CN102746870A - FT synthesis technology - Google Patents
FT synthesis technology Download PDFInfo
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- CN102746870A CN102746870A CN2012102041346A CN201210204134A CN102746870A CN 102746870 A CN102746870 A CN 102746870A CN 2012102041346 A CN2012102041346 A CN 2012102041346A CN 201210204134 A CN201210204134 A CN 201210204134A CN 102746870 A CN102746870 A CN 102746870A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to an FT synthesis technology which is characterized by comprising the following steps of: feeding purified synthetic gas, circulation gas from a recycle compressor, and hydrogen with adjusted carbon-hydrogen ratio all at once into a mixer to adjust the carbon-hydrogen ratio, and then feeding the obtained gas into a reactor to perform the FT synthesis; isolating the oil-gas mixture after the reaction, wherein the isolated end gas is divided into two parts, one part is fed into the compressor as circulation gas and the other part is fed to recovery process as purge gas from which inert gas, carbon dioxide and hydrogen are isolates and the rest of the purge is fed to a CO shift process to synthesize hydrogen which is fed to the recycle compressor along with the isolated hydrogen. After pressure boost the hydrogen is fed back into the mixer to be cycled as circulation gas for adjusting the H2/CO ratio of the synthetic gas fed into the reactor. Compared with the prior arts, the technology of the invention is advantageous in that the carbon monoxide and the methane gas in the purge gas are all turned to hydrogen which is recovered along with the hydrogen originally contained in the purge gas, so the useful components in the purge gas are recovered furthest, minimizing the raw gas waste, reducing production and operation cost and improving economic benefit.
Description
Technical field
The present invention relates to chemical technique, specifically refer to a kind of Fischer-Tropsch synthesis process.
Background technology
Since this century, coal and Sweet natural gas will progressively replace oil, dominate in energy structure.Change this inexorable trend in order to adapt to the energy and industrial chemicals route, alleviate the bavin, the gasoline imbalance between supply and demand that are becoming tight day, research and develop replacement liquid fluid fuel production technology, just become current domestic and international petrochemical complex professional and technical personnel's important mission.
The production technology of replacement liquid fluid fuel is divided into direct coal liquefaction technology and coal or Sweet natural gas indirect liquefaction technology.So-called indirect liquefaction technology is for the high-pressure coal hydrogenation route of DCL/Direct coal liquefaction, and it is earlier coal or natural gas gasifying reformation to be processed synthetic gas, and synthetic through catalysis then, obtaining with the liquid hydrocarbon is the technology of main products.The theoretical basis of coal or Sweet natural gas indirect liquefaction technology is Fischer-Tropsch synthesis, promptly at high temperature coal is gasified, and it is synthetic to carry out catalysis at a lower temperature.Different reaction conditions, the speed of reaction of Fischer-Tropsch synthesis, transformation efficiency, product distribute different.The major influence factors of Fischer-Tropsch synthesis has: the H of catalyzer, type of reactor, unstripped gas
2/ CO ratio, temperature of reaction, reaction pressure, air speed and running time.
The H of unstripped gas
2The product yield and the selectivity of/CO comparison Fischer-Tropsch synthesis have crucial influence, and different catalyst is for H
2/ CO ratio has different requirement.For same catalyzer, H
2/ CO is than increasing, and the hard wax productive rate descends, and methane production increases.So for indirect liquefaction technology, H
2/ CO is than different, and resulting product distributes also different.For an ICL for Indirect Coal Liquefaction project, gasification technology selects to receive the influence of project construction ground practical situation.In case the feed coal that supplies confirm that gasification technology confirms that the synthetic gas component of gasification gained is also just confirmed.In general, the CO component is higher in the synthetic gas of gasification gained, expect the desired H of ICL for Indirect Coal Liquefaction project Fischer-Tropsch synthesis
2/ CO ratio just needs to convert a part of carbon monoxide in the synthetic gas to hydrogen through transformationreation earlier, to regulate H
2/ CO is than the requirement of satisfying the reaction of Fischer-Tropsch synthesis catalytic.Carbon monodixe conversion reaction (Water-Gas Shift Reaction is called for short WGSR) is one and waits the mole reversible exothermic reaction, need under certain reaction conditions, catalyst action, could react quickly and reach balance.Present carbon monodixe conversion has normal pressure and pressurization; Have two sections middle temperature transformations, three sections middle temperature transformations, height to become a plurality of flow processs such as series connection, specifically adopt which kind of requirements of process according to CO content and conversion in synthetic gas working method, the synthetic gas after the factors such as requirement of remaining CO content definite.The carbon monodixe conversion operation is occupied sizable capital investment shares in whole synthetic gas production process.
Fischer-Tropsch is synthetic be with the synthetic gas be raw material under the effect of catalyzer, be the multiple reaction system of main products with the liquefied hydrocarbon.In actual production,, usually increase the air speed of catalyzed reaction in order to increase the throughput of device.Air speed increases, and conversion of raw material can corresponding decline.Therefore usually adopt tail gas to circulate in the actual production and guarantee conversion of raw material.The tail gas circulation can make the non-reaction component that gets in the reactive system, like enrichments such as nitrogen, argons, when these component enrichments just need discharging to certain content, in order to avoid influence the throughput of device.Contain many useful components in the off-gas of Fischer-Tropsch synthesis system discharging; Be about 40% ~ 50% like hydrogen butt volume content in the off-gas, carbon monoxide butt volume content is 20% ~ 30%, and methane butt volume content (comprising other lighter hydrocarbons such as C2 ~ C7) is 13% ~ 26%; These useful component low-sulfurs; Added value is high, can not burn easily, should recycle.
