CN101538483B - Poly-generation technique for using coal gas and coke oven gas as raw materials - Google Patents
Poly-generation technique for using coal gas and coke oven gas as raw materials Download PDFInfo
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- CN101538483B CN101538483B CN2009100741012A CN200910074101A CN101538483B CN 101538483 B CN101538483 B CN 101538483B CN 2009100741012 A CN2009100741012 A CN 2009100741012A CN 200910074101 A CN200910074101 A CN 200910074101A CN 101538483 B CN101538483 B CN 101538483B
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Abstract
The invention relates to a poly-generation technique for using coal gas and coke oven gas as raw materials. The poly-generation technique comprises the following steps of: carrying out mixing on part of H2 prepared by purified water gas and coke oven gas through pressure swing adsorption and tail gas obtained by Fischer-Tropsch synthesis, carrying out Fischer-Tropsch synthesis and obtaining hydrocarbon mixture and tail gas. The CO2 separated from tail gas separate by first pressure swing adsorption enters a urea synthesis unit for reaction, the CO and the hydrogen respectively obtained by separation of second pressure swing adsorption and third pressure swing adsorption of the residual tail gas are circulated back to a Fischer-Tropsch synthesis unit for reaction; and the residual gases can be used for generating power or obtaining SNG by secondary condensation. The coke oven gas enters pressure swing adsorption after being purified and desulphurized so as to separate H2; wherein one part of H2 is used as supplementation of H2 needed by Fischer-Tropsch synthesis and the other part of H2 is mixed with N2 for ammonia synthesis so as to obtain synthetic ammonia; and the synthetic ammonia is mixed with CO2 obtained by the first condensation and CO2 separated from the Fischer-Tropsch synthesis for urea synthesis so as to obtain urea. The CO2 separated from the first condensation of desorption gas by pressure swing adsorption of the coke oven gas is used for urea synthesis; and the residual gases is treated by the second condensation to obtain SNG and mixed gas of CO and N2. The invention has no emission of greenhouse gases, uses richness in carbon and deficiency in hydrogen of the coal gas and the richness in hydrogen and deficiency in carbon of the coke oven gas to carry out complementation, realizes modulation of product structure by Fischer-Tropsch synthesis and improves the economical efficiency of the process of Fischer-Tropsch synthesis.
Description
Technical field
The invention belongs to a kind of is the technique of raw material Poly-generation by coke(oven)gas and gas maked coal.
Background technology
Coal is as the fossil energy of high carbon emission, and its traditional direct burning utilizes mode and transformation technology can not satisfy the requirement of more and more higher economy and environment.Chemical by Fischer-Tropsch synthetic acquisition Coal-based Liquid Fuel and high added value is brand-new industrial forward position of present coal chemical technology, has broad application prospects and economic benefit.Urea is the nitrogenous fertilizer of present usage quantity maximum, and synthetic natural gas (SNG) belongs to the comparatively rare clean fuel of China (at present domestic needs is vigorous, and breach is very large).This just requires can plan as a whole economic benefit, environmental benefit and social benefit on estate planning, technical research, has optimized product structure and corresponding technological line, could realize the sound development of Modern Coal-based Chemical industry.
Coke(oven)gas is the by product in the coal destructive distillation Coking Process, and main component is: H
258-66%; CH
421-25%; CO 5-8%; C
mH
n1.6-2.0%; CO
21.9-2.3%; N
22-6%.Take coke(oven)gas as raw material, needing wherein, about 20% methane generates reforming gas, reforming gas H by steam reforming or partial oxidation separately
2/ CO mol ratio is used for Fischer-Tropsch synthesis unstripped gas H up to 4
22 times of/CO show as Fu Qing and lack carbon, so be used for Fischer-Tropsch synthesis, closely half hydrogen is because can not effectively utilizing without the CO coupling.As for the production of synthetic ammonia, need transform simultaneously and conversion, complex technical process, investment is high.
The typical composition of producing prepared water-gas take gasification of coal as: CO 47.14%; H
234.35%; CO
217.6%; CH
40.117%; Other is 0.793% years old.H in the water-gas
2/ CO mol ratio only is 0.73, far below the Fischer-Tropsch synthetic gas to H
2The requirement of/CO mol ratio shows as rich carbon and lacks hydrogen.This atmosphere forms and can not satisfy in Fischer-Tropsch synthesis process.For this reason, must adopt water-gas shift technique with the total tolerance of water-gas nearly 50%.According to the following anti-further hydrogen manufacturing of conversion: the CO+H that carries out
2O=CO
2+ H
2, gaseous constituent is behind the Partial Transformation: CO 21.24%; H
246.02%; CO 31.99%; CH
40.093%; Other is 0.657% years old.Cause a large amount of carbon to have neither part nor lot in Fischer-Tropsch synthesis, and with greenhouse gases CO
2Emission loss causes the huge waste of coal resources.
