CN102517108A - Technology for preparing liquefied natural gas and liquid ammonia by using coke oven gas - Google Patents
Technology for preparing liquefied natural gas and liquid ammonia by using coke oven gas Download PDFInfo
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- 239000007789 gas Substances 0.000 title claims abstract description 192
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 239000000571 coke Substances 0.000 title claims abstract description 101
- 238000005516 engineering process Methods 0.000 title claims abstract description 41
- 239000003949 liquefied natural gas Substances 0.000 title claims abstract description 35
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 137
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 79
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 79
- 239000001257 hydrogen Substances 0.000 claims abstract description 79
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000000926 separation method Methods 0.000 claims abstract description 54
- 230000006835 compression Effects 0.000 claims abstract description 5
- 238000007906 compression Methods 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 136
- 238000000034 method Methods 0.000 claims description 91
- 229910052757 nitrogen Inorganic materials 0.000 claims description 67
- 230000008569 process Effects 0.000 claims description 43
- 230000015572 biosynthetic process Effects 0.000 claims description 35
- 238000003786 synthesis reaction Methods 0.000 claims description 35
- 238000001179 sorption measurement Methods 0.000 claims description 32
- 230000009466 transformation Effects 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000005194 fractionation Methods 0.000 claims description 18
- 150000002431 hydrogen Chemical class 0.000 claims description 18
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 16
- 238000006477 desulfuration reaction Methods 0.000 claims description 12
- 230000023556 desulfurization Effects 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 239000005864 Sulphur Substances 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 8
- 235000018553 tannin Nutrition 0.000 claims description 8
- 229920001864 tannin Polymers 0.000 claims description 8
- 239000001648 tannin Substances 0.000 claims description 8
- 238000011160 research Methods 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000013461 design Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 18
- 239000000047 product Substances 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000000274 adsorptive effect Effects 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 12
- 239000003345 natural gas Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 239000002918 waste heat Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000005108 dry cleaning Methods 0.000 description 5
- 239000011269 tar Substances 0.000 description 5
- 241000282326 Felis catus Species 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910017116 Fe—Mo Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Hydrogen, Water And Hydrids (AREA)
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Abstract
The invention discloses a technology for preparing liquefied natural gas and liquid ammonia by using coke oven gas. The coke oven gas is subjected to the steps of compression, purification, methanation, cryogenic separation and liquefaction of synthetic natural gas, variable pressure adsorptive separation and liquid ammonia preparation with hydrogen rich gas, so that the liquefied natural gas (LNG) of which methane purity is more than 99 percent and the liquid ammonia reaching national first level standard are obtained. By the technology, the hydrogen byproduct of the coke oven gas for preparing the LNG is fully utilized; effective ingredients of the coke oven gas such as H2, N2, CH4, CO and CO2 are furthest utilized; the CO and the CO2 are methanated, so that the yield of the CH4 is improved by about 1/3; the liquefied CH4 is used as the LNG and sold; and the rest nitrogen-containing hydrogen-rich gas is used as a raw material for synthesizing ammonia, so that the additional value of the coke oven gas is improved, and reliable raw material guarantee is provided for developing downstream products with high additional values and prolonging the product chain.
Description
Technical field
The invention belongs to the applied technical field of coke(oven)gas, particularly a kind of technology of utilizing coke(oven)gas preparing liquefied natural gas coproduction liquefied ammonia.
Background technology
China is first in the world coke production state, and the coke aggregated capacity is about 4.0 hundred million tons at present, and coke output was 3.88 hundred million tons in 2010, and coke output accounts for about 62% of global ultimate production, and the coke(oven)gas of by-product enormous amount.By the about 400m of coke by-product per ton
3Coke(oven)gas calculates, and heating is personal to reach civilian (making town gas), production synthetic ammonia or the methyl alcohol about 20,000,000,000 Nm of the coke(oven)gas that diffuses every year except that melting down
3
In recent years; Domestic had many relevant elaborations about the technology of coke(oven)gas through methanation system synthetic natural gas and natural gas liquids; CN1919985A, CN101709237A, CN101709238A, CN101508922, CN101391935, CN101747965A, CN101649232, CN101434879, CN101280235 etc. all disclose the method with circulation of coke(oven)gas multistage or the disposable methanation process preparing natural gas that passes through; But the shortcoming of the whole bag of tricks all is fully effectively to utilize the hydrogen in the coke(oven)gas, and economic benefit is limited.
