CN104893748A - Method for producing tar and hydrocarbon fuel products from coal - Google Patents
Method for producing tar and hydrocarbon fuel products from coal Download PDFInfo
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- CN104893748A CN104893748A CN201510333159.XA CN201510333159A CN104893748A CN 104893748 A CN104893748 A CN 104893748A CN 201510333159 A CN201510333159 A CN 201510333159A CN 104893748 A CN104893748 A CN 104893748A
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Abstract
The invention relates to a method for producing tar and hydrocarbon fuel products from coal. The method comprises steps of pyrolysis, raw gas purification and desulfurization, a methanation process, a methane separation process, a gasification process, a conversion process, a purification process, a sulfur recovery process, a fine desulfurization process, a synthesis process and the like. With the adoption of the method, raw coal is firstly subjected to low-temperature pyrolysis and then subjected to gasification conversion, the types of coal chemical products are increased, and the utilization efficiency of the coal raw material is improved; the problem that low-rank coal cannot be gasified and utilized by a wet-process entrained-flow bed is solved, the raw material consumption during gasification is reduced, the waste water discharge is reduced, the greenhouse gas production amount in the process is reduced, and efficient class-based and quality-based utilization of the coal resource is realized.
Description
[technical field]
The invention belongs to coal resources processing technique field.More specifically, the present invention relates to a kind of method utilizing coal to produce tar and hydrocarbon fuel product.
[background technology]
China rich coal, oil starvation, weak breath, utilizing comparatively plentiful coal resources to produce the Sweet natural gas, the oil fuel (hydrocarbon fuel) that comparatively lack is the basic energy strategy route of China, is ensure that Chinese society is stablized, the important technology of national security ensures.Utilize coal production hydrocarbon fuel product be generally by coal through gasification after recycling gasification produce the method that raw gas carries out resynthesis, the method ripening degree that possesses skills is high, raw gas product is single, following process route feature flexibly, it is existing coal chemical industry focus route, but along with China is to the intensification of Coal Industrial and the awareness of coal resources own, the problem adopting this route to expose in the Appropriate application of adaptability to raw material and coal manifests day by day.
In Coal Gasification Technology adaptability to raw material, although domestic comparatively advanced and apply more entrained flow bed gasification technology fine coal can be adopted to be raw material, but still there is the problems such as Feedstock treating process is loaded down with trivial details, energy consumption is high when directly utilizing and account for the most low-rank coal of coal resources in China total reserves (brown coal, long-flame coal) resource in this technology, limits the heavy industrialization chemical utilization of such coal.Gasification installation domestic at present mostly select meta-bituminous coal even hard coal as gasified raw material, and low-rank coal (brown coal, long-flame coal) is all taken as resource inferior mostly for combustion power generation, small part is used to simple pyrolysis process and extracts tar, all there is environmental pollution and the not high realistic problem of efficiency of energy utilization in its production process, affects the efficient and rational utilization of coal resources particularly above-mentioned low-rank coal resource.
As everyone knows, coal can obtain coal-tar products by pyrolysis (coking), this material is important natural compounds treasure-house, wherein contained a lot of compound monomer components cannot be obtained by the mode of synthetic, therefore coal tar itself has important chemistry and chemical utilization value, tackles it and keeps higher attention degree.Coal tar derives from natural macromolecular organic substance contained in coal, but in the same comparatively violent gasification of similar combustion processes, Macromolecule in coal material seldom or at all cannot realize its long chain break and effusion activity, the overwhelming majority or be converted into CO and H completely
2cause the utility value of macromolecular substance in coal seldom to can not get reasonable embodiment even at all, waste this precious resources in coal, reduce the utilising efficiency of coal resources on the whole, in the low-rank coal efficiency utilization that coal utilization is particularly higher containing volatile matter, the classification sub-prime of carrying out coal utilizes and is considered at present the most reasonably coal utilization mode.
[summary of the invention]
[technical problem that will solve]
The object of this invention is to provide a kind of method utilizing coal to produce tar and hydrocarbon fuel product.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of method utilizing coal to produce tar and hydrocarbon fuel product.
The step of the method is as follows:
A, pyrogenic processes
Preprocessing grinding powder coal is sent into pyrogenic processes, described coal dust decomposes 35-80min at temperature 450 ~ 800 DEG C with the condition of pressure-0.05 ~ 0.05MPa, generate a kind of tar light oil in gaseous state and raw gas mix products with a kind of be solid-state semicoke product, then allow described tar light oil and raw gas mix products by dedusting, cooling washing and oily water separation, obtain a kind of tar products and a kind of raw gas product;
B, raw gas purifying desulfurization
The raw gas product allowing steps A obtain is at air speed 1000 ~ 3000h
-1, under temperature 60 ~ 80 DEG C and the condition of pressure 0.05 ~ 0.1MPa by being equipped with scavenging agent bed and desulfurizing agent bed cleaner successively, remove the micro-heterogeneous ring compound and sulfocompound that wherein contain, obtain the clean raw gas of heterogeneous ring compound content <0.02ppm and sulphur content <0.1ppm by weight;
Allow a part of clean raw gas product return pyrogenic processes as heating fuel and pyrolysis atmosphere, rest part delivers to follow-up methanation operation;
C, methanation operation
The clean raw gas allowing step B obtain is at air speed 3000 ~ 10000h
-1, under temperature 250 ~ 600 DEG C and the condition of pressure 2.0 ~ 3.0MPa by methanation catalyst reactor, make H wherein
2respectively with CO and CO
2carry out methanation reaction, obtain a kind of methane-rich gas mixture;
D, methane separation operation
The methane-rich gas mixture obtained by step C is delivered in methane separation operation, is separated under the condition that conventional pressure-variable adsorption is separated, and obtains concentration for CH by volume
4the gas product of >95% and containing H
2, CO and CO
2the gas mixture of main ingredient;
E, gasification process
The semicoke product obtained by steps A and high purity oxygen gas, water or water vapor carry out wet method at temperature 1200.0 ~ 1400.0 DEG C with the condition of pressure 1.0 ~ 10.0MPa or dry gasification reacts, and obtains mainly containing CO and H
2crude synthesis gas;
F, shift conversion step
A crude synthesis gas part obtained in step e is at air speed 1500 ~ 3500h
-1, under temperature 300 ~ 500 DEG C and the condition of pressure 0.8 ~ 9.5MPa by transformation catalyst reactor, the CO allowing described crude synthesis gas contain and water vapor carry out transformationreation, described crude synthesis gas is transformed into and mainly contains H
2hydrogen-rich gas, then it mix with the crude synthesis gas of remainder, obtains a kind of mixing transformation gas;
G, cleaning section
The conversion gas obtained by step F is mixed with the gas mixture obtained by step D, obtain a kind of mixed gas, then with under the existence of described gas mixture volumeter 0.5 ~ 2% absorption agent, at temperature-60 ~ 0 DEG C with the condition of pressure 0.6 ~ 9.0MPa, carry out purifying treatment, remove whole CO that described mixed gas contains
2with most of sulfocompound, be purified synthetic gas, high-purity CO respectively
2gas and sulfocompound gas; The CO of described decontaminating syngas
2content is less than 10ppm, and sulfocompound content is less than 0.1ppm;
H, sulfur recovery process
The sulfocompound gas allowing step G obtain delivers to the oxidation unit of sulfur recovery process, and incite somebody to action wherein a part of selective oxidation of sulfur containing compounds in particular, then with remaining sulfocompound gas and vapor permeation, the gas mixture obtained is again at air speed 250 ~ 550h
-1, under temperature 150 ~ 450 DEG C and the condition of pressure 0.2 ~ 3.5MPa by sulphur synthetic catalyst reactor, allow the sulphur of wherein sulfocompound change into elemental sulfur, obtain a kind of sulfur product;
I, fine de-sulfur operation
By the decontaminating syngas that obtained by step G at air speed 1000 ~ 3000h
-1, carry out desulphurization reaction by sweetening agent cleaner under temperature 60 ~ 80 DEG C and the condition of 0.5 ~ 8.5MPa, make the sulfur component of described decontaminating syngas be down to below 0.01ppm by volume, obtain a kind of pure synthetic gas;
J, synthesis procedure
The pure synthetic gas obtained by step I is at air speed 800 ~ 2500h
-1, carry out methanation reaction by methanation catalyst reactor under temperature 300 ~ 650 DEG C and the condition of pressure 0.3 ~ 8.0MPa, obtain a kind of Sweet natural gas, or at air speed 350 ~ 500h
-1, carry out building-up reactions by synthetic oil catalyst reactor under temperature 190 ~ 300 DEG C and the condition of pressure 2.0 ~ 4.0MPa, obtain described hydrocarbon fuel oil production.