Present ICL for Indirect Coal Liquefaction technology all is to adopt feed coal gasification → crude synthesis gas purification → carbon monodixe conversion → hydrogenation adjustment synthetic gas H
2/ CO ratio → Fischer-Tropsch synthesis → gas-oil separation → most of tail gas loops back reactor drum, and remainder separates inertia component → useful component Returning reacting system recycle wherein as off-gas.Carbon monodixe conversion reaction purpose is to produce hydrogen as much as possible, produces to be used to adjust synthetic gas H
2The hydrogen of/CO ratio, and hydrogen, carbon monoxide and lower carbon number hydrocarbons recovery process also to be set with the consumption of reduction product before the off-gas discharging, so technical process is long, process control parameter is complicated, and required investment in fixed assets is big.And the off-gas recovery process of synthetic oil operation back segment needs to separate the useless component in the off-gas, like inertia component N
2, discharging such as Ar and carbonic acid gas, with residue get off useful component C O, H
2, CH
4Reclaim Deng lower carbon number hydrocarbons, send reactive system together back to as the virgin gas utilization.Only hydrogen and the CO in the recovering discharging gas of some technologies also arranged, as the virgin gas recycle.
Off-gas reclaims technology and mainly contains four kinds at present, i.e. pressure swing adsorption process (PSA), separation by deep refrigeration, membrane separation process and combination process.Pressure swing adsorption process is under higher pressure, to adsorb, and under lower pressure, accomplishes desorb, and high to the pressure requirement of virgin gas, facility investment is big.Separation by deep refrigeration is traditional low temperature processing, and it utilizes the boiling point difference of charging each component that raw material compression, cooling, liquefaction are reached separating effect, and this method investment is bigger, and working cost is higher, is applicable to the project that extensive, many components reclaim simultaneously.The membrane separation process principle is under pressure-driven, and by the difference in the Rong Xie – diffusion in lip-deep adsorptive power of polymeric membrane and film of each component in the gas, promptly the infiltration rate difference is come separating gas mixture.
Fischer-Tropsch (F-T) synthesis technique off-gas component is complicated, and wherein hydrogen volume (butt) content is 40% ~ 50%; Carbon monoxide volume (butt) content is 20% ~ 30%; Carbonic acid gas volume (butt) content is 0.3% ~ 0.6%; Methane volume (butt) content (comprising other lighter hydrocarbons such as C2 ~ C7) is 13% ~ 26%; Nitrogen (comprising argon etc.) volume (butt) content is 7% ~ 9%.Adopt the present single recovery technology can not be with useful component C O, H
2, CH
4All reclaim Deng lower carbon number hydrocarbons, adopt and respectively reclaim the complicated technology of technology series combination, though can useful component all be reclaimed, too small because of amounts of hydrogen, can not satisfy and regulate the H that gets into the reactive system virgin gas
2The requirement of/CO ratio.
Summary of the invention
Technical problem to be solved by this invention is that the present situation to prior art provides a kind of and can the useful component in the off-gas all be changed into hydrogen, saves carbon monodixe conversion operation in the prior art, regulates the H in the synthetic gas
2/ CO ratio is to satisfy the requirement that Fischer-Tropsch synthesis process is formed raw material.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: this Fischer-Tropsch synthesis process is characterized in that comprising the steps:
Virgin gas obtains synthetic gas after purifying and dedusting, desulfurization, decarburization; The circulation gas of sending here with recycle compressor is sent into mixing tank with the hydrogen of adjustment hydrogen-carbon ratio, the synthetic gas hydrogen-carbon ratio is adjusted to 1.8～2.2 backs send into reactor drum as virgin gas and carry out Fischer-Tropsch synthesis;
The oil that obtains after the reaction, gas mixture are discharged the back from reactor drum and are got into the gas-liquid separation operation, isolate product oil and tail gas; Separate the product oil that obtains and deliver to oil storage equipment;
Separate the tail gas separated into two parts that obtains, first part delivers to described compressor as circulation gas;
Another part gets into recovery process, isolates rare gas element, carbonic acid gas and hydrogen, and rest part is delivered to the synthetic hydrogen of CO shift conversion step as off-gas; Wherein, Isolated rare gas element and carbonic acid gas emptying; Separated hydrogen and deliver to described recycle compressor together through CO shift conversion step synthetic hydrogen is sent described mixing tank recycle back to as circulation gas behind the pressure-raising, is used for regulating the H of the synthetic gas that gets into said reactor drum
2/ CO ratio;
The volume ratio of said first part and another part is 3～6;
The CO shift conversion step of said off-gas comprises the steps:
1. off-gas is warmed up to 160 ~ 500 ℃, mixes with high-temperature vapor; Steam/hydrocarbons ratio in control off-gas and the high-temperature vapor is sent into the carbon monodixe conversion reactor drum then together and is carried out the carbon monodixe conversion reaction between 4 ~ 8, and the carbon monodixe conversion in the off-gas is become carbonic acid gas and hydrogen;
2. the mixed gas after the conversion is heated to 800 ~ 1000 ℃, sends into the methane vapor reforming reactor drum and carry out reforming reaction, the methane in the mixed gas all is reformatted into carbon monoxide and hydrogen;
3. it is 500 ~ 800 ℃ that the heat transfer of mixture gas that will from the methane vapor reforming reactor drum, discharge makes its temperature, sends into then in the quicklime removing carbon dioxide reactor drum and removes CO
2Control CaO/CO
2Equivalence ratio be 1.5 ~ 3;
4. send into membrane separation apparatus after will removing heat transfer of mixture gas behind the carbonic acid gas, pressurization, from mixed gas, isolate hydrogen.
