CN102459526A - Integrated coal-to-liquids process - Google Patents

Integrated coal-to-liquids process Download PDF

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CN102459526A
CN102459526A CN2010800286935A CN201080028693A CN102459526A CN 102459526 A CN102459526 A CN 102459526A CN 2010800286935 A CN2010800286935 A CN 2010800286935A CN 201080028693 A CN201080028693 A CN 201080028693A CN 102459526 A CN102459526 A CN 102459526A
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algae
synthetic gas
coal
urea
raw material
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R·A·菲亚托
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Accelergy Corp
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Accelergy Corp
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Abstract

A process for converting coal and algae feeds to liquids including converting the coal to liquids by direct liquefaction, gasifying an algae or algae residue containing biomass feed to produce syngas, converting syngas to liquids, increasing the hydrogen content of the coal feed in the direct liquefaction by supplementing it with hydrogen in the syngas produced from the algae or algae residue, producing algae by photosynthesis using CO2 produced by the direct liquefaction and gasification steps, and supplying algae or algae residue produced by hydroprocessing the algae, as the algae or algae residue feed in the gasification step.

Description

Integrated coal liquefaction method
Technical field
The present invention relates to integrated coal liquefaction method and system, especially, relate to so integrated gelatin liquefaction (ICTL) method and system, wherein CO through will during liquifying method, producing 2Be converted into useful chemical such as methylcarbonate or higher alcohols and reduce CO greatly 2Discharging.
Background technology
The increase of oil cost and cause the concern of other carbonaceous energy such as coal, Tar sands, shale and composition thereof is increased about the misgivings of following shortage.Coal is most important in these alternate resources, because be included in global a few part the fact that has mineral substance that a large amount of, the coal deposit thing that is easy to obtain and all the other resources contain much higher ratio and lower carbon content.Propose several different methods so that this material is changed into the liquids and gases fuel Products, comprised gasoline, diesel oil fuel, aviation fuel and heated oil, in some situation, changed into other products such as lubricant and chemical.
Many problems have hindered being widely used of coal and other solid fossil energy, comprise the synthetic low relatively thermo-efficiency that transforms with methyl alcohol liquefaction (MTL) of indirect gelatin liquefaction (CTL) conversion method such as Fischer-Tropsch (FT).To be about 1: 1 coal cause carbon half at least in the coal to change into CO to the ratio of hydrocarbon product such as H/C less times greater than the conversion of 2: 1 fuel to the ratio of H/C 2, cause waste thus.Therefore, a large amount of in coal discharging in useful products transforms as the greenhouse gases (GHG) of waste product, especially with CO 2Form, can be unfavorable to the CTL method because of many considerations that are derived from environment.
Propose, through carbonic acid gas being refilled in the subsurface formations to catch and isolated carbonic acid gas can overcome the GHG problem at least in part.The inferior position of this arrangement is costliness, requires near the somewhere conversion facilities can obtain suitable subsurface formations, and carbonic acid gas is escaped subsequently and got into the misgivings in the atmosphere, and the waste of the energy potentiality of the carbon content of carbonic acid gas.Coal transforms to valuable liquid product through indirect method, relates to the generation of synthetic gas.Can be with synthetic gas as the raw material of producing extensive product, said synthetic gas is the mixture that is mainly carbon monoxide and hydrogen, said product comprises liquid fuel, methyl alcohol, acetate, dme, contains oxygen alcohol, isocyanic ester etc.Can produce synthetic gas by carbonaceous material such as coal or by biomass through gasification.Use is purchased the gasifier of acquisition, can produce H from coal 2The ratio of/CO is about synthetic gas of 0.5～about 1.Yet, when or MTL synthetic through FT are converted the manufacturing product liquid, expectation H 2The ratio of/CO is about 2 synthetic gas.Utilize water gas shift reaction, the H of the synthetic gas that can coal be produced 2The ratio of/CO rises to expected range.Yet it can cause the discharging of great amount of carbon dioxide.
The exercise question of submitting to national energy technology experiment chamber is that the report DOE/NETL2007/1298 of " Increasing Security and Reducing Carbon Admissions of the US Transportation Sector:A Transformational Role for Coal with Biomass " proposes, with the higher H of having of coal and 10-15% 2Biomass such as Wooden Biomass, switchgrass or the corn stalk of/CO ratio gasify jointly, can be with being used for the CO that the FT synthetic is produced by gasification 2Quantity discharged reduce about 20%.Yet, in the method that proposes, have a large amount of problems.The thermo-efficiency of said method is low relatively, because typically through partially oxidation and use synthetic coal and biomass are gasified of indirect FT to need energy.Needed land area also is restricted to maximum every day of about 5000～10000 barrel equivalents with the amount of the biomass that can use economically around being used for needed land area of production biomass and ICTL facility.In addition, contain carbon resource with respect to mineral, biomass are significantly more expensive synthetic gas resources, have improved production cost thus.