According to another kind of preferred implementation of the present invention, in step e, when described semicoke product and high purity oxygen gas, water carry out wet method gasification reaction, steps A to use the size-grade distribution of coal dust should be that less than 500 μm is less than 100%, 125 μm be by weight less than 50 ~ 70%, 75 μm be less than 40 ~ 50%, 44 μm is 25 ~ 30%; Described semicoke product and high purity oxygen gas, water vapor carry out dry gasification when reacting, steps A use the size-grade distribution of coal dust should be by weight less than 100 μm be 100%.
According to another kind of preferred implementation of the present invention, in steps A obtain the composed as follows of raw gas product: by volume
According to another kind of preferred implementation of the present invention, in stepb, described scavenging agent is selected from gac, porous ceramics, silica type or molecular sieve porous adsorbent.
According to another kind of preferred implementation of the present invention, in step C and J, described methanation catalyst is selected from Ni base or Fe methylmethane catalyzer.
According to another kind of preferred implementation of the present invention, in step e, described catalyst for water-gas shift reaction is selected from that Fe is catalyst based, Co-Mo system sulfur-resistant transformation catalyst or Cu-Zn series catalysts.
According to another kind of preferred implementation of the present invention, in step F, described absorption agent is selected from methyl alcohol, Polyethylene glycol dimethyl ether or methyldiethanolamine.
According to another kind of preferred implementation of the present invention, in step G, described sulphur synthetic catalyst is selected from that Al is catalyst based or Ti is catalyst based.
According to another kind of preferred implementation of the present invention, in step B and H, described sweetening agent is selected from ZnO, FeO or carbonate solution class sweetening agent.
According to another kind of preferred implementation of the present invention, in step D, described Sweet natural gas is composed as follows: by volume, CH
495.0 ~ 98.5%, CO 0.28 ~ 0.95%, H
20.17 ~ 0.55%, CO
20.75 ~ 1.30% and N
20.45 ~ 1.05%.
In more detail the present invention will be described below.
The present invention is directed to the deficiency of current coal hydrocarbon fuel (Sweet natural gas, oil fuel) product tradition usual manner, adopt mode fine coal external-heat moving bed pyrolysis technology combined with efficient, clean entrained flow bed gasification technology, utilize and account for the smalls (granularity≤10mm) exploiting total raw coal quality more than 70% at present, especially low order smalls (long-flame coal, brown coal) realizes the production of tar and hydrocarbon fuel for raw material.Fine coal is first extracted tar products by pyrogenic processes by the method, more respectively to pyrogenic processes by product raw gas and semicoke processing and utilization to produce hydrocarbon fuel product.Wherein, raw gas by product is successively through desulfurizing and purifying operation, methanation operation and methane separation operation production high purity methane product; Semicoke by product is successively through gasification process, shift conversion step, cleaning section, fine de-sulfur operation, sulfur recovery process, synthesis procedure production high purity methane product or fuel oil.The reasonable conversion that the present invention had both achieved Macromolecule in coal material is collected; reach again the effect of feed change coal surface properties and unit calorific value; take into account coal and utilize the environmental protection problem in process; the classification sub-prime really achieving coal resources utilizes, and is particularly suitable for utilizing occasion with the Poly-generation that coal especially low-rank coal is raw material.
The present invention relates to a kind of method utilizing coal to produce tar and hydrocarbon fuel product, concrete technology flow process is see accompanying drawing 1.
The step of the method is as follows:
A, pyrogenic processes
Preprocessing grinding powder coal is sent into pyrogenic processes, described coal dust decomposes 35-80min at temperature 450 ~ 800 DEG C with the condition of pressure-0.05 ~ 0.05MPa, generate a kind of tar light oil in gaseous state and raw gas mix products with a kind of be solid-state semicoke product, then allow described tar light oil and raw gas mix products by dedusting, cooling washing and oily water separation, obtain a kind of tar products and a kind of raw gas product.
Feed coal to certain granularity, is the flow process of wet entrained flow bed gasification by crushing grinding for gasification process, and this size-grade distribution is for 100% being less than 500 μm by weight, and 50 ~ 70% are less than 125 μm, and 40 ~ 50% are less than 75 μm, and 25 ~ 30% are less than 44 μm; For the flow process that gasification process is dry method entrained flow gasification, this granularity is for 100% being less than 100 μm by weight, and size-grade distribution freely distributes in broken.
Then, by grinding coal dust continus convergence to pyrogenic processes.The pyrolysis plant used in pyrogenic processes is a kind of external-heat moving bed pyrolysis reactor, and this pyrolysis plant is that Lanzhou Tianhua Chemical Machinery & Automation Design Inst releases product sold with trade(brand)name WR-800 type pyrolysis reactor furnace.
Feed coal occurs converting by pyrogenic processes processing treatment, obtains the tar light oil in gaseous state and rough mixed gas on the one hand, obtains the solid-state semicoke product of butt bomb calorific value >=24000MJ on the other hand.In the present invention, described semicoke product should be appreciated that it is a kind of flammable solid product, black gray expandable, porous, and main component is carbon, ash content and volatile constituent, and compared with coke, its volatile component content is high, and physical strength is low.
Then, allow described tar light oil and rough mixed gas successively by dedusting, cooling washing and oily water separation, the basic object of this step is to remove a small amount of solid semicoke dust entrained in tar light oil and rough mixed gas, and realize being separated of tar light oil and raw gas by the method for cooling condensation, finally obtain a kind of light low temp tar tar liquid product of less than 350 DEG C cut mass yield>=50% and a kind of indifferent gas (N
2+ CO
2) volume content≤11%, effectively gas (CO+H
2+ CH
4+ C
nh
m) the high heating value gaseous raw coal gas product of volume content>=85%.The dedusting that the present invention adopts, cooling washing and oily water separation technique are all the routine techniquess in the art, such as dedusting technology is the metal sintering pipe high-temperature dust removal technology, bed of packings dust removal by filtration technology etc. that those skilled in the art of the present technique know, the standing separation technology that cooling washing technology to be the cooling of ammonia circulation spray-type washing technology, oily water separation technique that those skilled in the art of the present technique know be those skilled in the art of the present technique are common.The equipment that these technology use also is all product sold in the market.
In this step, the standard method of analysis (GB/T28901-2012) in employing the art is to CO, the CO in obtained raw gas product
2, H
2with CH
4content measures, and determines that described raw gas is composed as follows: by volume
B, raw gas purifying desulfurization
The raw gas product allowing steps A obtain is at air speed 1000 ~ 3000h
-1, under temperature 60 ~ 80 DEG C and the condition of pressure 0.05 ~ 0.1MPa by being equipped with scavenging agent bed and desulfurizing agent bed cleaner successively, remove the micro-heterogeneous ring compound and sulfocompound that wherein contain, obtain the clean raw gas of heterogeneous ring compound content <0.02ppm and sulphur content <0.1ppm by weight;
Allow a part of clean raw gas product return pyrogenic processes as heating fuel and pyrolysis atmosphere, rest part delivers to follow-up methanation operation.
In the present invention, described scavenging agent should be appreciated that it is a kind of absorption purifier with selective adsorption function and refresh function.The scavenging agent that the present invention uses is selected from gac, porous ceramics, silica type or molecular sieve porous adsorbent.