Perhaps,
A kind of Fischer-Tropsch synthesis process is characterized in that comprising the steps:
Virgin gas obtains synthetic gas after purifying and dedusting, desulfurization, decarburization; The circulation gas of sending here with recycle compressor is sent into mixing tank with the hydrogen of adjustment hydrogen-carbon ratio, the synthetic gas hydrogen-carbon ratio is adjusted to 1.8～2.2 backs send into reactor drum as virgin gas and carry out Fischer-Tropsch synthesis;
The oil that obtains after the reaction, gas mixture are discharged the back from reactor drum and are got into the gas-liquid separation operation, isolate product oil and tail gas; Separate the product oil that obtains and deliver to oil storage equipment;
Separate the tail gas separated into two parts that obtains, first part delivers to described compressor as circulation gas;
Another part gets into recovery process, isolates rare gas element, carbonic acid gas and hydrogen, and rest part is delivered to the synthetic hydrogen of CO shift conversion step as off-gas; Wherein, Isolated rare gas element and carbonic acid gas emptying; Separated hydrogen and deliver to described recycle compressor together through CO shift conversion step synthetic hydrogen is sent described mixing tank recycle back to as circulation gas behind the pressure-raising, is used for regulating the H of the synthetic gas that gets into said reactor drum
2/ CO ratio;
The volume ratio of said first part and another part is 3～6;
The CO shift conversion step of said off-gas comprises the steps:
1. send into membrane separation apparatus after off-gas heat exchange, the pressurization, isolate the hydrogen in the off-gas;
2. the off-gas after the dehydrogenation is warmed up to 160 ~ 500 ℃, mixes with high-temperature vapor; Steam/hydrocarbons ratio after the control dehydrogenation in off-gas and the high-temperature vapor is sent into the carbon monodixe conversion reactor drum then together and is carried out the carbon monodixe conversion reaction between 4 ~ 8, and the carbon monodixe conversion in the off-gas is become carbonic acid gas and hydrogen;
3. the mixed gas after the conversion is heated to 800 ~ 1000 ℃, sends into the methane vapor reforming reactor drum and carry out reforming reaction, the methane in the mixed gas all is reformatted into carbon monoxide and hydrogen;
4. it is 500 ~ 800 ℃ that the heat transfer of mixture gas that will from the methane vapor reforming reactor drum, discharge makes its temperature, sends into then in the quicklime removing carbon dioxide reactor drum and removes CO
2Control CaO/CO
2Equivalence ratio be 1.5 ~ 3;
5. send into membrane separation apparatus after will removing heat transfer of mixture gas and the compression behind the carbonic acid gas, from mixed gas, isolate hydrogen.
In the such scheme, described membrane separation apparatus is a hollow fiber membrane separator; Said off-gas or gas mixture get into needs heat exchange to 35 ~ 50 ℃ before the hollow fiber membrane separator, be compressed to more than the 8Mpa.
Compared with prior art; The invention has the advantages that: 1. convert carbon monoxide in the off-gas and methane gas to hydrogen, reclaim, most possibly useful component in the off-gas is reclaimed with the former hydrogen that contains; Reduce the unstripped gas waste, reduced production cost.2. adopt off-gas to reclaim the hydrogen of gained, the hydrogen-carbon ratio that the adjustment material synthesis gas requires no longer is provided with the carbon monodixe conversion hydrogen manufacturing operation in the Fischer-Tropsch synthesis system leading portion virgin gas preparation section, has reduced investment in fixed assets 5.0%～15%.3. reduce two sections low-temperature rectisol operations after the carbon monodixe conversion operation, reduced process cost, improved the economic benefit of project.
Description of drawings
Fig. 1 is the process flow sheet of the embodiment of the invention;
Fig. 2 is an off-gas CO conversion process schema in the embodiment of the invention.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Comparative Examples
The F-T synthetic oil technology of joining fixed-bed reactor with SHELL coal gasification in the prior art is example, and traditional Fischer-Tropsch synthesis oil technology comprises: feed coal gasification → crude synthesis gas purification → carbon monodixe conversion → hydrogenation adjustment H
2/ CO ratio → Fischer-Tropsch synthesizes → gas-oil separation → tail gas circulation → off-gas recycle and reuse → steps such as rare gas element discharging.Details are as follows:
Coal is worn into coal dust (by quality, 90% granularity < 100 μ m) in coal pulverizer, send in the moisture eliminator dryly, sends into the opposed nozzle of SHELL vapourizing furnace bottom then with nitrogen.Mix from the pressurization preheating of the oxygen of air separation facility and with middle pressure superheated vapour and also to send into nozzle.Coal dust and oxygen, water vapour is the generating gasification reaction in vapourizing furnace; The about 1500 ℃ coal gas of high temperature of top of gasification furnace reclaims sensible heat with getting into waste heat boiler about the cooled cooled coal gas of dedusting Quench to 900 ℃, is sent to purification system through dry method dust and wet scrubbing then.Purification system adopts two sections low-temperature rectisol desulfurization and decarburization, one section be arranged on carbon monodixe conversion before, one section be arranged on carbon monodixe conversion after.Synthetic gas after dry method dust and wet scrubbing is sent into first tower, and methyl alcohol sprays into from top of tower, and synthetic gas gets at the bottom of tower, under-60 ℃, removes H
2S and COS.Synthetic gas after the desulfurization gets into 230 ℃ of smart desulfurization of zinc oxide desulfurization tower.Synthetic gas after the smart desulfurization is divided into two portions, and a part is directly sent into the mixing tank before the synthesis reactor, and another part gets into the carbon monodixe conversion operation.