CN101818087A, CN101597527A, CN101100622A disclose a kind of carbon of in coke(oven)gas, mending, and benefit carbon form once property benefit is gone into system or repeatedly mended, and mends the carbon amount and also has nothing in common with each other.Though this method has made full use of the H in the coke(oven)gas
2Resource, but mend carbon technology need to increase the depth decarburization device after methanation exists that long flow path, investment are big, methane and the low shortcoming of heat energy recycle rate.This technical process simultaneously needs near this device suitable carbon source is arranged, like converter gas, blast furnace gas and stack gas etc.If with stack gas is carbon source, wherein CO
2Content has only 7～8%, purifies and the big (CO of purification investment
2About 0.4～0.5 yuan/Nm of production cost
3), therefore with the cost that increases the coke(oven)gas preparing liquefied natural gas greatly, be that raw material is mended carbon the method that hydrogen unnecessary in the coke(oven)gas is converted into methane is not suitable for this project with stack gas.If near this device Iron And Steel Plant are arranged, utilize and contain a large amount of CO, CO in converter gas or the blast furnace gas
2Mend carbon, then can increase the output of natural gas liquids, better economy.But China 62% is coal chemical enterprise independently, does not generally have steel mill around the coke-oven plant, makes the application of this method be restricted.If set up a cover coal generating gas device to this project, coke(oven)gas mended carbon (CO+CO
2) produce natural gas liquids, this formula investing is higher relatively, and the price of coal and gas purification cost are all higher, need consider removing of sulphur in the water-gas simultaneously.
Therefore, utilize coke(oven)gas to produce natural gas liquids parallel connection production fluid ammonia, can be effectively, make full use of the coke(oven)gas resource, be the realization energy-saving and emission-reduction, one of the important content of developing a circular economy.
CN1919985A discloses and has a kind ofly returned coke oven combustion to the coke(oven)gas hydrogen rich gas, and calorific value and added value are lower, fail effectively to make full use of the H in the coke(oven)gas
2Resource.
CN101280235 A makes pure hydrogen with hydrogen-rich gas through behind the pressure-changed adsorption concentrating, and added value is relatively low.To produce bigger economic benefit if utilize pure hydrogen to do further deep processing.
Summary of the invention
The purpose of this invention is to provide a kind of above problem that overcomes; Utilize the technology of coke(oven)gas preparing liquefied natural gas coproduction liquefied ammonia; The present invention can obtain the high natural gas liquids of calorific value effectively; And the heat generation 0.5 ~ 10MPa higher-grade steam that utilizes reaction to generate, the power as compressor has reduced power consumption.Aspect composition, the present invention has made full use of the active principle in the coke(oven)gas, with CO and CO
2Methanation makes CH
4It is about 1/3 that output improves, and sell as natural gas liquids (LNG) the liquefaction back, and remaining nitrogenous hydrogen-rich gas has extended product chain as the raw material of synthetic ammonia, has improved the added value of coke(oven)gas, and economic benefit is considerable.The present invention has not only made full use of CH in the coke(oven)gas
4, H
2, N
2, CO, CO
2Etc. resource, and realize the zero release of continuous production and pollutent, not only helped protecting environment and optimize China's energy structure, also helped upgrading transition of coal chemical enterprise simultaneously.
For realizing the purpose of foregoing invention, the technical scheme that the present invention adopts is following:
A kind of technology of utilizing coke(oven)gas preparing liquefied natural gas coproduction liquefied ammonia may further comprise the steps:
(1) compression section: coke(oven)gas is compressed to 0.5 ~ 5.5Mpa;
(2) coke(oven)gas purifies: remove impurity such as coke(oven)gas is coal-tar middle oil, naphthalene, ammonia, sulphur;
(3) coke-oven gas methanation: adopt 2 ~ 5 grades of methanation reactions, obtaining with methane is main high methane gas, outlet CO
2Less than 50ppm;
(4) synthetic natural gas low temperature separation process liquefaction:
Get into low temperature separation process liquefaction operation after the high methane gas cooled dehydrated that step (3) obtains, adopt the low temperature separation process liquefaction process of band rectifying, obtain LNG at the tower still of fractionate, the yield of LNG is 96 ~ 99%; Cat head obtains hydrogen, nitrogen and contains the hydrogen-rich gas of a small amount of methane, and hydrogen-rich gas gets into transformation fractionation by adsorption operation after reclaiming cold;
(5) transformation fractionation by adsorption operation and hydrogen rich gas system liquefied ammonia: hydrogen-rich gas separates hydrogen, nitrogen and methane in the transformation adsorption separation device, obtains hydrogen, nitrogen and methane respectively, mixes the back then nitrogen pressure and with hydrogen according to f=n
H2: n
N2=2.95 ~ 3.05:1 proportioning hydrogen and nitrogen get into the ammonia synthesis operation; Replenish the nitrogen of part purity in 99.995%～99.999% scope; Nitrogen source employing deep cooling low ternperature separation process technology or PSA nitrogen producing craft and the non-low ternperature separation process technology of film separation and nitrogen-making technology are carried out air separation, are forced into 12.0～32.0MPa after hydrogen that satisfies condition and nitrogen mix and get into ammonia synthesis converter production liquefied ammonia.
The described gas booster compressor of step (1) is reciprocating type or radial compressor, and coke(oven)gas is compressed to 0.5 ~ 2.5MPa.
The described sulphur that removes in the coke(oven)gas of step (2) adopts dry method to add the wet method sulfur removal technology.