Developed direct gelatin liquefaction (DCL) method with carbonaceous material such as gelatin liquefaction, said method than having advantage through synthetic conversion of FT, comprises significantly higher thermo-efficiency and CO a little still less in many application 2Discharging.This direct liquefaction method typically relates at catalyzer, typically is in the presence of very fine dispersive iron or molybdenum or its mixture; In the atmosphere of hydrogen, carbonaceous material and solvent be heated to the temperature of about 775 ° of F～850 ° F; So that texture of coal fracture and become radical, but said radical quencher and produce product liquid.Proposed to relate to the mixing coal liquefaction system of synthetic both or direct liquefaction and Wood Adhesives from Biomass of direct liquefaction and FT, the synthetic or Wood Adhesives from Biomass of wherein said FT provides the other hydrogen that is used for direct liquefaction, has reduced emission of carbon-dioxide thus.Also proposed to relate to direct liquefaction, FT is synthetic and all threes' of Wood Adhesives from Biomass mixing coal liquefaction system.Yet, the arrangement of these propositions all be unrealized thermo-efficiency, low cost and reduce the combination of GHG discharging greatly, for economically and attractive on the environment, they are necessary.Also have a kind of important needs, descend and can effectively use under the condition of carbon resource in Carbon emission, coal and biomass are to the economic means of liquid conversion.
Summary of the invention
The present invention provides the ICTL method and system that relates to direct gelatin liquefaction, indirect gelatin liquefaction and Wood Adhesives from Biomass method, wherein will be by the CO of gelatin liquefaction method and Wood Adhesives from Biomass generation 2, make that emission of carbon-dioxide is minimum and effectively utilize carbon resource to produce algae and product liquid such as liquid fuel and fuel dope as raw material.In indirectly gelatin liquefaction and Wood Adhesives from Biomass, at first with coal and gasifying biomass to change into synthetic gas and by product CO 2Randomly, the methane-steam reforming method through routine also can become synthetic gas with conversion of natural gas.The part of the synthetic gas that will produce through aforesaid method is supplied in the direct coal liquefaction method, be supplied to the synthetic method for transformation of FT, and be supplied in a preferred embodiment of the invention in the synthetic method for transformation of methyl alcohol.Will be through the CO of aforesaid method generation 2With ammonia react to produce urea.With the methyl alcohol that produces and urea reaction with generation methylcarbonate (DMC) and ammonia.With being derived from the synthetic and/or ammonia that is derived from direct coal liquefaction method of DMC with the ammonia that acts on urea synthesis.
In alternate embodiment of the present invention, not to produce methyl alcohol by the synthetic gas that is used to produce DMC, but through CO and H under high temperature and high pressure 2Higher alcohols is produced in reaction on catalyzer.
According to an aspect of the present invention, through direct gelatin liquefaction about 70～90% the coal that is used for the ICTL method is transformed, and about 10～30% coal is gasified to be used for direct method.Except in the situation of using algae, all biomass are all gasified to produce synthetic gas and by product CO 2Said biomass can be the resistates of timber, straw, corn cob, algae, the pyrolysis that is derived from timber etc. or hydrolysis, any other material or its combination of plant derivation.In a preferred embodiment of the invention, biomass comprise the CO that is produced by aforesaid method through using 2The algae that carries out photosynthesis with water and produce.The part of the urea that randomly, will in urea synthesis method, produce is as the nutrition of algae working method.In one embodiment of the invention, if the lipid content of algae is enough high, then algae is carried out hydrotreatment so that the lipid that is contained is directly changed into hydrocarbon.Through partially oxidation the resistates of algae hydrotreatment is changed into synthetic gas.Perhaps, particularly under the lower situation of the lipid content of algae, algae is gasified to produce synthetic gas.In the also other aspect according to the inventive method; When the photosynthesis output of algae descends during cycle time such as night; Store a part of urea, with as raise when the throughput rate of algae as by day during the time photosynthetic nutrition and/or be used for DMC and synthesize.In this way, producing urea is to store CO 2Means.Produce DMC or in algae grows untapped urea can sell as independent product.According to also other aspect of the present invention, the resistates that is derived from direct gelatin liquefaction method is mixed with biomass residuals and gasifies.
The accompanying drawing summary
Fig. 1 is the simplified flow chart according to an embodiment of integrated gelatin liquefaction method of the present invention.
Fig. 2 is the synoptic diagram according to direct coal liquefaction system of the present invention.
The mode of embodiment of the present invention
Various direct gelatin liquefaction (DCL) methods and system have been proposed, for example at U.S. Patent number 4,077,867,4,485; 008,4,637,870,5,200,063,5; In 338,441 and 5,389,230 disclosed those, here through with reference to their complete form is incorporated herein.The advantage of DCL method is, is merely about 45～52% indirect method such as FT is synthetic has obviously higher thermo-efficiency with the MTL conversion method than thermo-efficiency, is 60～65%.The efficient that FT and DCL method self can change into useful products with the carbon in the coal is up to about 50%.