High temperature shift and low temperature shift serial flow are adopted in carbon monodixe conversion.The synthetic gas that gets into the carbon monodixe conversion operation at first gets into the saturator bottom; 170 ℃ hot water under 2.1Mpa pressure the counter current contact next with water heater; By steam-laden, get into high temperature shift reactor after adding a part of water vapour and attemperation to 350 ℃ again.Under the siderochrome catalyst action, in 300 ℃～530 ℃ TRs, carry out carbon monodixe conversion in the high temperature shift reactor.460 ℃ of conversion gas that come out from the hypermutation top are through the interchanger heat exchange, get into low temperature shift reactor after temperature is reduced to 200 ℃.Under the effect of copper base transformation catalyst, in 180 ℃～260 ℃ TRs, carries out carbon monodixe conversion in the low temperature shift reactor, make that carbon monoxide content drops to 0.3% in the synthetic gas.Synthetic gas after the completion carbon monodixe conversion is through the interchanger heat exchange, and the adjustment temperature gets into second tower of two sections low-temperature rectisols at-22 ℃, under-60 ℃, removes the CO in the synthetic gas
2Absorb H
2S, COS and CO
2The methyl alcohol desorb after recycle.
The hydrogen that generates after synthetic gas after the desulfurization, the conversion, the circulation gas that loops back and off-gas reclaim CO, the H of gained
2Be mixed together adjustment H
2/ CO ratio is that 1.8～2.2 backs get into the F-T synthesis reactor, under 230 ℃, 3.0MPa and catalytic condition, carries out the F-T building-up reactions.The synthetic oil-air that reaction generates gets into interchanger, with the circulation gas heat exchange that comes from the gas-liquid surge tank, and the circulation gas recycle after the heating.The gas-oil mixture that is cooled to 140 ℃ gets into hot high score jar, and gas is discharged from cat head, gets into synthetic oil-air-de-salted water interchanger; Liquid is discharged at the bottom of the tower, gets into that heat is low divides jar, and light oil gas is discharged from cat head, gets into the flash steam water cooler, through the recirculated water cooling, gets into cold low branchs jar.The heavy synthetic oil is discharged at the bottom of tower, gets into heavy synthetic oil basin and stores.The gas-oil mixture that from hot high score jar, comes out; In synthetic oil-air-de-salted water interchanger, come from de-salted water house steward's de-salted water cooling; Be cooled to get into the water cooling that is come from circulating water main in synthetic oil-air-recirculated water interchanger after 120 ℃, get into cold high score jar after being cooled to 60 ℃, light oil gas is the lime set separator separates through the suction port of compressor; Liquid returns cold high score jar, and gas goes the compressor cycle utilization.Liquid cools off but the synthetic gas of device and gets into cold low branch jar with coming from flashed vapour, and phlegma goes the lightweight oil basin to store.Also being admitted to the lightweight oil basin from the low light synthetic of dividing pot bottom to discharge of heat stores.From the gas that comes out in cold separating tank top, most of pressurized circulation is returned in the mixing tank before the reactor drum, and small portion gets into off-gas and reclaims technology.
In actual production, the ratio of off-gas and circulation gas can confirm that the ratio of general circulation gas and off-gas is 3～6 according to the content of nonreactive gas components such as nitrogen the gas that comes out from cold separating tank top.
From the off-gas of F-T synthetic oil pilot plant after strainer is removed small impurity; Get into the well heater preheating; Get into tubular fibre formula membrane separation apparatus after being preheating to 60 ℃; Hydrogen is in the per-meate side enrichment, as hydrogen product with send into the recycle of F-T synthetic oil device after CO that follow-up workshop section separates mixes.Ooze and be mainly CO, CH in the residual air
4, N
2With a small amount of light hydrocarbon component, get into light hydrocarbon recovery system, through the organic steam membrane sepn, lighter hydrocarbons send storage tank stores to do it in addition and use.Tail gas gets into the PSA-CO purifier units, through the pressure drop of absorption → all press → contraryly put → vacuumize → all voltage rise pressures → purified gas gas lift is pressed six process cycle alternations, carries out the CO separation.Attaches the weak absorbed component (CH in the tower dead space
4, N
2, H
2) torch reduces internal heat.Off-gas reclaims the H of gained
2Return in the mixing tank before the reactor drum with CO pressurized circulation together.