Said dry-desulphurizer adopts the JT-8 type hydrogenation catalyst of northwest chemical research designing institute, and wet desulphurization adopts PDS method or PDS to add the tannin extract method.
Be provided with the fine desulfurization process by dry tower before step (3) methanator, Zinc oxide desulfurizer is adopted in smart desulfurization, makes the synthetic gas total sulfur less than 0.1mg/Nm
3
Step (3) adopts 2 ~ 4 grades of methanation reactions, and obtaining with methane is main gaseous mixture, the synthetic rope TREMP of Top that adopts of methane
TMThe band circulation adiabatic methanation process of methanation process, the CRG methanation process of wearing dimension or Southwest Chemical Research and Design Institute.
Said methanation catalyst adopts the rope MCR-2X of Top methanation catalyst, the CEG-LH methanation catalyst of Dai Wei company or the CNJ-5 type methanation catalyst of Southwest Chemical Research and Design Institute.
Silica gel or molecular sieve dehydration are adopted in the described dehydration of step (4).
In the step (5), the nitrogen source is the nitrogen production by air separation technology, and ammonia synthesis pressure is 15.0～26.0MPa.
Wherein:
(1) compression section: coke(oven)gas is compressed to 0.5 ~ 5.5MPa, and evaluation method selecting optimal equipment is reciprocating type or radial compressor, and coke(oven)gas compresses preferably to 0.5 ~ 2.5MPa.
(2) coke(oven)gas purifies:
Raw coke oven gas is handled through preliminary cleaning, removed impurity such as wherein tar, naphthalene, benzene, the coke(oven)gas after being purified.
This purifying method can adopt conventional coke(oven)gas purifying method.Purification means to impurity composition in the coke(oven)gas (removing the sulfuration beyond the region of objective existence) are a lot, take off naphthalene method, TH (wet oxidation ammonia) method, FRC (catalyzed oxidation) method or improvement ADA method, coagulation, absorption method etc. like the burnt method of electric fishing, oil wash.Also can adopt China invention application number is disclosed purifying treatment method in 200810045657.4 " coke(oven)gas dry cleaning temperature swing adsorption process ".
The thick desulfurization of coke(oven)gas adopts PDS method or PDS to add the tannin extract method, and dry desulfurization is adopted in smart desulfurization.
The JT-8 type hydrogenation catalyst of northwest chemical research designing institute is a kind of novel organic sulfur hydroconversion catalyst.This catalyzer is mainly used in CO content below 10%, and olefin(e) centent is the hydrocracking organic sulfide removal and the unsaturated hydrocarbons process of raw material at 5% left and right sides coke(oven)gas.At air speed 500～2000h
-1, 250～450 ℃ of temperature of reaction under the condition of pressure 0.8～5.0MPa, are 100～400mg/Nm to containing organosulfur
3Coke(oven)gas, the organosulfur transformation efficiency can reach more than 97%.
Coke(oven)gas add through PDS method or PDS method tannin extract or after remove most inorganic sulfur; Getting into hydrogenation catalyst layer (available main reactive metal is the hydrogenation catalyst of Co-Mo, Ni-Mo or Fe-Mo); Through fine desulfurization catalyst layer (available zinc oxide or special typed active carbon), purify total sulfur≤0.1mg/Nm in the coke(oven)gas of back then
3
(3) coke-oven gas methanation:
Adopt multistage adiabatic methanation reactor drum to carry out multistage methanation reaction (2 ~ 5 grades), preferred 2 ~ 4 grades.
Methanation working pressure: 0.5 ~ 2.5MPa, air speed: 2000 ~ 20000h
-1, service temperature: 250 ~ 650 ℃.
Methanation process can adopt no circulation primary by the adiabatic methanation process of methanation process with the band circulation.Band round-robin adiabatic methanation process flow process need be provided with recycle compressor, is to adopt the mode of Control Circulation ratio to control the temperature rise of methanation furnace, smooth operation.Adopt useless pot to produce the vapor recovery heat between the methanation furnace, but by-product 0.5 ~ 10MPa higher-grade steam.
No circulation adiabatic methanation process is in virgin gas, to add the disposable methanator that passes through behind a certain amount of water vapor.The temperature of this technology methanator outlet is higher, add quantity of steam and strengthen, and the investment of waste heat boiler is relatively large, but can save recycle compressor and reduce power consumption.
The rope TREMP of Top
TMFirst reactor drum of circulation methanation technology and second reactors in series utilize first reactor outlet gas to circulate, and the setting that replenishes methanator then requires to decide according to virgin gas composition and synthetic natural gas methane content.Top's rope methanation process adopts steam injector to replace recycle compressor, a large amount of superheated vapours are joined in the process system, so the rich steam total amount of producing of methanation operation is less, and tooling cost is higher, and the consumption of water is also bigger simultaneously.Methanation catalyst is high temperature resistant MCR-2X type catalyzer.