Summary of the invention
The objective of the invention is to utilize the scarce hydrogen of rich carbon of gas maked coal and the scarce carbon of rich hydrogen of coke(oven)gas to carry out complementation generation coal derived fuel and chemical, produce simultaneously urea and fuel gas generation, the Poly-generation of implementation procedure and carbon " zero release ".
Preparation method of the present invention comprises the steps:
(1) raw coal, water vapour and oxygen generate water-gas through gasification of coal, and water-gas obtains the coal gas of just purifying waste water through rough purification;
(2) the water-gas penetration depth after the just purification purifies, and obtains product S, CO and H
2, the CO after the purification and H
2The H next with pressure-variable adsorption
2And and Fischer-Tropsch synthesis cycle tail gas (CO+H
2) be mixed into the Fischer-Tropsch synthetic raw gas, the Fischer-Tropsch synthetic raw gas carries out Fischer-Tropsch synthesis under the fischer-tropsch synthetic catalyst effect, obtain hydrocarbon mixture and tail gas, hydrocarbon mixture separates through prior art can obtain the multiple products such as paraffin, gasoline, diesel oil, solvent oil and petroleum naphtha;
(3) tail gas after Fischer-Tropsch synthesizes is through the separating obtained CO of the first pressure-variable adsorption
2Go to the urea synthesis unit; CO and H that residual exhaust obtains respectively through second, third fractionation by adsorption
2Circulation goes Fischer-Tropsch synthetic; Remaining tail gas obtains product SNG behind time condensation, also can obtain the product electricity through gas turbine power generation with air mixed;
(4) coke(oven)gas carries out cleaning and desulfurization after compression, and the gas behind the cleaning and desulfurization obtains H through pressure-variable adsorption
2With the desorb gas mixture, pressure-variable adsorption gained hydrogen partly goes Fischer-Tropsch synthetic, and the part deammoniation is synthetic; The desorb gas mixture is through for the first time condensation and separation of CO
2Remove urea synthesis, isolate CO
2After residual gas obtain the remaining mixed gas of synthetic natural gas (SNG) product and CO and N2 through the condensation second time;
(5) the isolated a part of hydrogen of pressure-variable adsorption and N
2Under the synthetic ammonia catalyst effect, carry out ammonia synthesis, obtain synthetic ammonia;
(6) synthetic ammonia with for the first time condensation and separation of CO
2, the CO that separates of gasified water coal gas
2And the synthetic rear isolated CO of Fischer-Tropsch
2Gas carries out urea synthesis after mixing, and obtains urea synthesis.
Aforesaid gasification of coal is to adopt the ash fusing fluidized bed powdered coal pressuring gasified technology of U.S. Texaco air flow bed coal water slurry gasification technology, the powdered coal pressuring gasified technology of Dutch shell Xie Er, Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences etc.
Aforesaid water-gas rough purification is can wash tower washing, dedusting through Venturi scrubber, carbon owing to contain a small amount of dust, impurity in the water-gas.When the pressure that generates water-gas through gasification of coal when raw coal, water vapour and oxygen is lower than the synthetic required pressure of Fischer-Tropsch, before carrying out gas compression, the water-gas rough purification also need be carried out preliminary desulfurization, and preliminary desulfurization can be adopted the techniques such as mimosa extract doctor treatment, modified ADA method or complex iron.
The technique that aforesaid deep purifying adopts comprises: low-temperature rectisol (Rectisol) Technology, Polyethylene glycol dimethyl ether (NHD) method.H in the methyl methanol syngas after the purification
2S content is not higher than 0.1ppm.
Aforesaid Fischer-Tropsch is synthetic to be at H:Cmoleratio: (H
2-CO
2)/(CO+CO
2)=1.5-2.2, reaction pressure 1.5-5.0Mpa, temperature of reaction 140-300 ℃, air speed 300-5000h
-1Condition under carry out Fischer-Tropsch synthesis.Can adopt Arge technique, SAS technique, the SSPD technique of South Africa Sasol company, SMDS technique, the MFT of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences technique and the SMFT technique etc. of Shell company.