Embodiment
As depicted in figs. 1 and 2, the Fischer-Tropsch synthesis process that the SHELL coal gasification of employing patent art is joined fixed-bed reactor comprises the steps:
Feed coal 1 is gasificated into raw gas 2 through gasification operation 1 '; Get into the synthetic gas 3 after the 2 ' dedusting of raw gas purifying operation, desulfurization, decarburization are purified then; Circulation gas with recycle compressor 7 ' comes is sent into mixing tank 3 ' with the hydrogen 12 of adjustment hydrogen-carbon ratio, the synthetic gas hydrogen-carbon ratio is adjusted to about 2.0 backs send into reactor drum 4 ' as virgin gas 4 and carry out the F-T building-up reactions.Reaction finishes to get into gas-liquid separation operation 5 ' from the synthetic oil-air mixture 5 that reactor drum 4 ' is discharged and separates oil product and tail gas.Isolated product oil 13 send the oil storage facility.Isolated synthesis tail gas 6 separated into two parts, a part gets into off-gas recovery process 6 ' conversion recover hydrogen as off-gas 7.Another part tail gas 8 advances compressor 7 ' as the part of circulation gas.Remaining nitrogen (comprising argon etc.) and carbonic acid gas 10 emptyings or processing after off-gas recovery process 6 ' conversion recover hydrogen, the hydrogen 9 of recovery gets into recycle compressor 7 ' with tail gas 8 as circulation gas 11 and behind pressure-raising, sends mixing tank 3 ' recycle back to as circulation gas.Details are as follows:
Coal is worn into coal dust (by quality in coal pulverizer; 90% granularity 100 μ m); Send into drying in the moisture eliminator, send into the opposed nozzle of SHELL vapourizing furnace bottom then with nitrogen, mix from the oxygen pressurization preheating of air separation facility and with middle pressure superheated vapour and also send into nozzle.Coal dust and oxygen, water vapour is the generating gasification reaction in vapourizing furnace.The about 1500 ℃ coal gas of high temperature of top of gasification furnace reclaims sensible heat with getting into waste heat boiler about the cooled cooled coal gas of dedusting Quench to 900 ℃, is sent to purification system through dry method dust and wet scrubbing then.Purification system adopts low-temperature rectisol desulfurization and decarburization, and the synthetic gas after dry method dust and wet scrubbing is sent into adsorption tower, and methyl alcohol sprays into from top of tower, and synthetic gas gets at the bottom of tower, under-60 ℃, removes H
2S, COS and carbonic acid gas.Synthetic gas behind the desulfurization and decarburization gets into 230 ℃ of smart desulfurization of zinc oxide desulfurization tower.The mixing tank that synthetic gas after the smart desulfurization is delivered to before the synthesis reactor reclaims gained H with circulation gas that loops back and off-gas
2Be mixed together adjustment H
2/ CO ratio is that 1.8～2.2 backs get into the F-T synthesis reactor, under 230 ℃, 3.0MPa and catalytic condition, carries out the F-T building-up reactions.The synthetic synthetic oil-air that generates gets into interchanger, and with the circulation gas heat exchange that comes from the gas-liquid surge tank, the circulation gas after the heating goes the mixing tank recycle.The gas-oil mixture that is cooled to 140 ℃ gets into hot high score jar, and gas is discharged from cat head, gets into synthetic oil-air-de-salted water interchanger; Liquid is discharged at the bottom of the tower, gets into that heat is low divides jar, and light oil gas is discharged from cat head, gets into the flash steam water cooler, through the recirculated water cooling, gets into cold low branchs jar.The heavy synthetic oil is discharged at the bottom of tower, gets into heavy synthetic oil basin and stores.The gas-oil mixture that from hot high score jar, comes out; In synthetic oil-air-de-salted water interchanger, come from de-salted water house steward's de-salted water cooling; Be cooled to get into the water cooling that is come from circulating water main in synthetic oil-air-recirculated water interchanger after 120 ℃, get into cold high score jar after being cooled to 60 ℃, light oil gas is the lime set separator separates through the suction port of compressor; Liquid returns cold high score jar, and gas goes the compressor cycle utilization.Liquid gets into cold low branch jar with the synthetic gas that comes from the flashed vapour water cooler, and phlegma goes the lightweight oil basin to store.Also being admitted to the lightweight oil basin from the low light synthetic of dividing pot bottom to discharge of heat stores.The gas that comes out from cold separating tank top is tail gas, tail gas component more complicated, and wherein hydrogen volume (butt) content is 40% ~ 50%; Carbon monoxide volume (butt) content is 20% ~ 30%; Carbonic acid gas volume (butt) content is 0.3% ~ 0.6%; Methane volume (butt) content (comprising other lighter hydrocarbons such as C2 ~ C7) is 13% ~ 26%; Nitrogen (comprising argon etc.) volume (butt) content is 7% ~ 9%.With the butt volume is 1000Nm
3Off-gas be example, its gas composition such as table 1.
Most of tail gas pressurized circulation is returned in the mixing tank before the reactor drum, and small portion gets into as off-gas and reclaims technology, isolates wherein hydrogen, CO
2And rare gas element; Wherein hydrogen returns recycle compressor, and remaining off-gas gets into the CO shift conversion step.
The ratio of above-mentioned off-gas and circulation gas can be carried out the routine adjusting according to the content of nonreactive gas components such as nitrogen the gas that comes out from cold separating tank top, and the ratio of general circulation gas and off-gas is 3～6.Both ratios are 4.33 in the present embodiment.
Off-gas reclaims technology, and details are as follows:
The off-gas of the outer cooler discharge of Fischer-Tropsch synthesis process off-gas is sent into compressor 61 be pressurized to about 8.0Mpa; Send into about interchanger 62 adjustment gas temperatures to 40 ℃; Send into first hollow fiber membrane separator 63 then, control air speed 2.5m/s, inlet outlet pressure differential 60kg/cm
2Hydrogen from separator infiltrates together with the hydrogen that infiltrates from following second hollow fiber membrane separator 610, send the hydrogen-carbon ratio of Fischer-Tropsch synthesis process gas mixer adjustment synthetic gas.
After first hollow fiber membrane separator 63 separates, separablely go out in the off-gas about 45% hydrogen, also contain have an appointment 37% ~ 56% carbon monoxide and 23% ~ 48% methane in the off-gas after the dehydrogenation, these two kinds of gases adopt membrane separation apparatuss can not with nitrogen separation.Off-gas after the dehydrogenation is sent into interchanger 64 be warmed up to 350 ℃; Mix with high-temperature vapor; Steam/hydrocarbons ratio is 5 in the adjustment gas mixture; Send into CO shift-converter 65 then together and carry out one section conversion, under the cobalt-molybdenum series catalyst katalysis, carry out the carbon monodixe conversion reaction, the carbon monodixe conversion in the mixed gas is become carbonic acid gas and hydrogen.