According to ICTL method of the present invention and system, mainly implement the conversion of coal through DCL, adopt vaporized coal and the biomass (preferably including algae or algae hydrotreatment resistates) of q.s, Sweet natural gas to be transformed randomly; With the manufacturing synthetic gas, thereby other hydrogen is provided, provides synthetic gas synthetic to implement FT to the DCL method; And; In the embodiment, be used to make methyl alcohol shown in of the present invention, this methyl alcohol and urea reaction and produce DMC and ammonia.Can be with being derived from the input that FT synthetic tail gas is supplied to the DCL that is used for supplying other reactants, said tail gas comprises unreacted hydrogen and CO.Will be through the CO of DCL with indirect CTL and the generation of gasifying biomass method 2Stream thigh is used for making algae through photosynthesis, with as all or part of of said biomass, and through making urea with the reaction of ammonia.Can be back in the urea synthesis step being derived from DMC synthetic ammonia, to supply needed ammonia react thing.Can also the ammonia through the direct liquefaction generating step be used for urea synthesis.
Preferably, make all to be minimized with the amount of biomass, both because the thermal efficiency ratio direct liquefaction thermo-efficiency of indirect method much lower, again because biomass, especially algae are enough high relatively and availability is limited by the ratio of gasification with the coal of preparation synthetic gas.Coal gasification produces H 2The ratio of/CO is about 0.5 synthetic gas.Can through with the water gas shift reaction that links to each other of gasification, if or that ferrum-based catalyst is used for FT is synthetic, can improve this ratio in the synthetic gas of coal generation.
Algae different more than 300000 kinds has been proposed.All algae mainly comprise protein, glucide, fat and the nucleic acid of different ratios.Various algae contain the lipid acid (lipid) based on their total mass about 2～40%.The carbon content of algae can also change in the scope of about 40～70 atom %.Algae is through CO 2Make with the photosynthesis of water and sunlight reaction.Said algae is nourished, and in water, promotes the production of algae because of the existence of nutrition such as urea.Have more that the algae of high lipid content is more favourable in the method for the invention, but often slower than algae grows with more higher protein content and carbohydrate content.Therefore, need between the lipid content of the algae that is used for said method and obtainable growth velocity, weigh usually.In the method for the invention, the more preferably algae shown in algae such as the following table and other families (strain) with about 20% above lipid content.
Table 1 is the chemical constitution (%) of the algae of basic representation with the dry-matter
Family Protein Glucide Lipid Nucleic acid
Dimorphism grid algae (scenedesmus dimorphus) 8～18 21～52 16～40 -
Chlamydomonas reinhardtii (chlamydomonas rheinhardii) 48 17 21 -
Chlorella (Chlorella vulgaris) 51～58 12～17 14～22 4～5
Spirogyra green alga (Spirogyra sp.) 6～20 33～64 11～21 -
For a short time, decide whip chrysophyceae (Prymnesium parvum) 28～45 25～33 22～38 1～2
If the lipid content of algae is enough high, then preferably algae is carried out hydrotreatment directly the lipid that is contained is changed into hydrocarbon.In the U.S. Patent application US2009/0077864A1 that announces, disclose the method and system that is used for algae is carried out hydrotreatment, its content has been incorporated herein through reference.Through conventional partially oxidation the resistates of algae hydrotreatment is changed into synthetic gas.Perhaps, can algae be changed into synthetic gas through hydrogenation-gasification or partially oxidation.Algae is being changed into H 2The ratio of/CO is up in about synthetic gas more than 3/1, and the efficient of hydrogenation-gasification is up to about 95%.Also can algae be changed into synthetic gas through partially oxidation, this will cause synthetic gas to have about 0.9/1 lower H 2The ratio of/CO.In a kind of arrangement, at first algae is carried out hydrogenation-gasification, and mix, to make other synthetic gas through partially oxidation with residual residual material self or with the resistates that derives from the DCL method.
In any given situation; The gasification of per-cent, biomass and the algae of direct and indirect gelatin liquefaction, through hydrotreatment algae is directly changed into liquid fuel and depend on the market requirement of characteristic and the cost of the for example various coals of parameter, biomass and algae, specific various products and the balance between economy and the environmental factors with respect to the best of breed of the mixture of the gasification of algae, the biological resistates that is used to gasify and DCL resistates and other processing parameters, it can change with the variation and the change of time of device.Consider the structure of typical commercial size, ICTL facility and the fact that operation can spend millions of even multi-million dollar; Be used for confirming medium relatively according to the needed experimental amount of the optimum configuration of ICTL facility of the present invention; In any case and should implement said experiment with as the design of said facility and the part of building method, thereby reduce risk.
With reference to the embodiment described in Fig. 1 of accompanying drawing, according to the integrated coal liquefaction method 100 of illustrative embodiments of the invention comprise utilize methyl alcohol synthetic 101 and FT synthesize 103 with the carbon raw material indirect reformer become product liquid and with this raw material direct liquefaction 105 both.Disclosed exemplary of the present invention uses coal as main carbon raw material.However, it should be understood that other solids or liquid carbon-containing raw material such as Tar sands, shale, mud coal and heavier petroleum fraction for example long residuum and vacuum resid, can mix or replace said coal with said coal.The type that is preferably used as the coal of the raw material in the system of the present invention comprises bituminous coal and sub-bituminous coal and brown coal.So not preferred hard coal.Can produce the synthetic gas that is used for the indirect reformer step through the gasification of in gasifier 107, coal being gasified and in gasifier 109, biomass are carried out.Other synthetic gas is produced by Sweet natural gas in methane-steam reformer unit 111.