Aforesaid fischer-tropsch synthetic catalyst comprises following catalyzer: (catalyzer forms the patent No. 02140487.9: cobalt contents 10-80%, zirconium white 15-85%, metal oxide 0-5%), (catalyzer forms the patent No. 00109594.3: cobalt contents 10-35%, without sodium silicon oxide 65-90%), (catalyzer forms the patent No. 01134919.0: the first active ingredient (Fe) content 4-40%, the second active ingredient (group VIII metallic element) content 0.01-10%, auxiliary element (IB, IIIB, IA family metallic element) content 0.01-20%, carrier is almond gac or cocoanut active charcoal), (catalyzer forms the patent No. 200610007543.1: cobalt contents 5-35%, zr element content 0.01-5%, all the other are amorphous Si O
2Carrier), (catalyzer forms US Patent No. 4585798: cobalt contents 5-30%, ruthenium content is the 1/200-1/3400 of cobalt contents, all the other are alumina supporter), (catalyst metal atomic ratio: Fe is 0.8-1.2 to US Patent No. 4719240, Zn is 0.05-0.08, Ti/Mn is 0.25-0.35, Ce is 0.01-0.15, K is 0.01-0.15), (catalyzer forms the patent No. 93106465.1: cobalt contents 5-60%, the second metal (platinum, iridium, rhodium) content is the 0.1-50% of cobalt contents, and all the other are alumina supporter), publication number CN101224425A (cobalt contents 5-35%, other is inert support, comprises indifferent oxide, molecular sieve and carbon material etc.) etc.
The condition of separating such as above-mentioned step (3) Fischer-Tropsch process exhaust the first pressure-variable adsorption is 0.5～3.0MPa, and temperature is less than 40 ℃.
The condition of separating such as above-mentioned step (3) Fischer-Tropsch process exhaust the second pressure-variable adsorption is 0.5～3.0MPa, and temperature is less than 40 ℃.
The condition of separating such as above-mentioned step (3) Fischer-Tropsch process exhaust the 3rd pressure-variable adsorption is 0.5～3.0MPa, and temperature is less than 40 ℃.
The pressure of aforesaid coke(oven)gas after the compression of contracting machine is 1.5-5.0MPa.
As above the described cleaning and desulfurization adopting process of (4) step includes: the modified ADA method, and the mimosa extract method, Fu Makesi one Lip river reaches Coase one elder brother Pa Kusifa etc.
As above the condition of the described pressure-variable adsorption of step (4) is pressure 1.5-4.5MPa, and temperature is less than 40 ℃.
Aforesaid ammonia synthesis technology condition be pressure at hydrogen nitrogen mol ratio 2.9-3.2, pressure 10-35Mpa, temperature 400-500 ℃, air speed is at 10000-30000
-1Between carry out ammonia synthesis reaction under the condition; Ammonia synthesis process comprises: Kellogg's technique, Blang's cryogenic purification technique, ICI AM-V technique, LCA technique and KPK technique.
Aforesaid synthetic ammonia catalyst is A102 type, A106 type, the A109 sections catalyzer of Nanjing Chemical Industry Company; The A110-2 of Zhejiang Polytechnical University, A301 type ammonia synthesis catalyst; IC174-1, ICI35-4, the ICI73-1 type ammonia synthesis catalyst of the iron one cobalt system of Britain ICI company exploitation; The A201 type catalyzer of University of Fuzhou; The KMI of Denmark, KMII, KMIII catalyzer; The C73-1 of the U.S., C73-2 C73-3 type catalyzer etc.
Aforesaid urea synthesis is at temperature 160-210 ℃, pressure 13-24MPa, ammonia carbon mol ratio 2.8-4.5, under the water carbon mol ratio 0.4-0.8 manufacturing condition, carry out urea synthesis reaction, can adopt synthesis technique is water solution total cycling method, air lift method, integrated ammonia urea process, SRR method, the HR of UTI company method etc.
Aforesaid first time, condensing temperature was :-70～-85 ℃, pressure is: 1.5-4.5MPa; Condensing temperature is for the second time :-160～-175 ℃, pressure is: 1.5-4.5MPa.
Internal combustion turbine is adopted in aforesaid generating, and tail gas is preheating to 100～500 ℃, and air is 1: 2～4 by volume, and total pressure is 0.5MPa～2.0MPa, mixes to pass into internal combustion turbine and carry out combustion power generation at 800～1600 ℃.