The mixed gas that obtains after the conversion is heated to 900 ℃ in interchanger 66, gets into methane vapor reforming reactor drum 7 and carry out two sections conversion, the methane in the mixed gas all is reformatted into carbon monoxide and hydrogen.
If the treatment capacity of gas mixture is bigger, interchanger 66 can the parallel connection bypass interchanger, gas mixture is shunted heat exchange.The mixed gas of discharging from methane vapor reforming reactor drum 67, gets in the quicklime removing carbon dioxide reactor drum 68 and carries out three sections conversion after temperature drops to 550 ℃ through interchanger 6 heat exchange, makes CO
2With an amount of quicklime reaction that the top sprays into, the calcium oxide content that sprays into is controlled to be CaO/CO
2Equivalence ratio is 2.5.The lime carbonate of discharging from reactor drum 68 bottoms send calcining furnace to be sintered into recycle behind the quicklime.
Mixed gas behind the decarbonation is mainly nitrogen, argon gas and hydrogen to be sent into interchanger 64 and cools to about 40 ℃; Send into compressor 69 then and be pressurized to about 8Mpa; Send into second hollow fiber membrane separator 610, carry out separating of hydrogen and nitrogen and argon gas in the mixed gas.Sepn process control air speed 2.5m/s, inlet outlet pressure differential 60kg/cm
2, 40 ℃ of separation temperatures.From the hydrogen that separator infiltrates, the hydrogen that infiltrates together with first hollow fiber membrane separator 63 send the Fischer-Tropsch synthesis process gas mixer to adjust the hydrogen-carbon ratio of synthetic gas.The not nitrogen and the argon gas emptying of infiltration.
This patent separates the gas products hydrogen of purifying and adopts the GC-930-DL refinery gas of Shanghai chaste tree and the production of analyser Instr Ltd. to analyze special-purpose gas chromatograph; The sampling of sampling valve place is installed detects collecting outlet that twice separated hydrogen loop back the synthesis technique pipeline, recording hydrogen purity and be 90% hydrogen recovery rate is 95%.
Present embodiment adopts two hollow fiber membrane separators i.e. first hollow fiber membrane separator 63 and second hollow fiber membrane separator 610.Hollow fiber membrane separator also can adopt the membrane separation apparatus of other separable hydrogen to substitute, and for example uses metallic membrane separator, ceramic membrane separator and carbon film separator.
The hollow fiber membrane separator that hollow fiber membrane separator in the present embodiment all adopts Wu Jing chemical plant, Shanghai to produce.This separator is made up of metal shell and core, and raw material is made the shell side of membrane separation apparatus leave with rage, and tube side is made in infiltration leave with rage.The metal casing physical efficiency is born high pressure, and core is by several ten thousand about 0.5mm of external diameter, and the ps hollow fiber uf membrane of internal diameter 0.2mm is formed tube bank.The ultimate principle of membrane separation apparatus is to utilize the partial pressure difference of film both sides gas to be impellent, through infiltration-dissolving-diffusion-analyzing step, thereby utilizes tubular fibre different from H to the selection perviousness of all gases
2With gas CO slowly
2, Ar, CO, CH
4And N
2Separately.Hollow-fibre membrane to the seepage velocity of all gases is: H
2O＞H
2＞He>=H
2S＞CO
2>=O
2>=Ar＞CO＞CH
4＞N
2, the feeding temperature of regulating membrane separation apparatus is 40 ℃, the about 8.0MPa of pressure, and air speed is 2.5m/s, hydrogen recovery rate is about 95%.
The CO shift-converter adopts the LYB-99 co-mo antisulphuric transforming catalyst that source, Shandong Zibo Shandong commercial catalysts ltd produces in the present embodiment, and range of reaction temperature is 160 ~ 500 ℃, and pressure range is that (0 ~ 0.6MPa), steam/hydrocarbons ratio is 4 ~ 6 to 0 ~ 6atm.The heat that reaction is emitted can add thermal material itself, its temperature is raise heat up in advance for next step methane steam reformation.Two sections except that proceeding carbon monodixe conversion, the temperature of charge that further raises carries out methane steam reformation reaction.
The catalyst for producing hydrogen from steam conversion nickel-base catalyst that the methane vapor reforming reaction adopts Shandong Gong Quan chemical inc to produce in the present embodiment, range of reaction temperature is 800 ~ 1000 ℃, and pressure is 0 ~ 6atm, and steam/hydrocarbons ratio is 4 ~ 6.Reaction is for thermo-negative reaction, for keeping temperature of reactor in required TR, can adopt the electric heater heat supply to replenish heat poor of carbon monodixe conversion reaction liberated heat and methane reforming absorption.Three sections conversion all are transformed into all carbon monoxide in the material carbonic acid gas and the hydrogen except that proceeding carbon monodixe conversion, also carry out carbonic acid gas and the combination reaction that sprays into quicklime.The temperature of reaction of this reaction is 500 ~ 800 ℃, thermopositive reaction.The heat that this reaction is emitted can be used for heating the into virgin gas temperature of first stage reactor.The highly active calcium oxide that quicklime in the present embodiment adopts the inferior industry and trade of Shandong Zibo ltd to produce.
If do not adopt first hollow fiber membrane separator 3 in the present embodiment; Off-gas is directly carried out sending into second hollow fiber membrane separator 10 after three sections conversions; Can accomplish the Separation and Recovery of hydrogen equally, the recovery of products obtained therefrom hydrogen is 85%, and the purity of hydrogen is 90%.Compare with the method that adopts first hollow fiber membrane separator, it is high a lot of that the facility investment of this method and operation energy consumption are all wanted.