Described gac is mineral raw material gac, cocoanut active charcoal, active fruit shell carbon or wood activated charcoal.The gac that the present invention uses is all product sold in the market, such as by Anhui Da Linxin carbon material company limited with trade(brand)name industrial activited carbon, the Zhong Mountain, Chongqing gac company limited with trade(brand)name cocoanut active charcoal or Jiangxi Jing Jie cellular activated carbon factory with trade(brand)name cellular activated carbon product sold.For the inventive method, they have following characteristic: bulk density 0.3 ~ 0.5g/ml, specific surface area>=700m
2/ g,
Described porous ceramics be with emergy, silicon carbide, trichroite etc. be raw material, the porous ceramic materials made through overmolding and high-sintering process, it has high temperature resistant, the advantages such as high pressure, acid and alkali-resistance and organic medium corrosion.The porous ceramics that the present invention uses is all product sold in the market, such as, fly chemical industry porcelain piece factory with trade(brand)name pottery random packing product sold with trade(brand)name industrial gaseous waste catalytic purification ceramic honey comb, Guangxi Yun Da waste-gas cleaning company limited with trade(brand)name ceramic honey comb or Zichuan roc by Jiangsu Province Yixing Nonmetallic Chemical Machinery Factory Co., Ltd..For the inventive method, they should have following characteristic: bulk density 400 ~ 700kg/m
3, specific surface area>=100m
2/ g.
The silica type adsorbent that the present invention uses is all product sold in the market, such as by Qingdao Shuo Yuan Chemical Co., Ltd. with trade(brand)name silica gel absorber or Qingdao company of Gui Chuan Fine Chemical Co., Ltd with trade(brand)name silica gel absorber product sold.For the inventive method, they should have following characteristic: pore volume 0.85 ~ 1l/g m
3, specific surface area 300 ~ 500m
2/ g.
Described molecular sieve adsorbent comprises natural zeolite and synthetic zeolite, and they are the many microporous crystals of a kind of silico-aluminate.The molecular sieve sorbing material that the present invention uses is such as have recruit to sieve company with trade(brand)name large pore molecular sieve product sold by the global chemical filler company limited of Pingxiang City with trade(brand)name bar shaped molecular sieve or Shanghai.For the inventive method, they should have following characteristic: bulk density ~ 600kg/m
3, specific surface area>=300m
2/ g.
In the present invention, described sweetening agent generally should be appreciated that it is the chemical substance removing free sulphur or sulphur compound in raw material or unclassified stores.The sweetening agent that the present invention uses is selected from ZnO, Fe
2o
3or carbonate solution class sweetening agent, the ZnO sweetening agent such as sold with trade(brand)name ZnO desulfurizing agent by Xibei Chemical Inst, the Fe sold with trade(brand)name ferric oxide desulfurizer by Wan Tong catalyzer company limited of Changge City
2o
3sweetening agent, the industrial magnesium phosphate sold with trade(brand)name industry base salt of wormwood by Guangzhou Sheng Hao Chemical Co., Ltd..For the inventive method, they should have following characteristic: sulphur mass content <0.1ppm in gas after desulfurization.
Allow a part of clean raw gas product return as heating fuel and adjustment pyrolysis atmosphere, rest part delivers to follow-up methanation operation process, and the object of process is like this to increase pyrolysis light component product productive rate, for pyrolytic reaction provides institute's heat requirement.The amount that clean raw gas product returns is determined according to needs of production and some other factorses, and usually, the amount that clean raw gas product returns is about 15 ~ 40% of total clean raw gas volumetric production.
C, methanation operation
The clean raw gas allowing step B obtain is at air speed 3000 ~ 10000h
-1, under temperature 250 ~ 600 DEG C and the condition of pressure 2.0 ~ 3.0MPa by methanation catalyst reactor, make H wherein
2respectively with CO and CO
2carry out methanation reaction, obtain being rich in methane gas blend;
In this step and subsequent step thereof, the methanation catalyst that the present invention uses is Ni base or Fe methylmethane catalyzer.These methanation catalysts are all product solds in the market, the Ni methylmethane catalyzer such as sold with trade(brand)name JRE type methanation catalyst by Xibei Chemical Inst, the Fe methylmethane catalyzer sold with trade(brand)name methanation catalyst by Dai Wei company of Britain.For the inventive method, they should have following characteristic: methane selectively>=96%, CO
2+ CO transformation efficiency 99%.
Methanation reaction particular case is with reference to the prior art such as CN 201010600076 or CN 201110267177.Under methanation catalyst exists, allow H in raw gas
2with CO and CO
2carry out methanation reaction, wherein CO, H
2and CO
2be converted into CH in a large number
4, obtain CH by volume
4content>=85%, containing a small amount of CO, H
2, N
2and CO
2the methane-rich gas mixture of component.
D, methane separation operation
The methane-rich gas mixture obtained by step C is delivered in methane separation operation, is separated under the condition that conventional pressure-variable adsorption is separated, and obtains concentration for CH by volume
4the gas product of >95% and containing H
2, CO and CO
2the gas mixture of main ingredient;
Adopt conventional PSA Technology separation of methane in the present invention.Relevant conventional PSA Technology please refer to CN103405993A.
It is that effluent south global landification equipment science and technology share wind company limited is with trade(brand)name pressure-swing absorber product sold that the conventional pressure-variable adsorption (PSA) of the present invention is separated the equipment used.
In the present invention, relevant CH
4, H
2, CO and CO
2analysis described above, repeat no more at this and further part thereof.
E, gasification process
The semicoke product obtained by steps A and high purity oxygen gas, water or water vapor carry out wet method at temperature 1200.0 ~ 1400.0 DEG C with the condition of pressure 1.0 ~ 10.0MPa or dry gasification reacts, and obtains mainly containing CO and H
2crude synthesis gas.
The present invention uses high-purity oxygen to be provided by the air separation facility of peripheral hardware, and water or water vapor are provided by tap water supply system or steam boiler.
The particular case of coal wet method gasification process and the equipment of use thereof can see files such as CN 200410073361, CN 200510111484, and the particular case of coal dry gasification operation and the equipment of use thereof can see files such as CN 200510080334, CN 200510053511.
If when this gasification process selects wet entrained flow bed evaporating method, the efflux wastewater that raw pulp water can use pyrogenic processes raw gas washing step to produce.If during this gasification process selection dry method entrained flow bed gasification technology, the semicoke product that pyrolysis step obtains can directly be sent to gasification step in the case of a high temperature and use as raw material.
Dustiness, through subsequent wash and udst separation process, is down to 1mg/m by described crude synthesis gas
3below deliver to subsequent conversion operation after to process.The particular case of described subsequent wash and udst separation treatment process and the equipment of use thereof is specifically see files such as CN 200410073361, ZL200320109792.3.
In described semicoke product, also responseless carbon and other inorganic contaminants form residue and discharge outside treatment system of the present invention after solidification treatment.
F, shift conversion step
A crude synthesis gas part obtained in step e is at air speed 1500 ~ 3500h
-1, under temperature 300 ~ 500 DEG C and the condition of pressure 0.8 ~ 9.5MPa by transformation catalyst reactor, the CO allowing described crude synthesis gas contain and water vapor carry out transformationreation, described crude synthesis gas is transformed into and mainly contains H
2hydrogen-rich gas, then it mix with the crude synthesis gas of remainder, obtains a kind of mixing transformation gas;
In this operation, the catalyst for water-gas shift reaction of use is selected from that Fe is catalyst based, Co-Mo system sulfur-resistant transformation catalyst or Cu-Zn series catalysts.For the inventive method, these catalyzer all should have following characteristic: CO transformation efficiency >=92%, strength retention ratio >=90%.
The catalyzer that the present invention uses is all product sold in the market, the Fe such as sold with trade(brand)name siderochrome transformation catalyst by rope company of Top of Denmark is catalyst based, by Xibei Chemical Inst with the Co-Mo system sulfur-resistant transformation catalyst of the wide temperature sulfur-resistant transformation catalyst sale of trade(brand)name, the Cu-Zn series catalysts sold with trade(brand)name low temperature shift catalyst by Xibei Chemical Inst.
In this operation, the crude synthesis gas from step e is divided into two portions, wherein a part of crude synthesis gas is by shift conversion step, and the crude synthesis gas by-passing of remainder.When described crude synthesis gas is by shift conversion step, CO wherein and water vapor carry out transformationreation, are transformed into this part crude synthesis gas with H
2be main hydrogen-rich gas, then this hydrogen-rich gas mixes with the crude synthesis gas from bypass, obtains a kind of conversion gas, then enters cleaning section.
