easy to safe handling.Hydrocarbon in the water stripping, and by using the vacuum distilling unit to concentrate.The spissated water of gained mercury carries out silicate distillation and the insoluble silicate crystal containerzation of gained height and is stored in the harmful waste place that stores the noxious metals regulation.

Embodiment 9: hydrolysing oil

Can use method of the present invention, produce the different oil of forming by the organic substance of broad range.Use tankage as raw material, the fuel that production exemplifies is also shunted from method of the present invention after hydrolysis section.Coming from the particulate emissions of using this fuel can ignore basically.This fuel provides the regenerated fuel of the 40+American Petroleum Institute (API) (American Petroleum Institute (API)) of refinery or blend person's close limit, and described regenerated fuel can or be used as alternative fuel, perhaps is used as the blend components of ignitable fuel.The outstanding performance of this fuel has been shown in the table 2.The test method of regulation is represented with ASTM (ASTM (American society for testing materials)) coding in this table.

Table 2

Embodiment 10: the fuel that is derived from liquid mixture

As previously mentioned, the liquid mixture of producing by this method can directly use or be used as food, fertilizer, fuel or other products with conc forms.The performance of two kinds of liquid mixture deutero-fuel that exemplify of the present invention has been shown in the following table 3, and wherein test method is with ASTM coding (for the standard with prefix " D " expression) or AOAC coded representation.Produce each fuel by the undressed material sample that contains the byproduct in animal muck, mud and food mfg and the distribution.

Table 3

Performance	Test method	Liquid mixture deutero-fuel No.1	Liquid mixture deutero-fuel No.2	Liquid mixture deutero-fuel No.3
					Ash oontent	AOAC923.03(Agri )	2.27％	2.32％	2.50％
Phosphorus content	AOAC958.01	＜0.02wt％	＜0.02wt％	N/A
					Sulphur content	D1552 (CBNO) sulphur	0.25wt％	0.30wt％	0.30wt％
BTU/LB	D240(CBNO)-LB	N/A high humidity sample	N/A high humidity sample	N/A high humidity sample
					Carbon	D5291(CBNO)	21.84wt％	28.64wt％	25.00wt％
Hydrogen	D5291(CBNO)	9.66wt％	10.01wt％	10.00wt％
					Nitrogen	D5291(CBNO)	2.35wt％	1.79wt％	2.20wt％
Oxygen	D5291-oxygen	59.59wt％	51.70wt％	60.00wt％
					Moisture		62.4wt％	67.6wt％	65.0％
Volatile matter		Be included in the moisture	Be included in the moisture

Embodiment 11: the embodiment of oil arrangement section reactor and chiller/condenser

Fig. 8 A and 8B show the schematic embodiment of the device that uses the inventive method.Fig. 6 also shows some important documents of preferred oil arrangement section reactor.

Fig. 8 A has schematically shown the preferred embodiment of the oil arrangement section of using the inventive method.Organic liquor 500 enters storage tank 812.Randomly, organic liquor and oil can direct in the liquid/liquid segregation device 814 and be divided into first part's rectifying liquid/oil 816 and second section or residual rectifying mother liquor/oil 822.First part's rectifying liquid/oil can direct in the running product storage 818 and as rectifying liquid/oil 820 and distribute, and described rectifying liquid/oil 820 can circulate or sell.Second section rectifying mother liquor/oil 822 directs in one or more preheater 830 again.

Already heated rectifying mother liquor/oil 822, perhaps parting liquid/oil 500 does not flow in the well heater 610, preferably is accompanied by water vapour 602 and flows in the well heater 610.Gained liquid and gasification liquid/oil 836 flow into reactor 620, for example in the spiral propeller, and are separated into hydrocarbon vapour and gas 148 and carbon solid 142.Hydrocarbon vapour and gas 148 flow in the chiller/condenser 850, further shown in Fig. 8 B.At the gentle intravital any residual saccharoid of oil vapour, for example residual carbon solid 844 is removed and turns back in the reactor 620.

Carbon solid 142 is guided through air-lock 846 and enters in the carbon solid cooling device 630, and wherein they mix with water 632.Gained water and carbon solid mixture flow enter in the finished product storage system 650 through another air-lock 854.The carbon solid 142 of the finished product can be assigned in one or more commercial applications.

In order to unite use with the device 800 shown in Fig. 8 A, Fig. 8 B shows chiller/condenser 850.Chiller/condenser 850 helps many partitioning cycle, wherein also can contain the oil vapour of water and saccharoid and the mixture of gas and carry out many different separating steps.The hydrocarbon vapour and the gas 148 that come from reactor 620 flow in the carbon saccharoid separator 842, isolate residual solid particulate at this, for example residual carbon solid 844, and guide this solid again and get back in the reactor 620.

Effusive hydrocarbon vapour and gas flow in the steam quench system 860 of the General Principle enforcement of understanding according to those of ordinary skill in the art from carbon saccharoid separator.Oil and gas 870 from the steam quench system flow in oil/water/gas separator 872, further separate various components, for example oil 862, waste oil 876, gas and LPG874, and oil/carbon slurry 881.

In oil 862 inflow heat exchangers 864, enter final product stock system 866 afterwards, and sell with oily 144 forms.