Advantage of the present invention:
1) this patent organically combines the gas maked coal of " rich carbon lacks hydrogen " and the coke(oven)gas of " Fu Qing lacks carbon ", and optimizes the synthetic and urea synthesis gas of Fischer-Tropsch by pressure-variable adsorption, prepares SNG by deep cooling.
2) this patent technique realized coke(oven)gas without transform, gas maked coal is without map function, greatly simplified technical process.
3) the present invention has without greenhouse gas emission, energy-conservation, water saving, saves investment, and technological process is simple, has realized economy, environment, the Trinitarian coordinated development of the energy.Simultaneously can realize the Fischer-Tropsch synthetic structure control in conjunction with market demand, improve the economy of Fischer-Tropsch building-up process, realize total process economy maximization.
Description of drawings
Fig. 1 is process flow sheet of the present invention
Embodiment
Embodiment 1:
In coal gasification processes, coal is carried out early stage process, spray into the molten poly-vapourizing furnace of ash 1000 ℃ of temperature, carry out chemical reaction with water vapour, the sky pure oxygen of assigning under the pressure 1.0MPa condition, generate and contain CO, H
2, CO
2, H
2O and a small amount of CH
4, H
2The water-gas of the composition such as S, COS.The water-gas that will contain a small amount of dust, impurity carries out rough purification.Because the dust-containing water coal gas that gasification comes still contains sour gas after Venturi scrubber, carbon are washed tower washing, dedusting, cooling.In order to protect compressor, also to adopt the desulfurization of mimosa extract method.Make H
2S content is less than 30mg/Nm
3, the water-gas after the rough purification is compressed to the pressure of 2.5MPa, carries out deep purifying again.Deep purifying adopts polyglycol dimethyl ether process (NHD) method desulfurization and decarburization.The H that removes
2S gas desulfuration recovery unit reclaims sulphur; The CO that removes
2Remove urea synthesis.Water-gas behind the deep purifying and coke(oven)gas pressure-variable adsorption make compressed hydrogen and the tail gas that loops back after synthetic of Fischer-Tropsch to 2.5MPa pressure, the three is mixed into fresh Fischer-Tropsch synthetic gas, H
2S content is lower than 0.1ppm, H:Cmoleratio=(H
2-CO
2)/(CO+CO
2)=2.0.Qualified fresh synthesis gas enters the Fischer-Tropsch synthesis device, and reactor is fixed-bed reactor, at reaction pressure 2.5MPa, and 220 ℃ of temperature of reaction, air speed is at 2000h
-1, adopt the Arge technique of Sasol and the catalyzer for preparing by patent CN1084153, the hydrocarbon mixture and the tail gas that after Fischer-Tropsch is synthetic, obtain.Adopt prior art can obtain the products such as paraffin, diesel oil, gasoline, lubricating oil and petroleum naphtha to the hydro carbons hybrid process.Tail gas is lower the separation in the first fractionation by adsorption device, and 40 ℃ of operational conditions, 2.5MPa condition obtain CO
2Go to the urea synthesis unit; Residual exhaust separates in second, third fractionation by adsorption device successively, 40 ℃ of operational conditions, 2.5MPa condition, and the next hydrogen of coal gas, pressure-variable adsorption after obtaining respectively the synthetic leading portion of CO and hydrogen recycle meeting Fischer-Tropsch and deeply purifying is mixed into the Fischer-Tropsch synthetic raw gas.Remaining tail gas can generate electricity or obtain SNG at two sections deep coolings.Under 2.15MPa pressure, service temperature is 35 ℃ to the extraneous coke(oven)gas that comes, and adopts the desulfurization of mimosa extract method through the coke(oven)gas compressor compresses, and the gas behind the cleaning and desulfurization enters pressure-variable adsorption, at 2.12MPa pressure, obtains H through pressure-variable adsorption under 35 ℃ of the temperature
2With the desorb gas mixture, pressure-variable adsorption gained hydrogen partly goes Fischer-Tropsch synthetic, and the part deammoniation is synthetic; The desorb gas mixture is through for the first time condensation and separation of CO
2Remove urea synthesis, isolate CO
2Residual gas be as cold as-175 ℃ through the condensation second time, obtain synthetic natural gas (SNG) product and CO and N
2Mixed gas, CO and N
2Mixed gas can be used as fuel.By the next H of pressure-variable adsorption
2The N next with air separation facility
2Press H
2: N
2Mol ratio is that 2.95: 1 ratios enter the ammonia synthesis operation, and is compressed at pressure 15MPa, 400 ℃ of conditions of temperature, and air speed is 10000h
-1Lower, carry out ammonia synthesis reaction at the A109 Fe-series catalyst.The ammonia that is synthesized enters urea synthesis.By first condensation and separation of CO
2, the isolated CO of deep purifying
2And the CO that separates of the tail gas of Fischer-Tropsch after synthetic
2Three and liquefied ammonia merge, and add respectively to be pressed into urea synthesizer, adopt the air lift method, and at pressure 13-14MPa, temperature 180-185 ℃, ammonia carbon mol ratio 2.8-2.9 under steam/hydrocarbons ratio 0.4 manufacturing condition, carries out urea synthesis reaction.Urea synthesis obtains 99.7% urea melt through evaporation, send the prilling tower granulation to get urea product.