In this operation, this step can by controlling the volume ratio that pass between the crude synthesis gas of shift-converter and bypass crude synthesis gas, regulate produce H in conversion gas
2/ CO mol ratio, and then reach subsequent purification operation to entering H in its inner refining synthetic gas
2the requirement of/CO mol ratio.
The transformationreation equipment that the present invention uses is the common sulfur-resisting transformation production unit of domestic Nitrogenous Fertilizer Production Installation, the sulfur-tolerant water gas shift device of such as Chemical Machinery Plant, Nanjing Chemical Industry Co., Ltd., China Petrochemic's process for processing.
G, cleaning section
The conversion gas obtained by step F is mixed with the gas mixture obtained by step D, obtain a kind of mixed gas, then with under the existence of described gas mixture volumeter 0.5 ~ 2% absorption agent, at temperature-60 ~ 0 DEG C with the condition of pressure 0.6 ~ 9.0MPa, carry out purifying treatment, remove whole CO that described mixed gas contains
2with most of sulfocompound, be purified synthetic gas, high-purity CO respectively
2gas and sulfocompound gas; The CO of described decontaminating syngas
2content is less than 10ppm, and sulfocompound content is less than 0.1ppm.
In this operation, the object of described mixed gas purification process is the almost whole CO removed contained by this mixed gas
2component and most of sulfocompound (H
2s, COS) component, obtain a kind of decontaminating syngas, determine its CO by analysis
2content is less than 10ppm, and sulfocompound content is less than 0.1ppm.
In this operation, described absorption agent is selected from methyl alcohol, Polyethylene glycol dimethyl ether (NHD) or methyldiethanolamine (MDEA), they are all product solds in the market, such as, by the Polyethylene glycol dimethyl ether of southern Shandong chemical industry group production and sales, the N methyldiethanolamine by Sichuan Fine Chemical Research and Design Inst.'s production and sales.
In this operation, the equipment that described mixed gas purification process uses is product sold in the market, such as by Dalian petrochemical machinery factory with trade(brand)name low-temperature rectisol absorption tower product sold.
For reaching the object of absorption agent recycle, the absorption agent in this operation is at absorption CO
2need through desorption operations after gas and sulfocompound gas, discharge the gas that it absorbs, obtain a kind of high-purity CO respectively simultaneously
2gas (CO
2volume fraction>=97%) and a kind of sulfocompound gas.This high-purity CO
2gas can be used as a kind of product application in multiple technical fields such as such as oilfield exploitation, material welding, food mfgs.
H, sulfur recovery process
The sulfocompound gas allowing step G obtain delivers to the oxidation unit of sulfur recovery process, and incite somebody to action wherein a part of selective oxidation of sulfur containing compounds in particular, then with remaining sulfocompound gas and vapor permeation, the gas mixture obtained is again at air speed 250 ~ 550h
-1, under temperature 150 ~ 450 DEG C and the condition of pressure 0.2 ~ 3.5MPa by sulphur synthetic catalyst reactor, allow the sulphur of wherein sulfocompound change into elemental sulfur, obtain a kind of sulfur product.
In this operation, the sulfocompound gas from step G is divided into two portions, wherein a part of sulfocompound gas is by the oxidation unit of sulfur recovery process, and the sulfocompound gas by-passing of remainder.Described sulfocompound gas is oxidized by sulfocompound during the oxidation unit of sulfur recovery process, this gas containing oxidized sulfocompound then with the sulfocompound gas and vapor permeation from bypass, again by being equipped with the reactor of sulphur synthetic catalyst, element sulphur is wherein changed into elemental sulfur, obtains sulfur product.
In this operation, described sulphur synthetic catalyst is selected from that Al is catalyst based or Ti is catalyst based, be all product sold in the market, the Al such as sold with trade(brand)name sulfur recovery catalyst by Bao Luojie company of U.S. Ti that is catalyst based, that sold with trade(brand)name sulphur synthetic catalyst by Deqing, Zhejiang three imperial catalyzer company limited is catalyst based.For the inventive method, Al is catalyst based or Ti is catalyst based all should have following requirement: total Recovery ratio >=98%.
I, fine de-sulfur operation
By the decontaminating syngas that obtained by step G at air speed 1000 ~ 3000h
-1, carry out desulphurization reaction by sweetening agent cleaner under temperature 60 ~ 80 DEG C and the condition of 0.5 ~ 8.5MPa, make the sulfur component of described decontaminating syngas be down to below 0.01ppm by volume, obtain a kind of pure synthetic gas;
The sweetening agent used in this step as preceding step B the sweetening agent that uses identical, therefore do not repeat them here.
The sweetening agent cleaner that this operation uses is multitower tandem fine de-sulfur equipment well-known to those skilled in the art, the multitower tandem fine de-sulfur equipment such as sold with trade(brand)name fine de-sulfur tower by company of Tianjin Chuangju Science and Technology Co., Ltd..
This operation is implemented to remove further to the sulfur component of the decontaminating syngas that step G obtains, and makes the sulfurous gas component of decontaminating syngas be down to below 0.01ppm, obtains a kind of pure synthetic gas.
J, synthesis procedure
The pure synthetic gas obtained by step I is at air speed 800 ~ 2500h
-1, carry out methanation reaction by methanation catalyst reactor under temperature 300 ~ 650 DEG C and the condition of pressure 0.3 ~ 8.0MPa, obtain a kind of Sweet natural gas.
The methanation catalyst used in this step and equipment thereof as preceding step C the methanation catalyst that uses identical, therefore do not repeat them here.
Adopt gas product conventional method of analysis to analyze to determine, described gas product is composed as follows: CH by volume
495.0 ~ 98.5%, CO 0.28 ~ 0.95%, H
20.17 ~ 0.55%, CO
20.75 ~ 1.30% and N
20.45 ~ 1.05%.
Or
The pure synthetic gas obtained by step I is at air speed 350 ~ 500h
-1, carry out building-up reactions by synthetic oil catalyst reactor under temperature 190 ~ 300 DEG C and the condition of pressure 2.0 ~ 4.0MPa, obtain described hydrocarbon fuel oil production.
The synthetic oil catalyst used in this step is product sold in the market, the synthetic oil catalyst such as sold with trade(brand)name synthetic oil catalyst by Zhong Ke synthetic oil limited-liability company.
The synthetic oil catalyst reactor used in this step is product sold in the market, such as by company of Jinzhou Dalian heavy-duty machinery company with trade(brand)name Fischer-Tropsch and the reactor becoming reactor, Jinxi at dawn Hua Ji company of Air China sells with trade(brand)name Fischer-Tropsch synthesis device.
The hydrocarbon fuel oil production obtained in this step adopts the standard method detections such as GB252-2011, GB17930-2011 to determine, this hydrocarbon fuel oil production meets the national standards such as No. 0 ordinary diesel oil standard and 93# gasoline standard completely, and can put goods on the market sale.
The processing method that the present invention utilizes coal high-efficiency to produce tar and hydrocarbon fuel product achieves the efficient transformation of feed coal, reaches the object of simultaneously producing tar and hydrocarbon fuel product.
[beneficial effect]
Compared with existing or routine techniques, the method that the present invention utilizes coal to produce tar and hydrocarbon fuel product has following beneficial effect:
1, be that lower molecular weight gaseous substance is different from coal direct gasification by complete for Macromolecule in coal material decomposition and inversion, the present invention takes the Land use systems transformed that gasifies after first for raw coal low temperature pyrogenation, natural macromolecular material contained by raw coal is recycled with tar products form, not only increase Coal Chemical Industry process product kind, for social production provides valuable starting material, improve the utilising efficiency of coal feedstock, the sub-prime really achieving coal utilizes simultaneously.
2, the coal feedstock of the present invention's use, especially the semicoke that obtains after pyrolysis processing of low order coal raw material, there is the unit mass calorific value of better slurry performance and Geng Gao compared with raw coal, meta-bituminous coal can only be utilized as the present situation of gasified raw material relative to conventional wet lay entrained flow gasification, method of the present invention not only solves the problem that low-rank coal is difficult to wet entrained flow bed gasification utilization, simultaneously because of the raising of raw material calorific value, gasification raw material consumption also reduces relatively.