Gaseous state and petroleum liquid gas (" LPG ") 874 flow in the condenser 890, isolates LPG and other gaseous fractions at this.Gas 894 flow in the superheater 892, obtains fuel gas 146, and described fuel gas 146 can be used as the energy and is transported in one or more device.LPG898 circulates in the following manner.At first, the LPG898 liquid/solid separator 884 of flowing through, and remove any residual carbon solid 886.Then, separate LPG with isolating oily blended from oil/carbon slurry 881 and turn back in oil/water/gas separator 872, and further separate.Wherein the circulation of gas and LPG mixture separation and condensation can optionally repeat repeatedly.

Oil/solid mixture, typically oil/carbon slurry 881 also can direct into the liquid/solid separator 884 from oil/water/gas separator 872, so that remove residual carbon solid 886.Optionally, preferably turn back to oil/water/gas separator for further guiding again with the isolating oil of LPG blended.

Flow in the oil/water separator 878 and water 880 is released or capable of circulation from the waste oil 876 of oil/water/gas separator 872.Flow back in oil/water/gas separator for further partitioning cycle repeatedly from the oil 882 of oil/water separator.

Above stated specification intends setting forth each side of the present invention.Do not plan to limit the scope of the invention with the embodiment that lists herein.Since the present invention has been described fully, those of ordinary skill in the art, it is apparent that, can under the situation of the spirit or scope that do not break away from claims, make many variations and improvement.

Claims (32)

1. by the method for raw material production fuel, this method comprises:

By the feedstock production slurry;

Slurry is carried out depolymerization process, form the composition that contains liquid mixture and at least a inorganics;

Separate described at least a inorganics and this liquid mixture; With

Derive by described liquid mixture and to obtain fuel.

2. the process of claim 1 wherein that described raw material comprises byproduct, plastic waste, rubber or the tire of animal excreta fertilizer, mud, food mfg and distribution.

3. the process of claim 1 wherein that described raw material is the alkyl raw material.

4. the method for claim 3, this method further are included in before described preparation or the heating, add organic solvent in this slurry.

5. the process of claim 1 wherein that described raw material is an organic raw material.

6. the process of claim 1 wherein that described deriving obtains comprising liquid mixture is carried out thermal conversion process.

7. the process of claim 1 wherein that described deriving obtains comprising this liquid mixture of hydrotreatment.

8. pass through the oil fuel of the method production of claim 1.

9. the method for fuel is provided to the device of combustion-driven, and this method comprises:

Supply with described device energy with the liquid mixture that the method for claim 1 is produced.

10. by the method for raw material production fertilizer, this method comprises:

By the feedstock production slurry;

Be enough to described raw material is depolymerized to this slurry of heating under the temperature of the composition that contains liquid mixture and at least a inorganics;

Separate described at least a inorganics and liquid mixture; With

Derive by described liquid mixture and to obtain fertilizer.

11. to the method for plant fertilising, this method comprises:

Apply the fertilizer of the method production of claim 10.

12. by the method for raw material production food, this method comprises:

By the feedstock production slurry;

Described raw material is depolymerized under the temperature of the composition that contains liquid mixture and at least a inorganics being enough to, heat this slurry;

Separate described at least a inorganics and liquid mixture; With

Derive by described liquid mixture and to obtain food.

13. give the method for animal-feed, this method comprises:

The food of the method production of claim 12 is provided to animal.

14. shredder residues is transformed olefiant method, and this method comprises:

Shredder residues is dissolved in the solvent;

Prepare slurry by this shredder residues;

This slurry is carried out the depolymerization step, produce liquid mixture;

To this liquid mixture step that is hydrolyzed, production organic liquor;

Derive by described organic liquor and to obtain oil.

15. the method for claim 14 is wherein carried out described depolymerization step in about 700-Yue 775 temperature range.

16. the method for claim 14 is wherein carried out described hydrolysing step in about 440-Yue 500 temperature range.

17. the method for claim 14 is wherein carried out described depolymerization step and carry out described hydrolysing step in about 440-Yue 500 temperature range in about 700-Yue 775 temperature range.

18. the method for claim 14, wherein said solvent are oil.

19. the method for claim 14, wherein said solvent are the oil that obtains from described conversion.

20. the rough circulation that will contain shredder residues and one or more tires changes into the method for fuel, this method comprises:

The undressed logistics that will contain shredder residues and one or more tires is dissolved in the solvent, produces slurry;

This slurry is carried out the depolymerization step, produce liquid mixture;

To this liquid mixture step that is hydrolyzed, produce organic liquor;

Derive by described organic liquor and to obtain oil.

21. the method for claim 20 is wherein carried out described depolymerization step in about 700-Yue 775 temperature range.

22. the method for claim 20 is wherein carried out described hydrolysing step in about 440-Yue 500 temperature range.

23. the method for claim 20 is wherein carried out described depolymerization step and carry out described hydrolysing step in about 440-Yue 500 temperature range in about 700-Yue 775 temperature range.

24. the method for claim 20, wherein said solvent are oil.

25. the method for claim 20, wherein said solvent are the oil that obtains from described conversion.

26. pass through the oil fuel that the method for claim 14 is made.

27. pass through the oil fuel that the method for claim 20 is made.

28. the process of claim 1 wherein that described deriving comprised:

To the described liquid mixture step that is hydrolyzed, form organic liquor;

Described organic liquor is changed into fuel.

29. the process of claim 1 wherein that described conversion comprises this liquid mixture of hydrotreatment.

30. the process of claim 1 wherein that described conversion comprises carries out thermal conversion process to this liquid mixture.

31. the process of claim 1 wherein that described raw material comprises fat, grease and/or protein source.

32. the process of claim 1 wherein described raw material comprise animal waste, plant waste, from the refuse of ethanol production facilities or the logistics of low value.

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