Dai Wei company has developed the HICOM methanation process on the basis of CRG methanation process.This Technology utilizes the hot gas of second methane reactor outlet to circulate, and dilution gets into the CO content of first methanator, thereby makes the temperature out of the methanator of winning be controlled at 620 ~ 650 ℃.The methanation catalyst that adopts is CEG-LH, and this catalyzer has certain mapping function.But this technology by-product high pressure, superheated steam.
Band round-robin adiabatic methanation process, can adopt the Chinese invention patent application number is disclosed methanation process in 200910058611.0 " a kind of methanation reaction process that utilizes coke(oven)gas to prepare synthetic natural gas ".The resurgent gases of utilizing purification section drives the steam turbine compressor then as the saturation steam that the overheated methanation operation of boiler oil produces, and can effectively improve full factory energy utilization ratio.It is disclosed catalyzer in 200810046429.9 " a kind of coke-oven gas methanation catalyst and preparation method thereof " that catalyzer can adopt the Chinese invention patent application number.
CNJ-5 type catalyzer is applicable to the speed venting etc. of coke(oven)gas, Methanol Plant and is rich in CO, CO
2And H
2Produce the methanation device of synthetic natural gas (SNG), compressed natural gas (CNG) and natural gas liquids (LNG) for raw material.
Through this technology, made full use of the heat that produces in the reaction process, effectively controlled CO+CO in the virgin gas
2Concentration, the gas circulation amount is little, and has effectively controlled the Outlet Gas Temperature of methanator, helps the selection of methanation reaction and reactor material.
(4) synthetic natural gas low temperature separation process liquefaction:
The method of utilizing low temperature separation process liquefaction is with the H in the synthetic natural gas
2, N
2Separate, to make clean energy and industrial chemicals-natural gas liquids.Separate the hydrogen-rich gas obtain and go out hydrogen, nitrogen and methane, make nitrogen, hydrogen and empty the branch 99.995% ~ 99.999% nitrogen and mixes entering ammonia synthesis operation after the pressurization then through the transformation fractionation by adsorption.
Low temperature separation process can be adopted the PRICO single loop azeotrope refrigeration techniques of rich Rec Wei Qi company, and treated virgin gas and produce the LNG product liquefies.
It number is disclosed technology in 200910310615.3 or 200910310655.8 " a kind of method of utilizing coke(oven)gas to prepare natural gas liquids " that low temperature separation process also can be adopted one Chinese patent application.
(5) transformation fractionation by adsorption operation and hydrogen rich gas system liquefied ammonia: hydrogen-rich gas separates hydrogen, nitrogen and methane in the transformation adsorption separation device, obtains hydrogen, nitrogen and methane respectively.
Hydrogen, nitrogen and empty branch make 99.995% ~ 99.999% nitrogen according to f=n
H2: n
N2=2.95 ~ 3.05:1 proportioning gets into the ammonia synthesis operation.
Because the nitrogen amount of low temperature separation process liquefaction operation by-product is not enough, needs to replenish the nitrogen of part purity in 99.995%～99.999% scope.N
2The source can adopt deep cooling low ternperature separation process technology or PSA (Pressure Swing Adsorption, transformation absorption) nitrogen producing craft and the non-low ternperature separation process technology of film separation and nitrogen-making technology to carry out air separation, preferred nitrogen production by air separation technology.
Gas mixture gets into interchanger after feed gas compressor is pressurized to 12.0～32.0MPa.In interchanger with from the reaction gas of feedwater preheater, be sent to ammonia synthesis converter after by preheating through heat exchange; In the ammonia synthesis catalyst bed, carry out building-up reactions; The volumetric concentration of outlet ammonia is increased to 12 ~ 15%, can control the into temperature of tower gas through tap line by-passing portions gas.Reaction gas can reclaim heat through waste heat boiler, produces saturation steam.
Ammonia synthesis reactor is the nucleus equipment of synthetic ammonia installation, can adopt the GC of Nanjing Guochang Chemical Industry Science Co., Ltd profile shaft radially ammonia synthesis reactor or Hu'nan Anchun High & New Technology Co. Ltd.'s diameter of axle to mixing the bed ammonia synthesis reactor.
Through above process step, can make methane purity greater than 99% natural gas liquids (LNG) with reach the liquefied ammonia of country-level standard.
Compared with prior art, the invention has the beneficial effects as follows:
(1) starts the novel method of industrial discharge gas coke(oven)gas comprehensive reutilization, protected environment, saved the energy.Technically, methanation reaction process of the present invention can reduce interchanger quantity, makes full use of the heat that produces in the reaction, and the higher-grade steam that the heat energy that reaction produces can by-product 0.5 ~ 10MPa is as the power of compressor; Secondly the ability better controlled gets into the virgin gas composition of methanators at different levels, and circulating flow rate reduces, and has reduced energy consumption; Effectively controlled the temperature of methanator exit gas, helped the selection of reactor material, thereby reduce cost.Improved the added value of coke(oven)gas, for development downstream high value added product, extension product chain reliable raw material guarantee is provided simultaneously.