3, in the present invention, the grinding to be operated in before raw coal enters pyrogenic processes of feed coal completes, and utilizes in process in follow-up gasification, semicoke without the need to more further grinding can reach gasified raw material granularity requirements, namely follow-up gasification process need not arrange grinding facility.Feed coal grinds and can adopt simple dry grinding mode, and the wet method adopted relative to conventional entrained flow gasification grinds or high temperature dry grinding+noble gas protected mode, can effectively reduce grinding machine specification, simplifies grinding process, and then significantly reduces grinding energy consumption level.
4, according to the present invention, if during gasification process selection wet entrained flow bed gasification technology, the efflux wastewater that raw pulp water can use pyrogenic processes raw gas washing room to produce, reduces wastewater discharge when even eliminating single pyrolysis processing; When adopting dry method entrained flow gasification technique, the high-temperature semi-coke going out pyrogenic processes directly can be sent to gasification process reactor, make full use of semicoke raw material sensible heat, reduce gasification reaction raw material consumption.
5, in the present invention, pyrogenic processes adopts external-heat pyrolytic process, and relative to internal heat type pyrolysis way, in raw gas, impurity component content is low, is convenient to processing and the utilization of follow-up raw gas.The separating mixed gas that methane separation operation obtains is mixed into the way of conversion synthetic gas, both effectively make use of this part containing energy gas, better make use of again the feature wherein containing higher hydrogen Gas content simultaneously, shift conversion step scale can be reduced to a certain extent, reduce process greenhouse gases growing amount.
[accompanying drawing explanation]
Fig. 1 is that the present invention utilizes coal to produce tar and hydrocarbon fuel method for product process flow sheet.
[embodiment]
The present invention can be understood better by following embodiment.
Embodiment 1: the present invention utilizes coal to produce tar and gas product
The implementation step of this embodiment is as follows:
Concrete implementation step is shown in accompanying drawing 1.
A, pyrolysis
With North Shaanxi long-flame coal for raw material, the method adopting GB212-91 and GB476-91 to specify is analyzed, and this coal analysis the results are shown in table 1.
This feed coal is ground to size-grade distribution for 100% being less than 500 μm by weight, wherein 50% is less than 125 μm, and 40% is less than 75 μm, 25% powder being less than 44 μm, and is delivered to pyrogenic processes according to the feeding quantity of 5000kg/h by feeding unit.The pyrolysis plant used in pyrogenic processes is such as release by Lanzhou Tianhua Chemical Machinery & Automation Design Inst the pyrolysis plant sold with trade(brand)name WR-800 type pyrolysis reactor furnace.Described coal dust carries out pyrolytic reaction 80min at temperature 450 DEG C with the condition of gauge pressure 0.05MPa.Generate a kind of tar light oil in gaseous state and raw gas mix products and a kind ofly count 2904kg/h with mass rate and through cooling process to the semicoke product 1 of temperature 60 C, then allow described tar light oil and raw gas mix products by after the inner dedusting of pyrogenic processes, cooling washing and workshop section's process such as settlement separate, obtain counting 512kg/h with mass rate respectively, water ratio be by weight 5.5% tar products, and count 1387m with volumetric flow rate
3the raw gas product of/h (butt, rear same).
Table 1: feed coal and semicoke analytical results, represent with % by weight
B, raw gas purifying desulfurization
By the raw gas that obtained by steps A at air speed 3000h
-1, temperature 60 C and pressure 0.05MPa condition under by being equipped with the desulfurizing agent bed cleaner of the ZnO that reaches the limited active carbon purifying agent bed sold with trade(brand)name industrial activited carbon of woods zinc carbon material by Anhui and sold with trade(brand)name ZnO desulfurizing agent by Xibei Chemical Inst successively, naphthalene in this raw gas and sulfur component are removed, and obtaining volumetric flow rate is 1368m
3the clean raw gas of the sulphur content of/h 0.06ppm and heterogeneous ring compound content 0.01ppm by weight.To wherein use with regulating pyrolysis atmosphere as heating fuel burning by the clean raw gas of part, be back to pyrolysis unit, the clean rough coal tolerance returned is 272m
3/ h, residue 1096m
3the clean raw gas of/h delivers to methanation operation.
C, methanation operation
The clean raw gas obtained by step B is at air speed 10000h
-1, temperature 250 DEG C, pressure 3.0MPa condition under by being equipped with the methanation catalyst reactor of the Ni methylmethane catalyzer sold with trade(brand)name JRE type by Xibei Chemical Inst, make H wherein
2respectively with CO and CO
2carry out methanation reaction, obtain being rich in methane gas blend, this is rich in methane gas blend with 599m
3the volumetric flow rate of/h is expelled to methane separation operation.
D, methane separation operation
The methane-rich gas mixture obtained by step C is delivered in methane separation operation, use the pressure-variable adsorption separating device that effluent south global landification equipment science and technology share wind company limited sells with trade(brand)name pressure-swing absorber, be separated under the condition that conventional pressure-variable adsorption is separated, obtain counting 514m with volumetric flow rate
3/ h, volume consist of CH
495.40%, CO 1.08%, H
20.46%, CO
21.68% and N
2the gas product of 1.38%, and volumetric flow rate is 85m
3/ h's contains H
2, CO and CO
2for the gas mixture of main ingredient;
E, gasification process
Gasification process is delivered to after 2904kg/h semicoke 1 product (forming in the table 1) cooling obtained by steps A.In gasification process, be directly uniformly mixed into 62% Jiao-water slurry body in mass with 1653kg/h fresh water.This Jiao-water slurry body and the 2380m from extraneous air separation facility
3/ h oxygen carries out gasification reaction at temperature 1400 DEG C with the condition of pressure 10.0MPa, then through subsequent wash and udst separation process, obtains counting 6092m with volumetric flow rate
3/ h's is main containing CO and H
2crude synthesis gas.
F, shift conversion step
By the crude synthesis gas that a part obtains in step e, by wherein partly (flow is 3655m
3/ h) deliver in the reactor that the Co-Mo system sulfur-resistant transformation catalyst sold with the wide temperature sulfur-resistant transformation catalyst of trade(brand)name by Xibei Chemical Inst is housed, at temperature 300 DEG C with pressure 9.5MPa condition, carry out transformationreation, (flow is 2437m to remaining crude synthesis gas
3/ h) do not reacted by transformation catalyst, directly mix with the conversion gas of being discharged by transformation catalyst reactor, obtaining volumetric flow rate is 7947m
3the conversion gas of/h.
G, cleaning section
The mixing transformation gas obtained by step F is mixed with the gas mixture obtained by step D, obtains 8032m
3/ h mixed gas all sends into cleaning section, under the methanol absorbing agent for described gas mixture volume 2.0% exists, carries out purifying treatment, be purified synthetic gas, high-purity CO respectively under the condition of temperature-60 DEG C with pressure 9.0MPa
2gas and sulfocompound gas, wherein sulfur component gas is with 4.45m
3/ h, CO
2gas is with 2975m
3/ h, decontaminating syngas are with 5053m
3/ h volumetric flow rate is discharged from cleaning section.
H, sulfur recovery process
The sulfocompound gas allowing step G obtain is delivered to and is delivered to sulfur recovery process, wherein a part of sulfocompound is oxidized by the oxidation unit oxygen-rich air of sulfur recovery process, its oxidation products again with the remaining sulfocompound gas and vapor permeation through bypass, the gas mixture obtained is with air speed 550h
-1by being equipped with the catalyst based sulphur synthetic catalyst reactor of the Al that sold with trade(brand)name sulfur recovery catalyst by Bao Luojie company of the U.S., sulfur recovery process is carried out at temperature 150 DEG C with the condition of pressure 3.5MPa, element sulphur in described gas mixture changes into elemental sulfur, trapping is reclaimed, and obtains the by product sulphur of 6.35kg/h.