Reclaim the technology separation through above-mentioned off-gas and obtain hydrogen 430.6Nm
3, carbon monodixe conversion obtains hydrogen 230.9Nm
3, the 988.4Nm of methane vapor reforming gained
3Three amount to 1649.9Nm
3
Table 1 gas composition (butt V/V%)
Different catalyst, different synthesis reactor, in general the Fischer-Tropsch synthesis oil technological cycle is controlled in 2～5 scopes than different, that is to say that the circulation gas and the volume ratio of the new synthetic gas that purifies laggard reactor drum are 2～5.With the SHELL gasifying process is example, if a Fischer-Tropsch synthesis oil device, the material gas quantity that per hour advances reactor drum is 60000Nm
3/ hour, the reaction cycle ratio is 3, requires H in the virgin gas of reactor drum
2/ CO ratio is 2, then:
V
Follow(gas vol that loops back)+V
Only(advancing the fresh synthesis gas amount of reactor drum)+V
Hydrogen(adjustment H
2/ CO is than required amounts of hydrogen)=60000
V
Hydrogen(adjustment H
2/ CO is than required amounts of hydrogen)=60000-V
Follow(gas vol that loops back)-V
Only(advancing the fresh synthesis gas amount of reactor drum) ... .... (1)
V
Follow(gas vol that loops back)/V
Only(advancing the fresh synthesis gas amount of reactor drum)=3 ... (2)
Require H in the virgin gas of reactor drum
2/ CO ratio is 2,, that is:
According to above-mentioned three equations, calculate:
V
Only(advancing the fresh synthesis gas amount of reactor drum)=11665.89Nm
3/ hour
V
Follow(gas vol that loops back)=34997.67Nm
3/ hour
V
Hydrogen(adjustment H
2/ CO is than required amounts of hydrogen)=13336.4Nm
3/ hour
13336.4Nm
3/ hour adjustment H
2/ CO amounts to become to discharge tolerance and be than required amounts of hydrogen:
13336.4 ÷ 1649.9 * 1000=8083.16Nm
3/ hour
That is: with 8083.16Nm
3/ hour tail gas send into off-gas as off-gas and recycle workshop section and reclaim, obtain 13336.4Nm
3/ hour hydrogen, with 34997.67Nm
3/ hour tail gas as circulation gas, together loop back reactive system, replenish 11665.89Nm to system again
3Fresh synthesis gas after the/hour purification can be formed 60000Nm
3/ hour H
2/ CO gets into reactor drum than the virgin gas that is 2, and the ratio of the off-gas of circulation gas and recovery is that 4.33, two indexs all can satisfy processing requirement in addition.
Compare Comparative Examples and embodiment, Comparative Examples adopts two sections conversion to generate hydrogen, removes the carbonic acid gas that shift conversion step generates with two sections low-temperature rectisols.At the off-gas recovery stage; Adopt the hollow-fibre membrane separating hydrogen gas; Adopt organic steam membrane sepn lighter hydrocarbons, adopt PSA-CO transformation absorption purifying plant, through the pressure drop of absorption → all press → contraryly put → vacuumize → equal voltage rise pressure → purified gas six tower cycle alternation separation of C O that boost.
Embodiment has then reduced two sections CO conversion and second section low-temp methanol eccysis CO in the synthetic gas production process
2Operation.At the off-gas recovery process, compare with embodiment 1, reduced lighter hydrocarbons recovery operation, PSA-CO transformation absorption purifying plant, increased by one section tubular fibre hydrogen recovery unit and two sections shift conversion steps.The gas vol that two periods shift conversion step unit time that increase handle is compared with Comparative Examples, and scale reduces to 35% of embodiment 1.Scale is reduced to 35%, and investment reduces by 25%～50% approximately.In same project; The lighter hydrocarbons recovery operation adds that the investment cost of PSA-CO transformation absorption purifying plant is about 3.0 times of one section tubular fibre hydrogen recovery unit; Therefore lighter hydrocarbons recovery operation, PSA-CO transformation absorption purifying plant have been reduced; Increase by one section tubular fibre hydrogen recovery unit and compared ratio, also reduced project investment to a certain extent.
A certain EPC project with Ningbo engineering corporation of China Petrochemical Industry is an example, and carbon monodixe conversion operation stage devices needed has high temperature shift reactor, low temperature shift reactor, interchanger, humidifier etc., and the engineering cost of investment is 7593.13 ten thousand yuan; One section low-temperature rectisol has equipment such as interchanger, washing tower, regenerator column, and the engineering cost of investment is 1,823 ten thousand yuan; The two adds up to the reduction engineering cost is 9,416 ten thousand yuan.The off-gas recovery process, the engineering cost of organic vapor film light ends unit investment is about 9,150,000 yuan; The investment cost of PSA-CO transformation absorption purifying plant is about 5,824 ten thousand yuan; The engineering cost that one cover hydrogen tubular fibre retrieving arrangement needs is about 2,340 ten thousand yuan, then adopts patent art, can reduce by ten thousand yuan of engineering cost: 7593 * (100%-40%)+1823-2340+5824+915=10779.This project gross investment is 1,800,000,000 yuan, and the then enforcement of present technique can reduce project investment 6.0%.