(2) process makes full use according to the invention the by-product hydrogen of coke(oven)gas system LNG, farthest utilized CH in the coke(oven)gas
4, H
2, N
2, CO, CO
2Active principle is with CO and CO
2Methanation makes CH
4It is about 1/3 that output improves, and makes that available resources obtain utilizing in the coke(oven)gas, and realized the zero release of continuous production and pollutent.
(3) H that low temperature separation process liquefies out among the present invention
2, N
2Press extraction on the active principle band, reduced the loss of compression work.Compare with mend carbon technology, reduced and mended of the restriction of carbon carbon source this technology.
Description of drawings
Fig. 1 is the coke(oven)gas system LNG coproduction liquefied ammonia process flow diagram in the inventive method, and as the coke(oven)gas system LNG coproduction liquefied ammonia process flow diagram of embodiment 1;
Fig. 2 is the hydrogen rich gas system liquefied ammonia process flow diagram in the inventive method, and as the hydrogen rich gas system liquefied ammonia process flow diagram of embodiment 1;
Mark among the figure: C1, C2 are compressors, and T1 is a mixing tank, and R1 is an ammonia synthesis converter, and E1-E4 is an interchanger, and T2 is a liquid ammonia storage tank.
Embodiment
Below in conjunction with embodiment foregoing invention content of the present invention is done further to describe in detail.
But should this be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.Not breaking away under the above-mentioned technological thought situation of the present invention, according to ordinary skill knowledge and customary means, make various replacements and change, all should comprise within the scope of the invention.
Embodiment 1
The present embodiment coke(oven)gas is formed (vol%): H
257.6, CH
426.9 CO 7.2, CO
22.1, N
24.1, C
2H
62.1.Coke(oven)gas tolerance is 50000Nm
3/ h, 40 ℃ of temperature.
(1) coke(oven)gas is compressed to 0.5 MPa;
(2) coke(oven)gas purifies
Adopt the dry cleaning temperature swing adsorption method, remove impurity such as tar in the virgin gas, naphthalene, ammonia, sulphur.Getting into PDS method or PDS then adds tannin extract method wet desulphurization operation, dry desulfurization operation the total sulfur in the coke(oven)gas is taken off to≤0.1mg/Nm
3, the coke(oven)gas after being purified.
(3) coke-oven gas methanation:
Adopt level Four band round-robin adiabatic methanation process.
Composition behind the coke-oven gas methanation (vol%) is: H
234.5, CH
459.5, N
26.0, CO
2≤50ppm.Synthetic natural gas tolerance after the methanation is 33950Nm
3/ h, 40 ℃ of temperature.At this by-product 3.8MPa ~ 10.0 MPa higher-grade steam.
(4) synthetic natural gas low temperature separation process liquefaction:
Adopt the low temperature separation process liquefaction process of band rectifying, the gas pressurization to 4.5 after the methanation ~ 5.5MPa dehydrates the back and gets into the low temperature separation process liquefying plant.Under the effect of rectifying tower rectifying, from product, isolate hydrogen/nitrogen to cat head, the tower still obtains the methane of 99% purity.
LNG output is 20200Nm in the present embodiment
3/ h, methane yield are 99%.
Nitrogenous hydrogen-rich gas output is 13750Nm
3/ h, its composition (vol%) is: H
285.1, CH
41.5, N
213.4,0.7MPa, 40 ℃ of temperature.Hydrogen-rich gas separates hydrogen, nitrogen and methane in the transformation adsorption separation device, obtains hydrogen, nitrogen and methane respectively.The nitrogen that the transformation fractionation by adsorption goes out is allocated back entering ammonia synthesis operation with hydrogen after dividing the nitrogen mixing that makes to be forced into 0.7MPa with sky.The methane that the transformation fractionation by adsorption goes out mix with synthetic natural gas and pressurize after go low temperature separation process liquefaction operation.
The nitrogen output that empty branch makes is 1988Nm
3/ h, its composition (vol%) is: N
299.995%, normal pressure, 40 ℃ of temperature.
(5) transformation fractionation by adsorption operation and hydrogen rich gas system liquefied ammonia:
Technical process as shown in Figure 2, employing ~ 12.0MPa synthesis technique.
According to f=n
H2: n
N2=3.05:1 proportioning gets into the hydrogen and the nitrogen of ammonia synthesis operation.Because nitrogen is not enough in the hydrogen of low temperature separation process liquefaction operation by-product and the nitrogen, needs to replenish part nitrogen.Additional nitrogen gas purity is generally in 99.995%～99.999% scope.The hydrogen that satisfies condition and nitrogen mix after feed gas compressor be pressurized to～12.0MPa after through being sent to ammonia synthesis converter after the preheating after the heat exchange; In the ammonia synthesis catalyst bed, carry out building-up reactions; The volumetric concentration of outlet ammonia is increased to 12 ~ 15%, can control the into temperature of tower gas through tap line by-passing portions gas.Reaction gas can reclaim heat through waste heat boiler, produces saturation steam.