In gelatin liquefaction step 107, the feedstock conversion of utilizing conventional partially oxidation will comprise coal, water and oxygen becomes H 2The ratio of/CO is about 0.5 synthetic gas and CO 2In gasifying biomass step 109, preferably utilize the initial hydrogenation-gasification and the partially oxidation of resistates, Wood Adhesives from Biomass is become H 2The ratio of/CO is about synthetic gas and CO more than 2 2Making in the step 111 of synthetic gas, change into H by the raw material that comprises natural G&W 2The ratio of/CO is about 2.0 synthetic gas.Preferably, the H that is used for and synthetic gas that FT synthesis step 101 and 103 provide synthetic to methyl alcohol 2The ratio of/CO is about 2.0.
Exist several kinds to can be used for hydrogen and the isolating industrial system of carbon monoxide.Transformation absorption (PSA) method depends under pressure, and gas is easy to by the fact of solid surface attraction or " absorption ".Pressure is high more, and the gas of absorption is many more; When pressure descended, gas was emitted, or desorption.Use PSA method can be with the gas delivery in the mixture, because different gas can stronger or inferior attracteding on the different solid surface doughtily.Can be through PSA to H 2, CO and CO 2Syngas mixture separate to make the stream thigh of enrichment hydrogen.Perhaps, at first synthetic gas is carried out water-gas shift, to make H 2And CO 2Two-component mixture, through PSA or through other means as known in the art such as membrane sepn (H wherein 2Compare CO 2Much efficient as to permeate to produce the flow of pure hydrogen thigh) can separate it.At last, can use the reactive metal film of palladium and other associated metal alloys that hydrogen and other gas delivery have also been made the option that is purchased acquisition.USP 5,792,239,6,332,913 and 6,379,645, and the application US2003/3190486 that announces and US2009/0000408 have described multiple this stripping technique and through with reference to said patent is incorporated herein with its complete form with applying for.
In step 101, the synthetic gas that is derived from previous said step is used as raw material, to make methyl alcohol and carbonic acid gas by the synthetic gas synthesizing methanol.In FT synthesis step 103, synthetic gas is used as raw material to make hydrocarbon product and carbonic acid gas.Can be with being derived from unreacted CO of containing of FT synthesis step 103 and H 2Tail gas be added in the DCL raw material, to supply other reactant.
In direct gelatin liquefaction step 105, will comprise that in containing the atmosphere of hydrogen coal, water and solvent or hydrogen body supply the feedstock conversion of solvent to become product liquid, during also produce by product ammonia.Will with the isolating enrichment H of synthetic gas 2Gas be supplied in the direct gelatin liquefaction step 105, with efficient and the output that improves direct coal liquefaction method, said synthetic gas derives from gelatin liquefaction step 107, gasifying biomass step 109 and/or is made the step 111 of synthetic gas by Sweet natural gas.The tail gas of FT synthesis step 103 comprises unreacted CO and/or H 2And also can be used in the direct gelatin liquefaction step 105.The resistates that is derived from direct gelatin liquefaction step 105 is mixed to change into other synthetic gas with biomass that are supplied to gasifier 109 or biomass residuals.
The biomass that are supplied to gasification step 109 can be the resistates of timber, straw, corn cob, algae, the pyrolysis that is derived from timber etc. or hydrolysis, any other material or its combination of plant derivation.Algae is the part or all of particularly advantageous source of this biomass, because it can use the CO that in each step of ICTL method of the present invention, produces 2Produce on the spot, greatly reduce the discharging of GHG thus and improved the carbon efficiencies of said method.Through the photosynthesis during its process of growth, other said biomass resource also can be removed CO from atmosphere 2Thereby, think that their use has also reduced the GHG elute that is derived from the ICTL method of the present invention.According to the importance of the inventive method, the GHG that greatly reduces from ICTL facility of the present invention discharges like CO 2, and through using most of CO 2Make useful chemical (in exemplary, being methylcarbonate (DMC)) and improved carbon efficiencies.In exemplary, will be through the CO of above-mentioned steps generation 2Reclaim and in urea synthesis step 113 with ammonia react to produce urea.Use the recovery method of various routines can carry out CO 2Recovery, said conventional recovery method includes but not limited to, absorption, absorb (for example transformation absorption (PSA) and displacement purge circulation (DPC)), subzero fractionation, membrane sepn, it makes up etc.Although need one or more recovery methods to come from synthetic gas or tail gas, to reclaim CO 2, the byproduct gas that is derived from reformer or C3+ product upgrading device will not contain the H of obvious amount 2Or H 2O is thus except carrying out the condensation, without any need for recovery method heavy hydrocarbon (C6+).In addition, although the CO that reclaims is used in expectation in the method for the invention 2, but the CO that derives from the alternative source in integrated association (integrated complex) scope also capable of using 2Replenish or substitute the CO that reclaims 2
Then, will be through urea synthesis step 213 urea of producing and the methyl alcohol reaction of producing, to produce DMC and ammonia through methyl alcohol synthesis step 101.
The ammonia that in DMC synthesis step 115, produce and/or the by product ammonia that is derived from direct gelatin liquefaction step 105 are as the reactant ammonia in the urea synthesis step 113.