I, fine de-sulfur operation
By the clean synthetic gas that obtained by step G with air speed 3000h
-1by being equipped with in the ZnO sweetening agent cleaner sold with trade(brand)name ZnO desulfurizing agent by Xibei Chemical Inst, under the condition of temperature 60 C and pressure 8.5MPa, carrying out desulfurization process, obtain volumetric flow rate 5049m
3the sulfur component of/h is the pure synthetic gas of below 0.01ppm by volume.
J, synthesis procedure
The pure synthetic gas obtained by step I is all sent in synthesis procedure, with air speed 800h
-1by being equipped with the methanation catalyst reactor of the Ni methylmethane catalyzer sold with trade(brand)name JRE type methanation catalyst by Xibei Chemical Inst, methanation reaction is carried out at temperature 480 DEG C with the condition of pressure 4.6MPa, obtain a kind of Sweet natural gas, it consists of CH by volume
496.10%, CO 0.83%, H
20.96%, CO
21.06%, N
21.05%, volumetric flow rate is 1367m
3/ h.
Embodiment 2: the present invention utilizes coal to produce tar, Sweet natural gas and fuel oil products
Outside this embodiment tar removing, also produce 2 kinds of hydrocarbon fuel products simultaneously.
A, pyrolysis
With the raw coal used in embodiment 1 for raw material, this feed coal is ground to after preliminary fragmentation size-grade distribution for 100% being less than 500 μm by weight, wherein 70% is less than 125 μm, 50% is less than 75 μm, 30% powder being less than 44 μm, and be delivered to pyrogenic processes according to the feeding quantity of 5000kg/h by feeding unit.The pyrolysis plant used in pyrogenic processes is such as release by Lanzhou Tianhua Chemical Machinery & Automation Design Inst the pyrolysis plant sold with trade(brand)name WR-800 type pyrolysis reactor furnace.Described coal dust carries out pyrolytic reaction 45min at temperature 600 DEG C with condition of normal pressure.Generate a kind of tar light oil in gaseous state and raw gas mix products and a kind ofly count 2831kg/h with mass rate and through cooling process to the semicoke product 2 of temperature 60 C, then allow described tar light oil and raw gas mix products by after the inner dedusting of pyrogenic processes, cooling washing and workshop section's process such as settlement separate, obtain counting 548kg/h with mass rate respectively, water ratio be by weight 5.1% tar products, and count 1465m with volumetric flow rate
3the raw gas product of/h (butt, rear same).
B, raw gas purifying desulfurization
By the raw gas that obtained by steps A with air speed 2000h
-1deliver to raw gas purifying desulfurization process, pass through to be equipped with successively by Qingdao company of Gui Chuan Fine Chemical Co., Ltd with trade(brand)name silica gel absorber the silica gel purification agent bed sold and the salt of wormwood water bath purifier sold with trade(brand)name industry base salt of wormwood by Guangzhou Sheng Hao Chemical Co., Ltd. under temperature 72 DEG C and the condition of pressure 0.06MPa, naphthalene in this raw gas and sulfur component are removed, and obtaining volumetric flow rate is 1431m
3the sulphur content of/h is the clean raw gas of 0.07ppm and heterogeneous ring compound content 0.01ppm by weight.To wherein use with regulating pyrolysis atmosphere as heating fuel burning by the clean raw gas of part, be back to pyrolysis unit, the clean rough coal tolerance returned is 358m3/h, and the clean raw gas of residue 1073m3/h delivers to methanation operation.
C, methanation operation
By the clean raw gas that obtained by step B with air speed 5500h
-1introducing in methanation operation, under the existence condition of temperature 400 DEG C, pressure 2.5MPa and methanation catalyst, by being equipped with the methanation catalyst reactor of the Ni methylmethane catalyzer sold with trade(brand)name JRE type by Xibei Chemical Inst, making H wherein
2respectively with CO and CO
2carry out methanation reaction, obtain being rich in methane gas blend, this is rich in methane gas blend with 603m
3the volumetric flow rate of/h is expelled to methane separation operation.
D, methane separation operation
The pressure-variable adsorption separating device that methane separation operation uses effluent south global landification equipment science and technology share wind company limited to sell with trade(brand)name pressure-swing absorber, the methane-rich gas mixture that methanation operation C produces is carried out separating treatment under transformation condition (PSA), obtains respectively counting 514m with volumetric flow rate
3/ h, volume consist of CH
496.13%, CO 0.95%, H
20.72%, CO
20.88%, N
2the substitute natural gas product of 1.32% and volumetric flow rate are 89m
3/ h is with H
2, CO and CO
2for the separating mixed gas of main ingredient.
E, gasification process
Gasification process is delivered to after 2831kg/h semicoke 2 product (forming in the table 1) cooling obtained by steps A.In gasification process, be directly uniformly mixed into 60% Jiao-water slurry body in mass with 1887kg/h fresh water.This Jiao-water slurry body and the 1982m from extraneous air separation facility
3/ h oxygen carries out gasification reaction at temperature 1380 DEG C with the condition of pressure 6.5MPa, then through subsequent wash and udst separation process, obtains counting 5825m with volumetric flow rate
3/ h's is main containing CO and H
2crude synthesis gas.
F, shift conversion step
Control the crude synthesis gas produced by gasification process E, incite somebody to action wherein part (2026m
3/ h) send into and be equipped with in the catalyst based shift conversion step reactor of Fe that rope company of Top of Denmark sells with trade(brand)name siderochrome transformation catalyst, temperature 400 DEG C, carry out transformationreation under pressure 6.0MPa condition, (flow is 3798m to rest part
3/ h) crude synthesis gas then directly mixes with the conversion gas going out shift-converter without transformationreation, and obtaining volumetric flow rate is 6756m
3the conversion gas of/h.
What above-mentioned conversion gas and methane separation operation produced by G, cleaning section be separated, and mixed air mixes 6845m altogether
3/ h all sends into cleaning section, for described gas mixture volume 1% by Sichuan Fine Chemical Research and Design Inst.'s production and sales N methyldiethanolamine absorption agent exist under, purifying treatment is carried out, by sulfur component wherein and CO under the condition of temperature-20 DEG C with pressure 5.0MPa
2gas is respectively with 20.38m
3/ h and 1863m
3the flow separation of/h out, deviates from the clean synthetic gas of impurity with 4961m
3the volumetric flow rate of/h sends cleaning section.
H, sulfur recovery process air speed
Isolated for cleaning section sulfur component gas is delivered to sulfur recovery process, incites somebody to action wherein a part of selective oxidation of sulfur containing compounds in particular, then with remaining sulfocompound gas and vapor permeation, and with air speed 400h
-1by being equipped with the catalyst based sulphur synthesis catalytic reactor of the Ti that sold with trade(brand)name sulphur synthetic catalyst by Deqing, Zhejiang three imperial catalyzer company limited, at temperature 350 DEG C with the condition of pressure 2.0MPa, carry out sulfur recovery process, obtain the by product sulphur counting 28kg/h with mass rate of production.
I, fine de-sulfur operation
The clean synthetic gas produced by cleaning section G is with air speed 1500h
-1by being filled with the Fe sold with trade(brand)name ferric oxide desulfurizer by Wan Tong catalyzer company limited of Changge City
2o
3desulfurizing purifier in, under the condition of temperature 70 C and pressure 3.5MPa, carry out fine de-sulfur process, obtaining volumetric flow rate is 4957m
3the refining synthetic gas of/h delivers to synthesis procedure.
J, synthesis procedure
The refining synthetic gas that fine de-sulfur operation produces all is sent in synthesis procedure, under the synthetic oil catalyst existence condition sold with trade(brand)name synthetic oil catalyst by Zhong Ke synthetic oil limited-liability company, the H in refining synthetic gas
2and CO component is with air speed 350h
-1, carry out synthesis under the condition of temperature 190 DEG C and pressure 2.0MPa and react, finally obtain the hydrocarbon fuel product counting 2370kg/h with total mass flow rate.
Embodiment 3: the present invention utilizes coal to produce tar, Sweet natural gas and fuel oil products
The implementation step of this embodiment is roughly the same with embodiment 2, and just selected by some operations, technique is different with technical parameter.