Liquefied ammonia output is 5.75t/h among this embodiment, i.e. 46033t/a, and by-product 1.6MPa saturation steam.
Embodiment 2
The present embodiment coke(oven)gas is formed (vol%): H
257.6, CH
426.9 CO 7.2, CO
22.1, N
24.1, C
2H
62.1.Coke(oven)gas tolerance is 50000Nm
3/ h, 40 ℃ of temperature.
(1) coke(oven)gas is compressed to 5.5 MPa;
(2) coke(oven)gas purifies
Adopt the dry cleaning temperature swing adsorption method, remove impurity such as tar in the virgin gas, naphthalene, ammonia, sulphur.Getting into PDS method or PDS then adds tannin extract method wet desulphurization operation, dry desulfurization operation the total sulfur in the coke(oven)gas is taken off to≤0.1mg/Nm
3, the coke(oven)gas after being purified.
(3) coke-oven gas methanation:
Adopt three grades of no circulation primary to pass through methanation process.
Composition behind the coke-oven gas methanation (vol%) is: H
234.5, CH
459.5, N
26.0, CO
2≤50ppm.Synthetic natural gas tolerance after the methanation is 33950Nm
3/ h, 40 ℃ of temperature.At this by-product 3.8MPa ~ 10.0 MPa higher-grade steam.
(4) synthetic natural gas low temperature separation process liquefaction:
Adopt the low temperature separation process liquefaction process of band rectifying, get into the low temperature separation process liquefying plant after the gas dewatering drying after the methanation.Under the effect of rectifying tower rectifying, from product, isolate hydrogen/nitrogen to cat head, the tower still obtains the methane of 99% purity.
LNG output is 19588Nm in the present embodiment
3/ h, methane yield are 96%.
Nitrogenous hydrogen-rich gas output is 14362Nm
3/ h, its composition (vol%) is: H
281.5, CH
41.3, N
217.2,0.7MPa, 40 ℃ of temperature.Hydrogen-rich gas separates hydrogen, nitrogen and methane in the transformation adsorption separation device, obtains hydrogen, nitrogen and methane respectively.The nitrogen that the transformation fractionation by adsorption goes out is allocated back entering ammonia synthesis operation with hydrogen after dividing the nitrogen mixing that makes to be forced into 0.7MPa with sky.The methane that the transformation fractionation by adsorption goes out mix with synthetic natural gas and pressurize after go low temperature separation process liquefaction operation.
The nitrogen output that empty branch makes is 1434Nm
3/ h, its composition (vol%) is: N
299.995%, normal pressure, 40 ℃ of temperature.
(5) transformation fractionation by adsorption operation and hydrogen rich gas system liquefied ammonia:
Technical process as shown in Figure 2, employing ~ 32.0MPa synthesis technique.
According to f=n
H2: n
N2=3.0:1 proportioning gets into the hydrogen and the nitrogen of ammonia synthesis operation.Because nitrogen is not enough in the hydrogen of low temperature separation process liquefaction operation by-product and the nitrogen, needs to replenish part nitrogen.Additional nitrogen gas purity is generally in 99.995%～99.999% scope.The hydrogen that satisfies condition and nitrogen mix after feed gas compressor be pressurized to～32.0MPa after through being sent to ammonia synthesis converter after the preheating after the heat exchange; In the ammonia synthesis catalyst bed, carry out building-up reactions; The volumetric concentration of outlet ammonia is increased to 12 ~ 15%, can control the into temperature of tower gas through tap line by-passing portions gas.Reaction gas can reclaim heat through waste heat boiler, produces saturation steam.
Liquefied ammonia output is 5.851t/h among this embodiment, i.e. 46805t/a, and by-product 1.6MPa saturation steam.
Embodiment 3
The present embodiment coke(oven)gas is formed (vol%): H
257.7, CH
421.8 CO 8.83, CO
24.38, N
24.69, C
2H
62.6.Coke(oven)gas tolerance is 50000Nm
3/ h, 40 ℃ of temperature.
(1) coke(oven)gas is compressed to 2.5 MPa;
(2) coke(oven)gas purifies:
Adopt the dry cleaning temperature swing adsorption method, remove impurity such as tar in the virgin gas, naphthalene, ammonia, sulphur.Getting into PDS method or PDS then adds tannin extract method wet desulphurization operation, dry desulfurization operation the total sulfur in the coke(oven)gas is taken off to≤0.1mg/Nm
3, the coke(oven)gas after being purified.
(3) coke-oven gas methanation:
Adopt secondary band round-robin adiabatic methanation process.
Composition behind the coke-oven gas methanation (vol%) is: H
215.9, CH
475.3, N
28.8, CO
2≤50ppm.Synthetic natural gas tolerance after the methanation is 26695Nm
3/ h, 40 ℃ of temperature.At this by-product 3.8MPa ~ 10.0 MPa higher-grade steam.