As the additive in the transport fuel; DMC is particularly useful, because it has about 105 high-octane rating, and can be as the additive in the gasoline; And when as the additive in the diesel oil fuel, can reduce greatly because of diesel oil as the burn discharging of the GHG that produces of transport fuel.For example, have been found that and in diesel oil fuel, add 2% DMC, the soot discharging of diesel powered vehicle is reduced up to 20%.In the chemical as fuel or fuel dope, DMC has other unique advantage, H in its molecule 2The ratio of/CO is 1/1, has reduced total stoichiometry H of ICTL facility thus 2The ratio of/CO.
The product stream thigh that is derived from the inventive method for example can comprise each product stream of synthetic crude product and other strand as LPG liquefied petroleum gas, and ((C5～C6), high-octane rating blend components (the stream thigh that contains C6～C10 aromatic substance), rocket(engine)fuel, diesel oil fuel, other distillment fuel, lubricating oil blend fuel or lubricating oil mediation raw material, they can carry out produce and market as independent product for C3～C4), condensation product.
FT is synthetic
Be used to implement FT synthetic reactor drum, catalyzer and condition to those of skill in the art be know and at many patents and other publications such as USP 7,198,845,6; 942,839,6,315; 891,5; Be described in 981608 and RE39,073, here through with reference to its content being incorporated herein with its complete form.In using fixed-bed reactor, moving-burden bed reactor, fluidized-bed reactor, ebullated bed reactor or the slurry reactor drum of various catalyzer and under the various operational conditionss of selecting based on the product group of expectation and other factors, it is synthetic to implement FT.Typical FT synthetic product comprises paraffinic hydrocarbons and alkene, uses formula nCH usually 2Expression.Through the reaction conditions that includes but not limited to that type of reactor, temperature, pressure, air speed, catalyst type and synthetic gas are formed, can confirm the productive rate and the selectivity of given product stream thigh.
Be used for FT synthetic stoichiometry synthetic gas H 2The ratio of/CO is about 2.0.By H in the synthetic gas of coal production 2The ratio of/CO typically is about 0.5 less than 2.Through the synthetic gas of coal production is mixed with synthetic gas by biomass or gas production, can improve this ratio.If this mixing step can not fully improve H 2The ratio of/CO, and conventionally can not obtain other hydrogen from other sources, then can further improve this ratio through water gas shift reaction.In using the synthetic situation about transforming of the FT that can not promote the cobalt-base catalyst of water gas shift reaction and implement; Before preferably in importing the FT synthesis reactor, through the steam reaction in a part of synthetic gas and the shift converter (not shown) is produced other hydrogen and CO 2, with the H of synthetic gas that coal is produced 2The ratio of/CO rises to about 2.0.If use can promote the ferrum-based catalyst of water gas shift reaction to implement the synthetic conversion of said FT, then needn't use independent shift converter.Yet in any one situation, said water gas shift reaction produces additional C O 2
Directly gelatin liquefaction
The exemplary according to system of the present invention (Fig. 1) that will be used for implementing direct gelatin liquefaction 105 is shown in Fig. 2 of accompanying drawing.Sweep in the formula roller mill 201 at the gas of routine the coal raw material is carried out drying and crushing so that its moisture content is 1～4%.To crush and the exsiccant coal is fed in the mixing tank 203, there it mixed with the solvent that contains recycling bottom material and catalyst precursor with formation slurry stream thigh.Catalyst precursor in exemplary is preferably the form of 5～10% phospho-molybdic acid (PMA) aqueous solution, and the amount of said phospho-molybdic acid is equivalent to the molybdenum that adds 50wppm～2% with respect to exsiccant coal raw material.
Said slurry leaves mixing tank under about 300～500 ° of F (139～260 ℃).Most of steam in the coal and the water in the PMA raw material since the thermal cycling solvent (650/1000 ° F or 353/538 ℃) that is fed to mixing tank with bottom material and quilt is expelled in this mixing tank.This steam and the volatile matter carried secretly are as sour water and (not shown among Fig. 2) gone out in condensation.Leave coal in the slurry of mixing tank and have about 0.1～1.0% steam.Through slurry pumping system 205, the coal slurry body is pumped from mixing tank and pressure is risen to about 2000～3000psig (138～206kg/cm 2G).The high pressure slurry that makes is carried out preheating in the interchanger (not shown), mix, further heating in stove 207 then with hydrogen.
The mixture of coal slurry body and hydrogen is fed to about 600～700 ° of F (343 ℃) and 2000～3000psig (138～206kg/cm 2G) in the input of liquefying reactor 209,211 that is connected in series and 213 fs.Reactor drum 209,211 and 213 is the upflowing tubular vessel, and the total length of three reactor drums is 50～150 feet.Because the height heat release of gelatin liquefaction reaction causes temperature to raise from a reactor drum stage to the next reactor drum stage.To be lower than 850～900 ° of F (454～482 ℃) in order in each stage, top temperature being remained, preferably to inject other hydrogen between the stage at reactor drum.The dividing potential drop of hydrogen preferably remains about 1000～2000psig (69～138kg/cm in each stage 2G).The elute of the liquefying reactor that is derived from final stage is divided into gas streams and liquid/solid stream thigh, and in separation and cooling system 215, makes the pressure of liquid/solid stream thigh descend.Gas streams cooled off with the vapour condensation with petroleum naphtha, overhead product and solvent become liquid.Then, remaining gas is handled to remove H 2S and CO 2
Then, the gas that major part is handled is sent in the hydrogen recovery system 17, to do further processing through conventional means, to reclaim the hydrogen that is wherein contained, then it is circulated to mix with the coal slurry body.Remainder to the gas handled purges, and accumulates in circulation loop to prevent lighting end.The hydrotreatment system that will be used for downstream from the hydrogen that wherein reclaims.