Embodiment 2:
In coal gasification processes, coal is carried out early stage process, make 65% coal water slurry and spray into Texaco gasifier 1300 ℃ of temperature, carry out chemical reaction with gasified water steam, the sky pure oxygen of assigning under the pressure 7.0MPa condition, generate and contain CO, H
2, CO
2, H
2O and a small amount of CH
4, H
2The water-gas of the composition such as S, COS.The dust-containing water coal gas that gasification comes, after Venturi scrubber, carbon were washed tower washing, dedusting, cooling, penetration depth purified, and adopted the low-temp methanol washing process desulfurization and decarburization in deep purifying.The H that removes
2S gas desulfuration recovery unit reclaims sulphur, the CO that removes
2Remove urea synthesis.Water-gas behind the deep purifying and coke(oven)gas pressure-variable adsorption make compressed hydrogen and the tail gas that loops back after synthetic of Fischer-Tropsch to 2.0MPa pressure, the three is mixed into fresh Fischer-Tropsch synthetic gas, H
2S content is lower than 0.1ppm, H:Cmoleratio: (H
2-CO
2)/(CO+CO
2)=2.1.Qualified fresh synthesis gas enters the Fischer-Tropsch synthesis device, at reaction pressure 2.0MPa, and 240 ℃ of temperature of reaction, air speed is at 3000h
-1, adopt the SMDS technique of Shell company and the catalyzer of patent CN1418933 description to carry out Fischer-Tropsch synthesis, obtain hydrocarbon mixture and tail gas.Adopt prior art can obtain the products such as paraffin, diesel oil, gasoline, lubricating oil and petroleum naphtha to the hydro carbons hybrid process.Tail gas is lower the separation in the first fractionation by adsorption device, and 40 ℃ of operational conditions, 2.5MPa condition obtain CO
2Go to the urea synthesis unit; Residual exhaust separates in second, third fractionation by adsorption device successively, 40 ℃ of operational conditions, 2.5MPa condition, and the next hydrogen of coal gas, pressure-variable adsorption after obtaining respectively the synthetic leading portion of CO and hydrogen recycle meeting Fischer-Tropsch and deeply purifying is mixed into the Fischer-Tropsch synthetic raw gas.Remaining tail gas can generate electricity or obtain SNG at two sections deep coolings.The extraneous coke(oven)gas that comes adopts the desulfurization of modified ADA method through the coke(oven)gas compressor compresses under 2.0MPa pressure, the gas of cleaning and desulfurization at 2.0MPa pressure, under 38 ℃ of the temperature, obtains H through pressure-variable adsorption
2With the desorb gas mixture, pressure-variable adsorption gained hydrogen partly goes Fischer-Tropsch synthetic, and the part deammoniation is synthetic; The desorb gas mixture is through for the first time condensation and separation of CO
2Remove urea synthesis, isolate CO
2Residual gas through the condensation second time, be as cold as-168 ℃, obtain synthetic natural gas (SNG) product and CO and N
2Mixed gas, CO and N
2Mixed gas can be used as fuel.By the next H of pressure-variable adsorption
2The N next with air separation facility
2Press H
2Mol ratio is that 3: 1 ratios enter the ammonia synthesis operation, and is compressed at pressure 30MPa, and under 450 ℃ of conditions of temperature, the inlet tower gas air speed is 20000h
-1, carry out ammonia synthesis reaction under the katalysis of the A201 of University of Fuzhou Fe-series catalyst.The ammonia that is synthesized enters urea synthesis.By first condensation and separation of CO
2, the isolated CO of deep purifying
2And the CO of Fischer-Tropsch process exhaust separation
2Add respectively with liquefied ammonia and to be pressed into urea synthesizer, adopt the UTI HR of company method, at pressure 20.6MPa, 193 ℃ of temperature, ammonia carbon ratio 4.2 under steam/hydrocarbons ratio 0.4 manufacturing condition, is carried out urea synthesis reaction.Urea synthesis obtains 99.7% urea melt through evaporation, send the prilling tower granulation.