(4) synthetic natural gas low temperature separation process liquefaction:
Adopt the low temperature separation process liquefaction process of band rectifying, the gas pressurization to 4.5 after the methanation ~ 5.5MPa dehydrates the back and gets into the low temperature separation process liquefying plant.Under the effect of rectifying tower rectifying, from product, isolate hydrogen/nitrogen to cat head, the tower still obtains the methane of 99% purity.
LNG output is 20105Nm among this embodiment
3/ h, methane yield are 99%.
Nitrogenous hydrogen-rich gas output is 6590Nm
3/ h, its composition (vol%) is: H
264.4, CH
43.1, N
232.5,0.7MPa, 40 ℃ of temperature.Hydrogen-rich gas separates hydrogen, nitrogen and methane in the transformation adsorption separation device, obtains hydrogen, nitrogen and methane respectively.The nitrogen pressure that the transformation fractionation by adsorption goes out is to 0.7MPa and hydrogen allotment back entering ammonia synthesis operation.The methane that the transformation fractionation by adsorption goes out mix with synthetic natural gas and pressurize after go low temperature separation process liquefaction operation.
(5) transformation fractionation by adsorption operation and hydrogen rich gas system liquefied ammonia:
Technical process as shown in Figure 2, employing ~ 15.0MPa synthesis technique.
According to f=n
H2: n
N2=3.0:1 proportioning gets into the hydrogen and the nitrogen of ammonia synthesis operation.The hydrogen that satisfies condition and nitrogen mix after feed gas compressor be pressurized to～15.0MPa after through being sent to ammonia synthesis converter after the preheating after the heat exchange; In the ammonia synthesis catalyst bed, carry out building-up reactions; The volumetric concentration of outlet ammonia is increased to 12 ~ 15%, can control the into temperature of tower gas through tap line by-passing portions gas.Reaction gas can reclaim heat through waste heat boiler, produces saturation steam.
Liquefied ammonia output is 2.123t/h among this embodiment, i.e. 16980t/a, and by-product 1.6MPa saturation steam.
Embodiment 4
The present embodiment coke(oven)gas is formed (vol%): H
257.7, CH
421.8 CO 8.83, CO
24.38, N
24.69, C
2H
62.6.Coke(oven)gas tolerance is 50000Nm
3/ h, 40 ℃ of temperature.
(1) coke(oven)gas is compressed to 1.5 MPa;
(2) coke(oven)gas purifies:
Adopt the dry cleaning temperature swing adsorption method, remove impurity such as tar in the virgin gas, naphthalene, ammonia, sulphur.Getting into PDS method or PDS then adds tannin extract method wet desulphurization operation, dry desulfurization operation the total sulfur in the coke(oven)gas is taken off to≤0.1mg/Nm
3, the coke(oven)gas after being purified.
(3) coke-oven gas methanation:
Adopt Pyatyi not have circulation primary and pass through methanation process.
Composition behind the coke-oven gas methanation (vol%) is: H
215.9, CH
475.3, N
28.8, CO
2≤50ppm.Synthetic natural gas tolerance after the methanation is 26695Nm
3/ h, 40 ℃ of temperature.At this by-product 3.8MPa ~ 10.0 MPa higher-grade steam.
(4) synthetic natural gas low temperature separation process liquefaction:
Adopt the low temperature separation process liquefaction process of band rectifying, get into the low temperature separation process liquefying plant after the gas dewatering drying after the methanation.Under the effect of rectifying tower rectifying, from product, isolate hydrogen/nitrogen to cat head, the tower still obtains the methane of 99% purity.
LNG output is 19496Nm in the present embodiment
3/ h, methane yield are 98%.
Nitrogenous hydrogen-rich gas output is 7199Nm
3/ h, its composition (vol%) is: H
258.9, CH
42.7, N
238.4,0.7MPa, 40 ℃ of temperature.Hydrogen-rich gas separates hydrogen, nitrogen and methane in the transformation adsorption separation device, obtains hydrogen, nitrogen and methane respectively.The nitrogen pressure that the transformation fractionation by adsorption goes out is to 0.7MPa and hydrogen allotment back entering ammonia synthesis operation.The methane that the transformation fractionation by adsorption goes out mix with synthetic natural gas and pressurize after go low temperature separation process liquefaction operation.
(5) transformation fractionation by adsorption operation and hydrogen rich gas system liquefied ammonia:
Technical process as shown in Figure 2, employing ~ 26.0MPa synthesis technique.
According to f=n
H2: n
N2=2.95:1 proportioning gets into the hydrogen and the nitrogen of ammonia synthesis operation.The hydrogen that satisfies condition and nitrogen mix after feed gas compressor be pressurized to～26.0MPa after through being sent to ammonia synthesis converter after the preheating after the heat exchange; In the ammonia synthesis catalyst bed, carry out building-up reactions; The volumetric concentration of outlet ammonia is increased to 12 ~ 15%, can control the into temperature of tower gas through tap line by-passing portions gas.Reaction gas can reclaim heat through waste heat boiler, produces saturation steam.