With the liquid/solid stream of decompression strand and during gas cooling the hydrocarbon of condensation be sent in the atmospheric fractionator 219, in said atmospheric fractionator 219, said material is divided into lighting end, petroleum naphtha, overhead product and tower bottom distillate.Lighting end is handled with recover hydrogen and the C that can be used in fuel gas and other purposes 1～C 4Hydrocarbon.Petroleum naphtha is carried out hydrotreatment with saturated diolefine and other reactive hydrocarbon compounds.160 ° of F+ cuts to petroleum naphtha carry out hydrotreatment and powerful the reformation to make gasoline.Can carry out hydrotreatment to make product to the overhead product cut such as diesel oil and rocket(engine)fuel.
Preferably operation under sufficiently high pressure of atmospheric fractionator 219 makes it possible to a part with the tower bottom distillate of 600～700 ° of F+ (315～371 ℃) and under the condition of not carrying out pumping, is circulated in the slurry mixing tank 203 with as solvent.The pumping of this stream thigh will be difficult, because its viscosity height and solids content are high.
The residue bottom material that originates from atmospheric fractionator 219 is fed in the vacuum fractionation device 221, therein to be divided into the branch of 1000 ° of F-cuts and 1000 ° of F+.Said 1000 ° of F-cuts are added in the solvent streams thigh to the slurry mixing tank 203 to be recycled.1000 ° of F+ cuts are fed in the bottom material partially oxidation gasifier 223, utilize partially oxidation and water gas shift reaction to make itself and oxygen reaction there to make hydrogen and CO 2If directly carry out gelatin liquefaction and its product is carried out upgrading processing needing other hydrogen, then will be derived from gas and sweep the part of the coal of formula roller mill 201 and be fed in the coal partially oxidation gasifier 225 to produce other needed hydrogen.To be sent to landfill yard or be used to make material of construction such as cement brick, road surface paving material and other construction applicationies by the ash that in gasifier 223 and 225,1000 ° of F+ cuts and coal is carried out partially oxidation and produce.
If the coal that transforms through DCL is H 2O and O 2Content then preferably like US 5,026, carries out pre-treatment to coal described in 475 than bituminous coal or the high brown coal of sub-bituminous coal in containing the environment of aqueous carbon monoxide, here through being incorporated herein with its complete form with reference to the content with said patent.
If operation DCL method under the low relatively catalyst concn of about 50wppm～500wppm; Wherein about 70～80% of the coal of importing is changed into product, the part circulation of the catalyzer that is contained in the then preferred economically only solvent streams thigh with charging is back in the slurry mixing tank 203.Under the more high catalyst concentration of about 1～5wt%; Wherein about 80～95% of the coal of importing is changed into product; Then preferred through such as at USP 4; Method described in 417,972 reclaims remaining catalyzer from the ash that is produced by bottom material partially oxidation 223, here through being incorporated herein with its complete form with reference to the content with said patent.
At USP 5,198, the method that the product liquid to direct gelatin liquefaction step 105 carries out upgrading is disclosed, here through being incorporated herein with its complete form with reference to the content with said patent in No. 099.The catalyzer that can be used in the DCL method also is included in U.S. Patent number 4,077, and those disclosed in 867,4,196,072 and 4,561,964 is here through being incorporated herein with its complete form with reference to the content with said patent.
Synthesizing of methyl alcohol
The technology that is purchased acquisition of use standard can synthesizing methanol in methyl alcohol synthesis step 101 (Fig. 1).At USP 4,339, described some in 413,6,921,733 and 7,189,379 and be applicable to methyl alcohol synthetic method, here through being incorporated herein with its complete form with reference to content with said patent.
Synthesizing of urea
Through the urea production technology that is purchased acquisition of standard, in step 113 by CO 2With ammonia can urea synthesis.At U.S. Patent number 5,096,599 and 5,359, the method described in 140 is to can be used in to put into practice typical method of the present invention.
DMC's is synthetic
In the catalystic rectifying reactor of the catalyzer in having the conversion zone that is loaded in reactor drum (being also referred to as the catalytic distillation reactor drum); Perhaps in moving-burden bed reactor; Implement urea and the catalyzed reaction of methyl alcohol, in said moving-burden bed reactor, make the catalyzer physical transfer and pass through conversion zone with the reaction kinetics and the balance of control method better to DMC.Get into the beds from the top that contains catalyst section through urea being dissolved in the urea methanol solution that forms in the methyl alcohol; Urea in the solution gets into beds, and the methyl alcohol in the solution gets into the rectifying section of catalystic rectifying reactor owing to higher temperature.Reaction raw materials methyl alcohol gets into the beds from the bottom that contains catalyst section.Urea and reaction raw materials methyl alcohol react in catalyst section and form DMC.