Embodiment 3:
In coal gasification processes, coal is carried out early stage process, make 65% coal water slurry and spray into Texaco gasifier 1450 ℃ of temperature, carry out chemical reaction with gasified water steam, the sky pure oxygen of assigning under the pressure 6.0MPa condition, generate and contain CO, H
2, CO
2, H
2O and a small amount of CH
4, H
2The water-gas of the composition such as S, COS.The dust-containing water coal gas that gasification comes, after Venturi scrubber, carbon were washed tower washing, dedusting, cooling, penetration depth purified, and adopted the low-temp methanol washing process desulfurization and decarburization in deep purifying.The H that removes
2S gas desulfuration recovery unit reclaims sulphur, the CO that removes
2Remove urea synthesis.Water-gas behind the deep purifying and coke(oven)gas pressure-variable adsorption make compressed hydrogen and the tail gas that loops back after synthetic of Fischer-Tropsch to 5.OMPa pressure, the three is mixed into fresh Fischer-Tropsch synthetic gas, H
2S content is lower than 0.1ppm, H:Cmoleratio: (H
2-CO
2)/(CO+CO
2)=1.9.Qualified fresh synthesis gas enters the Fischer-Tropsch synthesis device, at reaction pressure 5.0MPa, and 300 ℃ of temperature of reaction, air speed is at 5000h
-1, the catalyzer that adopts the SMFT of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences technique and patent CN200510026968.2 to describe carries out Fischer-Tropsch synthesis, obtains hydrocarbon mixture and tail gas.Adopt prior art can obtain the products such as paraffin, diesel oil, gasoline, lubricating oil and petroleum naphtha to the hydro carbons hybrid process.Tail gas is lower the separation in the first fractionation by adsorption device, and 40 ℃ of operational conditions, 2.5MPa condition obtain CO
2Go to the urea synthesis unit; Residual exhaust separates in second, third fractionation by adsorption device successively, 40 ℃ of operational conditions, 2.5MPa condition, and the next hydrogen of coal gas, pressure-variable adsorption after obtaining respectively the synthetic leading portion of CO and hydrogen recycle meeting Fischer-Tropsch and deeply purifying is mixed into the Fischer-Tropsch synthetic raw gas.Remaining tail gas can generate electricity or obtain SNG at two sections deep coolings.Extraneous next coke(oven)gas arrives under the 5.0MPa pressure through the coke(oven)gas compressor compresses, Fu Makesi-Luo Da Coase one elder brother Pa Kusifa desulfurization, and the gas behind the cleaning and desulfurization at 4.97MPa pressure, under the temperature 45 C, obtains H through pressure-variable adsorption
2With the desorb gas mixture, pressure-variable adsorption gained hydrogen partly goes methyl alcohol synthetic, and the part deammoniation is synthetic; The desorb gas mixture is through for the first time condensation and separation of CO
2Remove urea synthesis, isolate CO
2Residual gas through the condensation second time, be as cold as-160 ℃, obtain synthetic natural gas (SNG) product and CO and N
2Mixed gas, CO and N
2Mixed gas can be used as fuel.By the next H of pressure-variable adsorption
2The N next with air separation facility
2Press H
2: N
2Mol ratio=ratio entered the ammonia synthesis operation in 3.05: 1, and is compressed at pressure 30MPa, and under 450 ℃ of conditions of temperature, entering the tower air speed is 30000h
-1, at U.S. C73-1 Fe-series catalyst, carry out ammonia synthesis reaction.The ammonia that is synthesized enters urea synthesis.By first condensation and separation of CO
2With the isolated CO of deep purifying
2Merge and liquefied ammonia, add respectively and be pressed into urea synthesizer, adopt traditional water solution total cycling method, at pressure 20-22MPa, temperature 185-190 ℃, ammonia carbon ratio 4.5 under the steam/hydrocarbons ratio 0.6-0.7 manufacturing condition, is carried out urea synthesis reaction.Urea synthesis send the prilling tower granulation through the urea melt that evaporation obtains.