Liquefied ammonia output is 2.087t/h among this embodiment, i.e. 16700t/a, and by-product 1.6MPa saturation steam.
The sorbent material of each used model, hydrogenation catalyst, methanation catalyst and ammonia synthesis catalyst etc. are the commercially available prod among the above embodiment.
Claims (9)
1. technology of utilizing coke(oven)gas preparing liquefied natural gas coproduction liquefied ammonia is characterized in that may further comprise the steps:
(1) compression section: coke(oven)gas is compressed to 0.5 ~ 5.5Mpa;
(2) coke(oven)gas purifies: remove impurity such as coke(oven)gas is coal-tar middle oil, naphthalene, ammonia, sulphur;
(3) coke-oven gas methanation: adopt 2 ~ 5 grades of methanation reactions, obtaining with methane is main high methane gas, outlet CO
2Less than 50ppm;
(4) synthetic natural gas low temperature separation process liquefaction: get into low temperature separation process liquefaction operation after the high methane gas cooled dehydrated that step (3) obtains, adopt the low temperature separation process liquefaction process of band rectifying, obtain LNG at the tower still of fractionate, the yield of LNG is 96 ~ 99%; Cat head obtains hydrogen, nitrogen and contains the hydrogen-rich gas of a small amount of methane, and hydrogen-rich gas gets into transformation fractionation by adsorption operation after reclaiming cold;
(5) transformation fractionation by adsorption operation and hydrogen rich gas system liquefied ammonia: hydrogen-rich gas separates hydrogen, nitrogen and methane in the transformation adsorption separation device, obtains hydrogen, nitrogen and methane respectively, mixes the back then nitrogen pressure and with hydrogen according to f=n
H2: n
N2=2.95 ~ 3.05:1 proportioning hydrogen and nitrogen get into the ammonia synthesis operation; Replenish the nitrogen of part purity in 99.995%～99.999% scope; Nitrogen source employing deep cooling low ternperature separation process technology or PSA nitrogen producing craft and the non-low ternperature separation process technology of film separation and nitrogen-making technology are carried out air separation, are forced into 12.0～32.0MPa after hydrogen that satisfies condition and nitrogen mix and get into ammonia synthesis converter production liquefied ammonia.
2. the technology of utilizing coke(oven)gas preparing liquefied natural gas coproduction liquefied ammonia according to claim 1 is characterized in that: the described gas booster compressor of step (1) is reciprocating type or radial compressor, and coke(oven)gas is compressed to 0.5 ~ 2.5MPa.
3. the technology of utilizing coke(oven)gas preparing liquefied natural gas coproduction liquefied ammonia according to claim 1 is characterized in that: the described sulphur that removes in the coke(oven)gas of step (2) adopts dry method to add the wet method sulfur removal technology.
4. the technology of utilizing coke(oven)gas preparing liquefied natural gas coproduction liquefied ammonia according to claim 3 is characterized in that: said dry-desulphurizer adopts the JT-8 type hydrogenation catalyst of northwest chemical research designing institute, and wet desulphurization adopts PDS method or PDS to add the tannin extract method.
5. the technology of utilizing coke(oven)gas preparing liquefied natural gas coproduction liquefied ammonia according to claim 1 is characterized in that: be provided with the fine desulfurization process by dry tower before step (3) methanator, Zinc oxide desulfurizer is adopted in smart desulfurization, makes the synthetic gas total sulfur less than 0.1mg/Nm
3
6. the technology of utilizing coke(oven)gas preparing liquefied natural gas coproduction liquefied ammonia according to claim 1 is characterized in that: step (3) adopts 2 ~ 4 grades of methanation reactions, and obtaining with methane is main gaseous mixture, the synthetic rope TREMP of Top that adopts of methane
TMThe band circulation adiabatic methanation process of methanation process, the CRG methanation process of wearing dimension or Southwest Chemical Research and Design Institute.
7. the technology of utilizing coke(oven)gas preparing liquefied natural gas coproduction liquefied ammonia according to claim 6 is characterized in that: said methanation catalyst adopts the rope MCR-2X of Top methanation catalyst, the CEG-LH methanation catalyst of Dai Wei company or the CNJ-5 type methanation catalyst of Southwest Chemical Research and Design Institute.
8. the technology of utilizing coke(oven)gas preparing liquefied natural gas coproduction liquefied ammonia according to claim 1 is characterized in that: the described dehydration of step (4), adopt silica gel or molecular sieve dehydration.
9. the technology of utilizing coke(oven)gas preparing liquefied natural gas coproduction liquefied ammonia according to claim 1 is characterized in that: in the step (5), the nitrogen source is the nitrogen production by air separation technology, and ammonia synthesis pressure is 15.0～26.0MPa.
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