Perhaps, in the method that comprises the steps, in catalystic rectifying reactor, can implement the synthetic of DMC: (1) is dissolved in the methyl alcohol urea to form urea methanol solution, and wherein the weight percent of urea is 1%～99%; (2) feeding rate with 0.01～10ml/g catalyzer/min is fed to the top of urea methanol solution from the catalyst section of catalystic rectifying reactor the beds; And with the feeding rate of 0.01～20ml/g catalyzer/min with reaction raw materials methyl alcohol from the underfeed of the catalyst section of catalystic rectifying reactor to beds, wherein implement said reaction comprising under temperature at the bottom of 120 ℃～250 ℃ temperature of reaction, the reaction pressure of 0.1MPa～5MPa, 70 ℃～210 ℃ the still, 70 ℃～250 ℃ stripping section temperature, 70 ℃～280 ℃ the condition of reflux ratio of rectifying section temperature and 1: 1～20: 1.
The weight percent of urea is preferably 20%～50% in urea methanol solution.The feeding rate of urea methanol solution is preferably 0.1～2ml/g catalyzer/min.The feeding rate of reaction raw materials methyl alcohol is preferably 0.1～10ml/g catalyzer/min.Temperature of reaction is preferably 150 ℃～200 ℃.Reaction pressure is preferably 0.5MPa～3MPa.Temperature is preferably 110 ℃～180 ℃ at the bottom of the still.The stripping section temperature is preferably 150 ℃～190 ℃.The rectifying section temperature is preferably 150 ℃～200 ℃.Reflux ratio is preferably 1: 1～and 6: 1.
The suitable catalyst that is used for the DMC synthesis step has following composition: active ingredient: 20～50wt%; And carrier: 80～50wt%.Can include but not limited to gac, Alpha-alumina, gama-alumina, silicon oxide, molecular sieve or zeolite etc. or can be used for the only stone carrier of pottery in the catalytic distillation reactor assembly as the material of carrier.
The activeconstituents that is used for dmc catalyst can be selected from basic metal, earth alkali metal and transition element oxide compound and muriate, and composition thereof.Said basic metal comprises K, Na, Cs and Li.Said earth alkali metal comprises Ca and Mg.Said transition element comprises Zn, Pb, Mn, La and Ce.
Can prepare through the method that comprises the steps and to be used for DMC synthetic catalyzer:, form the aqueous solution of the soluble salt of preparation basic metal, earth alkali metal or transition element according to catalyzer by weight; With KOH or NH 3H 2O etc. are with pH regulator to 0～5 of solution; On carrier, spray and flood this aqueous solution (for example, spraying and pickling process), with the carrier of preparation active constituent loading through equal-volume; Carrier to active constituent loading under 100 ℃～250 ℃ temperature carries out drying and continues 2～24 hours; And last under 500 ℃～1000 ℃ temperature to the carrier calcining of exsiccant active constituent loading 2～12 hours.
Spendable soluble metallic salt comprises nitrate salt, acetate, oxalate, oxyhydroxide, halogenide of basic metal, earth alkali metal and transition element etc.Preferably the pH value is adjusted to 1～3.Calcining temperature is preferably 650 ℃～800 ℃.Calcination time is preferably 4～8 hours.In the Preparation of catalysts process, it is key point that pH value of aqueous solution, calcining temperature and calcination time are controlled.
USP 7,271 has been described the appropriate method that is used for preparing the synthetic employed catalyzer of DMC for No. 120 and through with reference to its complete form it being incorporated herein.At High-Yield Synthesis of Dimethyl Carbonate from Urea and then Methanol Using a Catalytic Distillation Process; Ind.Eng.Chem.Res.2007; 46; Also described the compound method of DMC among the 2683-2687, be incorporated herein with its complete form through reference at this.
Because the CO that in the ICTL method, produces 2Major part be used to form DMC, so can avoid or minimize CO 2Compression and seal up for safekeeping, improved the overall thermal efficiency of method thus.In the formation of DMC, use CO 2, to the combination of useful products and FT deutero-diesel oil and DMC higher material efficient is provided, because the fuel of blend provides tangible discharging advantage for the product that merges, make and can further reduce the footprint of total greenhouse gases in factory.
In integrated method 100, in fact only consume a spot of ammonia, because in said method, ammonia is circulated.Therefore, need not replenish a large amount of ammonia.Perhaps, the commercially available acquisition of said ammonia or can synthesize by nitrogen that from air separation, obtains and hydrogen.