A, pyrolysis
With the raw coal used in embodiment 1 for raw material, be ground to that 100% is less than 100 μm, size-grade distribution is in the broken powder freely distributed, and being delivered to pyrogenic processes according to the feeding quantity of 20t/h by feeding unit, the pyrolysis plant used in pyrogenic processes is such as release by Lanzhou Tianhua Chemical Machinery & Automation Design Inst the pyrolysis plant sold with trade(brand)name WR-800 type pyrolysis reactor furnace.Described coal dust carries out pyrolytic reaction 35min at temperature 800 DEG C with the condition of gauge pressure-0.05MPa.Finally obtain counting 2135kg/h with mass rate respectively, water ratio be by weight 5% tar, count the semicoke product 3 of 13350kg/h with mass rate and count 4396m with volumetric flow rate
3the raw gas product of/h.
B, raw gas purifying desulfurization
By the raw gas that obtained by steps A with air speed 1000h
-1deliver to raw gas purifying desulfurization process, pass through to be equipped with successively by Jiangsu Province Yixing Nonmetallic Chemical Machinery Factory Co., Ltd. with trade(brand)name industrial gaseous waste catalytic purification ceramic honey comb the porous ceramics scavenging agent bed sold and the Fe sold with trade(brand)name ferric oxide desulfurizer by Wan Tong catalyzer company limited of Changge City under temperature 80 DEG C and the condition of pressure 0.1MPa
2o
3desulfurizing agent bed cleaner, the naphthalene in this raw gas and sulfur component are removed, and obtaining volumetric flow rate is 4356m
3the sulphur content of/h is clean raw gas that 0.09ppm and heterogeneous ring compound content are 0.015ppm by weight.To wherein use with regulating pyrolysis atmosphere as heating fuel burning by the clean raw gas of part, be back to pyrolysis unit, the clean rough coal tolerance returned is 1742m3/h, and the clean raw gas of residue 2614m3/h delivers to methanation operation.
C, methanation operation
By the clean raw gas that obtained by step B with air speed 3000h
-1introducing in methanation operation, under the existence condition of temperature 600 DEG C, pressure 2.0MPa and methanation catalyst, by being equipped with the methanation catalyst reactor of the Ni methylmethane catalyzer sold with trade(brand)name JRE type by Xibei Chemical Inst, making H wherein
2respectively with CO and CO
2carry out methanation reaction, obtain being rich in methane gas blend, this is rich in methane gas blend with 1542m
3the volumetric flow rate of/h is expelled to methane separation operation.
D, methane separation operation
The pressure-variable adsorption separating device that methane separation operation uses effluent south global landification equipment science and technology share wind company limited to sell with trade(brand)name pressure-swing absorber, the methane-rich gas mixture that methanation operation C produces is carried out separating treatment under transformation condition (PSA), obtains respectively counting 1288m with volumetric flow rate
3/ h, volume consist of CH
495.79%, CO 1.05%, H
20.61%, CO
21.18%, N
2the substitute natural gas product of 1.37% and volumetric flow rate are 254m
3the separating mixed gas of/h.
E, gasification process
The 13350kg/h pyrolysis char 3 (forming in table 1) produced by pyrogenic processes A directly delivers to gasification process at 650 DEG C without cooling.In gasification process, the 7810m produced with extraneous air separation facility at temperature 1200 DEG C with the condition of pressure 1.0MPa
3/ h oxygen and outer confession steam 10500m
3/ h carries out gasification reaction jointly, then gasification process inside washing and purification section process under finally obtain 27830m
3the crude synthesis gas of/h.
F, shift conversion step
Control the crude synthesis gas produced by gasification process E, incite somebody to action wherein part (14168m
3/ h) send into and be equipped with in the catalyst based shift conversion step reactor of Fe that rope company of Top of Denmark sells with trade(brand)name siderochrome transformation catalyst, temperature 500 DEG C, carry out transformationreation under pressure 0.8MPa condition, (flow is 13662m to rest part
3/ h) crude synthesis gas then directly mixes with the conversion gas going out shift-converter without transformationreation, and obtaining volumetric flow rate is 36890m
3the conversion gas of/h.
G, cleaning section
The mixed air that is separated above-mentioned conversion gas and methane separation operation produced mixes 37149m altogether
3/ h all sends into cleaning section, under Polyethylene glycol dimethyl ether (NHD) absorption agent for described gas mixture volume 0.5% exists, at temperature 0 DEG C with the condition of pressure 0.6MPa, carries out purifying treatment, by sulfur component wherein and CO
2gas is respectively with 16.58m
3/ h and 10984m
3the flow separation of/h out, deviates from the clean synthetic gas of impurity with 26148m
3the volumetric flow rate of/h sends cleaning section.
H, sulfur recovery process
Isolated for cleaning section sulfur component gas is delivered to sulfur recovery process, incites somebody to action wherein a part of selective oxidation of sulfur containing compounds in particular, then with remaining sulfocompound gas and vapor permeation, and with air speed 250h
-1by being equipped with the catalyst based sulphur synthesis catalytic reactor of the Ti that sold with trade(brand)name sulphur synthetic catalyst by Deqing, Zhejiang three imperial catalyzer company limited, at temperature 450 DEG C with the condition of pressure 0.2MPa, carry out sulfur recovery process, obtain the by product sulphur counting 23kg/h with mass rate of production.
I, fine de-sulfur operation
The clean synthetic gas produced by cleaning section G is with air speed 1000h
-1by being filled with the Fe sold with trade(brand)name ferric oxide desulfurizer by Wan Tong catalyzer company limited of Changge City
2o
3desulfurizing purifier in, at temperature 80 DEG C with the condition of pressure 0.5MPa, carry out fine de-sulfur process, obtaining volumetric flow rate is 26140m
3the refining synthetic gas of/h delivers to synthesis procedure.
J, synthesis procedure
The refining synthetic gas that fine de-sulfur operation produces all is sent in synthesis procedure, under the synthetic oil catalyst existence condition sold with trade(brand)name synthetic oil catalyst by Zhong Ke synthetic oil limited-liability company, the H in refining synthetic gas
2and CO component is with air speed 500h
-1, carry out synthesis under the condition of temperature 300 DEG C and pressure 4.0MPa and react, finally obtain the hydrocarbon fuel product counting 12500kg/h with total mass flow rate.