Claims (3)
1. a Fischer-Tropsch synthesis process is characterized in that comprising the steps:
Virgin gas obtains synthetic gas after purifying and dedusting, desulfurization, decarburization; The circulation gas of sending here with recycle compressor is sent into mixing tank with the hydrogen of adjustment hydrogen-carbon ratio, the synthetic gas hydrogen-carbon ratio is adjusted to 1.8～2.2 backs send into reactor drum as virgin gas and carry out Fischer-Tropsch synthesis;
The oil that obtains after the reaction, gas mixture are discharged the back from reactor drum and are got into the gas-liquid separation operation, isolate product oil and tail gas; Separate the product oil that obtains and deliver to oil storage equipment;
Separate the tail gas separated into two parts that obtains, first part delivers to described compressor as circulation gas;
Another part gets into recovery process as off-gas, isolates rare gas element, carbonic acid gas and hydrogen, and rest part is delivered to the synthetic hydrogen of CO shift conversion step; Wherein, Isolated rare gas element and carbonic acid gas emptying; Separated hydrogen and deliver to described recycle compressor together through CO shift conversion step synthetic hydrogen is sent described mixing tank recycle back to as circulation gas behind the pressure-raising, is used for regulating the H of the synthetic gas that gets into said reactor drum
2/ CO ratio;
The volume ratio of said first part and off-gas is 3～6;
The recovery process of said off-gas comprises the steps:
1. off-gas is warmed up to 160 ~ 500 ℃, mixes with high-temperature vapor; Steam/hydrocarbons ratio in control off-gas and the high-temperature vapor is sent into the carbon monodixe conversion reactor drum then together and is carried out the carbon monodixe conversion reaction between 4 ~ 8, and the carbon monodixe conversion in the off-gas is become carbonic acid gas and hydrogen;
2. the mixed gas after the conversion is heated to 800 ~ 1000 ℃, sends into the methane vapor reforming reactor drum and carry out reforming reaction, the methane in the mixed gas all is reformatted into carbon monoxide and hydrogen;
3. it is 500 ~ 800 ℃ that the heat transfer of mixture gas that will from the methane vapor reforming reactor drum, discharge makes its temperature, sends into then in the quicklime removing carbon dioxide reactor drum and removes CO
2Control CaO/CO
2Equivalence ratio be 1.5 ~ 3;
4. send into membrane separation apparatus after will removing heat transfer of mixture gas behind the carbonic acid gas, pressurization, from mixed gas, isolate hydrogen.
2. a Fischer-Tropsch synthesis process is characterized in that comprising the steps:
Virgin gas obtains synthetic gas after purifying and dedusting, desulfurization, decarburization; The circulation gas of sending here with recycle compressor is sent into mixing tank with the hydrogen of adjustment hydrogen-carbon ratio, the synthetic gas hydrogen-carbon ratio is adjusted to 1.8～2.2 backs send into reactor drum as virgin gas and carry out Fischer-Tropsch synthesis;
The oil that obtains after the reaction, gas mixture are discharged the back from reactor drum and are got into the gas-liquid separation operation, isolate product oil and tail gas; Separate the product oil that obtains and deliver to oil storage equipment;
Separate the tail gas separated into two parts that obtains, first part delivers to described compressor as circulation gas;
Another part gets into recovery process as off-gas, isolates rare gas element, carbonic acid gas and hydrogen, and rest part is delivered to the synthetic hydrogen of CO shift conversion step as off-gas; Wherein, Isolated rare gas element and carbonic acid gas emptying; Separated hydrogen and deliver to described recycle compressor together through CO shift conversion step synthetic hydrogen is sent described mixing tank recycle back to as circulation gas behind the pressure-raising, is used for regulating the H of the synthetic gas that gets into said reactor drum
2/ CO ratio;
The volume ratio of said first part and off-gas is 3～6;
The recovery process of said off-gas comprises the steps:
1. send into membrane separation apparatus after off-gas heat exchange, the pressurization, isolate the hydrogen in the off-gas;
2. the off-gas after the dehydrogenation is warmed up to 160 ~ 500 ℃, mixes with high-temperature vapor; Steam/hydrocarbons ratio after the control dehydrogenation in off-gas and the high-temperature vapor is sent into the carbon monodixe conversion reactor drum then together and is carried out the carbon monodixe conversion reaction between 4 ~ 8, and the carbon monodixe conversion in the off-gas is become carbonic acid gas and hydrogen;
3. the mixed gas after the conversion is heated to 800 ~ 1000 ℃, sends into the methane vapor reforming reactor drum and carry out reforming reaction, the methane in the mixed gas all is reformatted into carbon monoxide and hydrogen;
4. it is 500 ~ 800 ℃ that the heat transfer of mixture gas that will from the methane vapor reforming reactor drum, discharge makes its temperature, sends into then in the quicklime removing carbon dioxide reactor drum and removes CO
2Control CaO/CO
2Equivalence ratio be 1.5 ~ 3;
5. send into membrane separation apparatus after will removing heat transfer of mixture gas and the compression behind the carbonic acid gas, from mixed gas, isolate hydrogen.
3. Fischer-Tropsch synthesis process according to claim 1 and 2 is characterized in that described membrane separation apparatus is a hollow fiber membrane separator; Said off-gas or gas mixture get into needs heat exchange to 35 ~ 50 ℃ before the hollow fiber membrane separator, be compressed to more than the 8Mpa.
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| CN112239196A (en) * | 2020-10-17 | 2021-01-19 | 大连理工大学 | Multi-heat source complementary hydrogen production device based on high-temperature heat pipe heat collection |
| CN114394594A (en) * | 2022-01-16 | 2022-04-26 | 四川天人化学工程有限公司 | Improved process for purifying low-hydrogen high-concentration carbon monoxide |
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