Hereinafter test, to CO in integrated gelatin liquefaction method through stoichiometry to the reaction that in integrated approach, takes place 2Discharging study.Two kinds of reactions that in gasification step 101, take place comprise that the following reaction equation of basis obtains 1 mole carbon monoxide and 1 mole hydrogen with 1 mole carbon and 1 mole water reaction:
C+H 2O→CO+H 2 (a)
In gasification step 101, according to following reaction equation, the reaction of the water of 1 mole carbon monoxide and 1 mole, so that 1 mole carbonic acid gas and 1 mole hydrogen (WGS reaction) to be provided:
CO+H 2O→CO 2+H 2 (b)
In methyl alcohol synthesis step 103, according to following reaction equation with the hydrogen reaction of 1 mole carbon monoxide and 2 moles so that 1 mole methyl alcohol to be provided:
CO+2H 2→CH 3OH (c)
In urea synthesis step 105,2 moles ammonia and 1 mole carbonic acid gas (deriving from the WGS reaction) are reacted so that 1 mole urea and 1 mole water to be provided according to following reaction equation:
2NH 3+ CO 2→ urea+H 2O (d)
In the synthesis step 107 of DMC, according to following reaction equation with the reaction of 2 mole, of methanol and 1 mole of urea (deriving from urea synthesis step 105) so that 1 mole DMC and 2 moles ammonia (reclaim and be used for urea synthesis step 105) to be provided:
2CH 3OH+ urea → DMC+2NH 3(e)
According to the material balance that carries out with above-mentioned reaction, the carbonic acid gas that in integrated gelatin liquefaction method, discharges is zero in theory.
As by the substituting of synthetic gas synthesizing methanol, the commercially available acquisition of methyl alcohol, this depends on price and availability when needing.In alternate embodiment of the present invention, through to FT synthetic transform and direct liquefaction step 103 and 105 in any one or the petroleum naphtha that produces among both reform respectively, can produce other hydrogen.The hydrogen that in naphtha reforming, produces can be used in the direct gelatin liquefaction, to improve the H of synthetic gas 2The ratio of/CO, and can also be used for other technology as the part of C5+ product being carried out hydrotreatment to remove alkene, oxygenatedchemicals and other trace heteroatoms.During petroleum naphtha being reformed, produce hydrogen through at least a portion C5+ Fischer-Tropsch product is changed into aromatic substance.Be used for C 6The type reaction of paraffinic hydrocarbons is:
C 6H 14→C 6H 6+4H 2
Aromatic products through above-mentioned naphtha reforming technology produces can be used in the multiple application, comprises the high-octane rating blend component that is used for gasoline, typically comprises the mixture of following each thing: C6～C10 aromatic substance; Be used for chemical, in particular for producing the benzene of hexanaphthene; Ethylbenzene and/or isopropyl benzene; Toluene as chemical; With as chemical, in particular for producing the xylene mixture of p-Xylol.
From Fischer-Tropsch product, remove hydrogen, cause clean C5+ product to have the stoichiometric ratio of lower hydrogen and carbon.That is, even the ratio of initial hydrogen and carbon is about 2.0, after a part of product changes into aromatic substance, the hydrogen of C5+ product and the stoichiometric ratio of carbon drop to less than about 2.0, preferably less than about 1.95, be more preferably less than about 1.90 value.For example, the stoichiometric ratio of the hydrogen of C5+ product and carbon drops to about 1.0 (for example benzene) even less than the value of 1.0 (for example naphthalenes).

Claims (9)

1. one kind will contain the method that the coal feedstock conversion becomes liquid, and said method comprises the steps:
A. through direct liquefaction the said major part at least that contains the coal raw material is changed into liquid;
B. the raw material that contains algae or algae resistates is gasified to produce synthetic gas;
C. will change into liquid through the synthetic gas that step b produces;
D. through the hydrogen in the synthetic gas of step b generation raw material described in the step a is replenished to improve the hydrogen content of this raw material;
E. use the CO that produces through step of one in the above-mentioned steps or multistep 2Carry out photosynthesis to produce algae; And
F. supply as the raw material that contains algae or algae resistates among the step b with the algae that produces among the step e or through the algae that produces among the step e being carried out the algae resistates that hydrotreatment produces.
2. the process of claim 1 wherein that step a comprises that utilization replenishes hydrogen that gasification the produced hydrogen content to said raw material.
3. the process of claim 1 wherein that the step that synthetic gas is changed into liquid comprises changes into methyl alcohol with said synthetic gas.
4. the method for claim 3 wherein contains the coal raw material to said among the step a and carries out direct liquefaction and also produce ammonia, and comprises that also at least a portion with said methyl alcohol and said ammonia changes into urea.
5. the method for claim 4 comprises that at least a portion with said urea is used as the nutrition of producing in the said algae.
6. the method for claim 1 comprises also the said sub-fraction that contains in the coal raw material is gasified to produce the step of synthetic gas that the wherein said synthetic gas that contains the coal raw material production is included in the synthetic gas that transforms among the step c.
7. the method for claim 1 comprises also Sweet natural gas is gasified to produce the step of synthetic gas that the synthetic gas of wherein said gas production is included in the synthetic gas that transforms among the step c.
8. the method for claim 4 also comprises at least a portion of said urea and at least a portion of said methyl alcohol are reacted with production methylcarbonate and ammonia, and use is produced said urea by at least a portion of the said ammonia of said urea and methanol production.
9. the method for claim 4, be included in also between the throughput rate decrement phase of algae that a part with said urea stores and during the throughput rate of said algae raises with the urea of said storage with acting on the nutrition of producing algae.
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