Claims (10)
1. utilize coal to produce a method for tar and hydrocarbon fuel product, it is characterized in that the step of the method is as follows:
A, pyrogenic processes
Preprocessing grinding powder coal is sent into pyrogenic processes, described coal dust decomposes 35-80min at temperature 450 ~ 800 DEG C with the condition of pressure-0.05 ~ 0.05MPa, generate a kind of tar light oil in gaseous state and raw gas mix products with a kind of be solid-state semicoke product, then allow described tar light oil and raw gas mix products by dedusting, cooling washing and oily water separation, obtain a kind of tar products and a kind of raw gas product;
B, raw gas purifying desulfurization
The raw gas product allowing steps A obtain is at air speed 1000 ~ 3000h
-1, under temperature 60 ~ 80 DEG C and the condition of pressure 0.05 ~ 0.1MPa successively by being equipped with scavenging agent bed and desulfurizing agent bed cleaner, remove the micro-heterogeneous ring compound and sulfocompound that wherein contain, obtain the clean raw gas of heterogeneous ring compound content <0.02ppm and sulphur content <0.1ppm by weight;
Allow a part of clean raw gas return pyrogenic processes as heating fuel and pyrolysis atmosphere, rest part delivers to follow-up methanation operation;
C, methanation operation
The clean raw gas allowing step B obtain is at air speed 3000 ~ 10000h
-1, under temperature 250 ~ 600 DEG C and the condition of pressure 2.0 ~ 3.0MPa by methanation catalyst reactor, make H wherein
2respectively with CO and CO
2carry out methanation reaction, obtain a kind of methane-rich gas mixture;
D, methane separation operation
The methane-rich gas mixture obtained by step C is delivered in methane separation operation, is separated under the condition that conventional pressure-variable adsorption is separated, and obtains concentration for CH by volume
4the gas product of >95% and containing H
2, CO and CO
2the gas mixture of main ingredient;
E, gasification process
The semicoke product obtained by steps A and high purity oxygen gas, water or water vapor carry out wet method at temperature 1200.0 ~ 1400.0 DEG C with the condition of pressure 1.0 ~ 10.0MPa or dry gasification reacts, and obtains mainly containing CO and H
2crude synthesis gas;
F, shift conversion step
A crude synthesis gas part obtained in step e is at air speed 1500 ~ 3500h
-1, under temperature 300 ~ 500 DEG C and the condition of pressure 0.8 ~ 9.5MPa by transformation catalyst reactor, the CO allowing described crude synthesis gas contain and water vapor carry out transformationreation, described crude synthesis gas is transformed into and mainly contains H
2hydrogen-rich gas, then it mix with the crude synthesis gas of remainder, obtains a kind of mixing transformation gas;
G, cleaning section
The conversion gas obtained by step F is mixed with the gas mixture obtained by step D, obtain a kind of mixed gas, then with under the existence of described gas mixture volumeter 0.5 ~ 2% absorption agent, at temperature-60 ~ 0 DEG C with the condition of pressure 0.6 ~ 9.0MPa, carry out purifying treatment, remove whole CO that described mixed gas contains
2with most of sulfocompound, be purified synthetic gas, high-purity CO respectively
2gas and sulfocompound gas; The CO of described decontaminating syngas
2content is less than 10ppm, and sulfocompound content is less than 0.1ppm;
H, sulfur recovery process
The sulfocompound gas allowing step G obtain delivers to the oxidation unit of sulfur recovery process, and incite somebody to action wherein a part of selective oxidation of sulfur containing compounds in particular, then with remaining sulfocompound gas and vapor permeation, the gas mixture obtained is again at air speed 250 ~ 550h
-1, under temperature 150 ~ 450 DEG C and the condition of pressure 0.2 ~ 3.5MPa by sulphur synthetic catalyst reactor, allow the sulphur of wherein sulfocompound change into elemental sulfur, obtain a kind of sulfur product;
I, fine de-sulfur operation
By the decontaminating syngas that obtained by step G at air speed 1000 ~ 3000h
-1, carry out desulphurization reaction by sweetening agent cleaner under temperature 60 ~ 80 DEG C and the condition of 0.5 ~ 8.5MPa, make the sulfur component of described decontaminating syngas be down to below 0.01ppm by volume, obtain a kind of pure synthetic gas;
J, synthesis procedure
The pure synthetic gas obtained by step I is at air speed 800 ~ 2500h
-1, carry out methanation reaction by methanation catalyst reactor under temperature 300 ~ 650 DEG C and the condition of pressure 0.3 ~ 8.0MPa, obtain a kind of Sweet natural gas, or at air speed 350 ~ 500h
-1, carry out building-up reactions by synthetic oil catalyst reactor under temperature 190 ~ 300 DEG C and the condition of pressure 2.0 ~ 4.0MPa, obtain described hydrocarbon fuel oil production.
2. method according to claim 1, it is characterized in that in step e, when described semicoke product and high purity oxygen gas, water carry out wet method gasification reaction, steps A to use the size-grade distribution of coal dust should be that less than 500 μm is less than 100%, 125 μm be by weight less than 50 ~ 70%, 75 μm be less than 40 ~ 50%, 44 μm is 25 ~ 30%; Described semicoke product and high purity oxygen gas, water vapor carry out dry gasification when reacting, steps A use the size-grade distribution of coal dust should be by weight less than 100 μm be 100%.
3. method according to claim 1, to it is characterized in that in steps A obtain the composed as follows of raw gas product: by volume
4. method according to claim 1, is characterized in that in stepb, and described scavenging agent is selected from gac, porous ceramics, silica type or molecular sieve porous adsorbent.
5. method according to claim 1, is characterized in that in step C and J, and described methanation catalyst is selected from Ni base or Fe methylmethane catalyzer.
6. method according to claim 1, is characterized in that in step e, and described catalyst for water-gas shift reaction is selected from that Fe is catalyst based, Co-Mo system sulfur-resistant transformation catalyst or Cu-Zn series catalysts.
7. method according to claim 1, is characterized in that in step F, and described absorption agent is selected from methyl alcohol, Polyethylene glycol dimethyl ether or methyldiethanolamine.
8. method according to claim 1, is characterized in that in step G, and described sulphur synthetic catalyst is selected from that Al is catalyst based or Ti is catalyst based.
9. method according to claim 1, is characterized in that in step B and H, and described sweetening agent is selected from ZnO, FeO or carbonate solution class sweetening agent.
10. hydrocarbon fuel product according to claim 1, is characterized in that in step D, and described Sweet natural gas is composed as follows: by volume, CH
495.0 ~ 98.5%, CO 0.28 ~ 0.95%, H
20.17 ~ 0.55%, CO
20.75 ~ 1.30% and N
20.45 ~ 1.05%.
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| CN105460890B (en) * | 2015-12-03 | 2018-03-13 | 东华工程科技股份有限公司 | A kind of method of UF membrane impermeable gas reforming hydrogen manufacturing of the coal liquifaction project oil wash dry gas after UF membrane |
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| CN106121616A (en) * | 2016-03-31 | 2016-11-16 | 中石化南京工程有限公司 | A kind of method separated based on underground coal gasification(UCG) gas purification |
| CN106121616B (en) * | 2016-03-31 | 2018-07-24 | 中石化南京工程有限公司 | A method of it is detached based on underground coal gasification(UCG) gas purification |
| CN106244239A (en) * | 2016-08-04 | 2016-12-21 | 中国五环工程有限公司 | Refuse gasification produces the process of synthetic natural gas |
| CN106244239B (en) * | 2016-08-04 | 2018-11-30 | 中国五环工程有限公司 | The process of refuse gasification production synthetic natural gas |
| CN106318430B (en) * | 2016-10-14 | 2018-03-23 | 神雾科技集团股份有限公司 | A kind of system and method using low-order coal |
| CN108998097A (en) * | 2018-08-28 | 2018-12-14 | 朋仁锋 | A kind of coal gasification method |
| CN109652138A (en) * | 2018-11-30 | 2019-04-19 | 浙江天禄环境科技有限公司 | A kind of method and system preparing synthesis gas using low-order coal |
| CN111253975A (en) * | 2018-11-30 | 2020-06-09 | 浙江天禄环境科技有限公司 | Method for grading and utilizing low-rank coal |
| CN111253974A (en) * | 2018-11-30 | 2020-06-09 | 浙江天禄环境科技有限公司 | Method and system for preparing synthesis gas by low-rank coal classification utilization |
| CN109652140A (en) * | 2018-12-13 | 2019-04-19 | 浙江天禄环境科技有限公司 | It is a kind of with waste water water-coal-slurry and to pass through the method and system of water-coal-slurry preparing synthetic gas |
| CN109652139A (en) * | 2018-12-13 | 2019-04-19 | 浙江天禄环境科技有限公司 | A kind of method and system preparing synthesis gas using volatile matter in low-order coal and waste water |
| CN109762606A (en) * | 2019-02-01 | 2019-05-17 | 浙江天禄环境科技有限公司 | A kind of method of the reduction of low order coal gasification hydrogen and carbon monoxide |
| CN109880654A (en) * | 2019-02-01 | 2019-06-14 | 浙江天禄环境科技有限公司 | A method of utilizing volatile matter Fischer Tropsch waxes in low-order coal |
| CN109762604A (en) * | 2019-02-01 | 2019-05-17 | 浙江天禄环境科技有限公司 | A method of utilizing low-order coal Fischer Tropsch waxes |
| CN110055104A (en) * | 2019-04-01 | 2019-07-26 | 浙江天禄环境科技有限公司 | A kind of method that the utilization of low-order coal sub-prime prepares natural gas |
| CN110093174A (en) * | 2019-04-01 | 2019-08-06 | 浙江天禄环境科技有限公司 | A kind of method of low-order coal hydrogen manufacturing |
| CN110055107A (en) * | 2019-04-03 | 2019-07-26 | 浙江天禄环境科技有限公司 | A kind of method that low-order coal sub-prime utilizes technique waste water zero-emission |
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