Claims (16)
1. one kind is utilized gas maked coal and coke(oven)gas for the technique of raw material Poly-generation, it is characterized in that comprising the steps:
(1), raw coal, water vapour and oxygen generates water-gas through gasification of coal, water-gas obtains the coal gas of just purifying waste water through rough purification;
(2), just the water-gas penetration depth after purifying purifies, and obtains product S, CO and H
2, the CO after the purification and H
2The H next with pressure-variable adsorption
2And and Fischer-Tropsch synthesis cycle tail gas be mixed into the Fischer-Tropsch synthetic raw gas, the Fischer-Tropsch synthetic raw gas carries out Fischer-Tropsch synthesis under the fischer-tropsch synthetic catalyst effect, obtain hydrocarbon mixture and tail gas, hydrocarbon mixture is isolated to paraffin, gasoline, diesel oil, solvent oil and petroleum naphtha multiple product;
(3), the tail gas after Fischer-Tropsch synthesizes is through the separating obtained CO of the first pressure-variable adsorption
2Go to the urea synthesis unit; CO and H that residual exhaust obtains respectively through second, third fractionation by adsorption
2Circulation goes Fischer-Tropsch synthetic; Remaining tail gas obtains product SNG behind time condensation, also can obtain the product electricity through gas turbine power generation with air mixed;
(4), coke(oven)gas carries out cleaning and desulfurization after compression, the gas behind the cleaning and desulfurization obtains H through pressure-variable adsorption
2With the desorb gas mixture, pressure-variable adsorption gained hydrogen partly goes Fischer-Tropsch synthetic, and the part deammoniation is synthetic; The desorb gas mixture is through for the first time condensation and separation of CO
2Remove urea synthesis, isolate CO
2After residual gas obtain synthetic natural gas product and CO and N through the condensation second time
2Remaining mixed gas;
(5), the isolated a part of hydrogen of pressure-variable adsorption and N
2Under the synthetic ammonia catalyst effect, carry out ammonia synthesis, obtain synthetic ammonia;
(6), synthetic ammonia and for the first time condensation and separation of CO
2, the CO that separates of gasified water coal gas
2And the synthetic rear isolated CO of Fischer-Tropsch
2Gas carries out urea synthesis after mixing, and obtains urea synthesis;
Described Fischer-Tropsch is synthetic to be at H:Cmoleratio: (H
2-CO
2)/(CO+CO
2)=1.5-2.2, reaction pressure 1.5-5.0Mpa, temperature of reaction 140-300 ℃, air speed 300-5000h
-1Condition under carry out Fischer-Tropsch synthesis, adopt Arge technique, SAS technique, the SSPD technique of South Africa Sasol company, SMDS technique, the MFT of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences technique or the SMFT technique of Shell company.
2. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 1 is characterized in that for the technique of raw material Poly-generation described gasification of coal is the ash fusing fluidized bed powdered coal pressuring gasified technology that adopts U.S. Texaco air flow bed coal water slurry gasification technology, the powdered coal pressuring gasified technology of Dutch shell Xie Er or Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences.
3. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 1 is the technique of raw material Poly-generation, it is characterized in that described water-gas rough purification be contain a small amount of dust in the water-gas, impurity is washed tower washing, dedusting through Venturi scrubber, carbon; When the pressure that generates water-gas through gasification of coal when raw coal, water vapour and oxygen is lower than the synthetic required pressure of Fischer-Tropsch, before carrying out gas compression, the water-gas rough purification also need be carried out preliminary desulfurization, and mimosa extract doctor treatment, modified ADA method or complex iron technique are adopted in preliminary desulfurization.
4. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 1 is characterized in that for the technique of raw material Poly-generation described deep purifying adopts low-temp methanol washing process technology, polyglycol dimethyl ether process, H in the methyl methanol syngas after the purification
2S content is not higher than 0.1ppm.
5. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 1 is the technique of raw material Poly-generation, it is characterized in that described fischer-tropsch synthetic catalyst comprises following catalyzer: catalyzer forms: cobalt contents 10-35%, form without sodium silicon oxide 65-90% or catalyzer: the first active ingredient Fe content 4-40%, the second active ingredient is group VIII metal element content 0.01-10%, auxiliary element is IB, IIIB, the metal element content 0.01-20% of IA family, carrier is almond gac or cocoanut active charcoal or catalyzer composition: cobalt contents 5-35%, zr element content 0.01-5%, all the other are amorphous Si O
2Carrier or catalyzer form: cobalt contents 5-30%, ruthenium content is the 1/200-1/3400 of cobalt contents, all the other are that alumina supporter or catalyst metal atomic ratio: Fe are 0.8-1.2, Zn is 0.05-0.08, Ti/Mn is 0.25-0.35, and Ce is 0.01-0.15, and K is that 0.01-0.15 or catalyzer form: cobalt contents 5-35%, other is inert support, comprises indifferent oxide, molecular sieve and carbon material.
6. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 1 is characterized in that for the technique of raw material Poly-generation the condition that described step (3) Fischer-Tropsch process exhaust the first pressure-variable adsorption separates is 0.5～3.0MPa, and temperature is less than 40 ℃.
7. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 1 is characterized in that for the technique of raw material Poly-generation the condition that described step (3) Fischer-Tropsch process exhaust the second pressure-variable adsorption separates is 0.5～3.0MPa, and temperature is less than 40 ℃.
8. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 1 is characterized in that for the technique of raw material Poly-generation the condition that described step (3) Fischer-Tropsch process exhaust the 3rd pressure-variable adsorption separates is 0.5～3.0MPa, and temperature is less than 40 ℃.
9. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 1 is characterized in that for the technique of raw material Poly-generation the pressure of described coke(oven)gas after the compression of contracting machine is 1.5-5.0MPa.
10. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 1 is the technique of raw material Poly-generation, and it is characterized in that the described cleaning and desulfurization adopting process of (4) step includes: modified ADA method, mimosa extract method or Fu Makesi one Lip river reach Coase one elder brother Pa Kusifa.
11. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 1 is characterized in that for the technique of raw material Poly-generation the condition of the described pressure-variable adsorption of step (4) is pressure 1.5-4.5MPa, temperature is less than 40 ℃.
12. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 1 is the technique of raw material Poly-generation, it is characterized in that described ammonia synthesis technology condition is that pressure is at hydrogen nitrogen mol ratio 2.9-3.2, pressure 10-35Mpa, temperature 400-500 ℃, air speed is carried out ammonia synthesis reaction under condition between the 10000-30000h-1; Ammonia synthesis process comprises: Kellogg's technique, Blang's cryogenic purification technique, ICI AM-V technique, LCA technique or KPK technique.
13. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 12 is characterized in that for the technique of raw material Poly-generation described synthetic ammonia catalyst is A102 type, A106 type or the A109 sections catalyzer of Nanjing Chemical Industry Company; The A110-2 of Zhejiang Polytechnical University or A301 type ammonia synthesis catalyst; IC174-1, ICI35-4 or the ICI73-1 type ammonia synthesis catalyst of the iron one cobalt system of Britain ICI company exploitation; The A201 type catalyzer of University of Fuzhou; The C73-1 of the KMI of Denmark, KMII or KMIII catalyzer or the U.S., C73-2 or C73-3 type catalyzer.
14. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 1 is the technique of raw material Poly-generation, it is characterized in that described urea synthesis is at temperature 160-210 ℃, pressure 13-24MPa, ammonia carbon mol ratio 2.8-4.5, under the water carbon mol ratio 0.4-0.8 manufacturing condition, carry out urea synthesis reaction, the employing synthesis technique is water solution total cycling method, air lift method, integrated ammonia urea process, SRR method or the HR of UTI company method.
15. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 1 is the technique of raw material Poly-generation, it is characterized in that described first time, condensing temperature was :-70～-85 ℃, pressure is: 1.5-4.5MPa; Condensing temperature is for the second time :-160～-175 ℃, pressure is: 1.5-4.5MPa.
16. a kind of gas maked coal and coke(oven)gas of utilizing as claimed in claim 1 is the technique of raw material Poly-generation, it is characterized in that described generating employing internal combustion turbine, tail gas is preheating to 100～500 ℃, with air be 1: 2～4 by volume, total pressure is 0.5MPa～2.0MPa, and mixing passes into internal combustion turbine and carries out combustion power generation at 800～1600 ℃.
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Effective date of registration: 20180427 Address after: 030001 78 building, 27 Taoyuan South Road, Yingze District, Taiyuan, Shanxi. Patentee after: Zhongke Lu'an Energy Technology Co., Ltd. Address before: 165 mailbox 030001, Shanxi City, Taiyuan Province Patentee before: Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences |