CN102585950A - Method for preparing synthetic natural gas by coke oven gas in combination with straw gas - Google Patents
Method for preparing synthetic natural gas by coke oven gas in combination with straw gas Download PDFInfo
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- CN102585950A CN102585950A CN2012100457450A CN201210045745A CN102585950A CN 102585950 A CN102585950 A CN 102585950A CN 2012100457450 A CN2012100457450 A CN 2012100457450A CN 201210045745 A CN201210045745 A CN 201210045745A CN 102585950 A CN102585950 A CN 102585950A
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Abstract
The invention discloses a method for preparing a synthetic natural gas by a coke oven gas in combination with a straw gas. The method comprises the following seven steps of: regulation of feed gas components, compression purification, pre-heating treatment and adding of water vapor, primary section of methanation reaction, secondary section of methanation reaction, gas-liquid separation, and pressure swing adsorption for purifying methanol to finally obtain the synthetic natural gas with CH4 concentration being more than 90%. According to the method for preparing the synthetic natural gas by the coke oven gas in combination with the straw gas, the coke oven gas and biomass renewable energy source straw gas are comprehensively used according to the characteristics of much hydrogen and less carbon in the coke oven gas and less hydrogen and much carbon in the straw gas to prepare the synthetic natural gas, energy exchange is fully utilized, circulating compression is reduced, energy is saved and emission is reduced, the economic benefit is improved, the environmental protection is facilitated, and the renewable biomass energy is developed to replace fossil energy.
Description
Technical field
The invention belongs to the comprehensive utilization technique field of coke-oven gas and Straw Gas, particularly, relating to a kind of is the method that raw material is produced synthetic natural gas with the cog joint Straw Gas.
Background technology
Coke-oven gas is the sub product in the coke production, and China is coke production big country, and annual throughput has 400m more than 300,000,000 tons according to per 1 ton of coke product approximately
3The coke-oven gas sub product generates, and the annual coke-oven gas that produces of China has 1,200 hundred million m approximately
3, coke is personal except producing, the heating, generating etc., 20,000,000,000 m are arranged approximately
3Rationally do not utilized.In recent years, the utilization of coke-oven gas more and more widely comprised behind hydrogen manufacturing, system methyl alcohol, deep purifying or the methanation reaction as gas etc.
Coke-oven gas component more complicated, H in its major ingredient
2Content accounts for 50 ~ 60%, CH
4Content accounts for 22 ~ 28%, and CO content accounts for 5 ~ 8%, CO
2Content accounts for 1 ~ 4%, N
2Content accounts for 2 ~ 7%, C
nH
mContent accounts for 1 ~ 3%, O
2Content accounts for 0.3 ~ 0.8%, also contains a spot of benzene, naphthalene, tar and sulfide etc. simultaneously.
H in the Straw Gas major ingredient
2Content accounts for 45 ~ 60%, CH
4Content accounts for 3 ~ 10%, and CO content accounts for 15 ~ 25%, CO
2Content accounts for 15 ~ 25%, N
2Content accounts for 0.3 ~ 3%, C
mH
nContent accounts for 0.2 ~ 2%, O
2Content accounts for 0.1 ~ 0.8%, also contains a spot of benzene, muriate, tar and sulfide etc. simultaneously.
The report of mending carbon in the coke-oven gas is also arranged in the existing open source literature, like " a kind of technology of employing coke-oven gas for production of methane " of CN101607859A, in this patent through adding 100% CO
2Or liquid CO
2Before being added into the coke-oven gas methanation reaction after the gasification, through adjustment CO
2Add-on is with unnecessary H
2React away; " a kind of carbon-replenishing hydrogen-returning process is realized the method for gas employing methanation of coke oven synthetic natural gas " of CN101712897A passed through in this patent stack gas through low dividing potential drop purification CO
2The H that back and transformation fractionation by adsorption are come out
2Turn back to carbon-replenishing hydrogen-returning workshop section simultaneously and carry out methanation reaction once more; " novel process of making synthetic natural gas by using coke-oven gas " of CN101818087A passes through to mend carbon gas (CO in this patent
2+ C=2CO) with before circulation gas joins methanation reaction, with unnecessary H
2React away.Power consumption in the whole methanation reaction process process more than 90% all is used on the gas compressor, the 1 volume CO that replenishes
2With 4 volume H
2Reaction generates 1 volume CH
4With 2 volume H
2No matter therefore O be to circulate before the gas behind the methanation reaction is returned first step methanation reaction, still with CO
2Add in the virgin gas and unnecessary H
2Reaction all can't be brought up to peak with economic benefit.
Summary of the invention
Technical problem to be solved by this invention provides the method that a kind of cog joint Straw Gas is produced synthetic natural gas; This method is few and many characteristics of the few carbon of hydrogen in the Straw Gas according to the many carbon of hydrogen in the coke(oven)gas; Comprehensive utilization coke-oven gas and biological renewable energy Straw Gas are produced synthetic natural gas, make full use of energy and exchange, and reduce loop compression; Energy-saving and emission-reduction are increased economic efficiency; And help environment protection, develop reproducible biomass new forms of energy and substitute fossil energy.
The present invention solves the problems of the technologies described above the technical scheme that is adopted:
A kind of cog joint Straw Gas is produced the method for synthetic natural gas, comprises the steps:
(1) adjustment virgin gas component: the flow size of adjustment coke-oven gas and Straw Gas makes H in the mixed gas mixture component of coke-oven gas and Straw Gas
2Mol ratio 3.0 ~ 4.0:1.0 with CO;
(2) adopt existing pressurization, purification, preconditioning technique, remove benzene, naphthalene, tar, heavy hydrocarbon compounds and sulfide;
(3) methanation reaction: with behind purified gas heat exchange to 300 ~ 350 ℃, add steam, accomplish the methanation reaction process through the reaction bed that nickel catalyst is housed again; The mol ratio of steam add-on and purified gas is 0.1～0.2:1;
(4) gas-liquid separation:, water coolant in the reactant gases is removed with existing method with the gas cooling to 30 behind the methanation reaction ~ 40 ℃;
(5) transformation absorption purification methane: IMPURITIES IN is removed after adopting pressure swing adsorption with gas-liquid separation, obtains CH
4The synthetic natural gas of concentration more than 90%.
Described methanation reaction adopts the reactor drum polyphone of two-stage different types to accomplish, and wherein one-level is an isothermal reactor, and the second stage is adiabatic reactor.
Perhaps described methanation reaction adopts a reactor drum to accomplish.
Existing methanation reaction is generally accomplished by 3 ~ 6 sections reactor drum polyphones, and the transformation efficiency of its CO of synthetic natural gas that so obtains after the reaction could be than higher, the gas mixture CH after purifying after it transforms
4Concentration just can reach the request for utilization of combustion gas; Adopt process method of the present invention, only need to adopt 1 section reactor drum or 2 sections polyphones to accomplish, so its CO just can reach higher transformation efficiency behind methanation reaction, the synthetic natural gas CH that the gas mixture after it transforms obtains after purifying
4Concentration can reach more than 90%, in terms of existing technologies, has reduced the hop count of reactor drum, can reduce input, loss and the maintenance cost of equipment, and the industrial application of being more convenient for is promoted.
The adsorption bed of described transformation absorption purification methane is to combine the CO under 0.5 ~ 1.5Mpa condition in the separating mixed gas by two or more sorbent materials at least in 3A molecular sieve, 4A molecular sieve, activated alumina, zeolite molecular sieve, activated carbon, the silica gel
2And N
2Zeolite molecular sieve can adopt the X zeolite molecular sieve of lithium X zeolite or low Si/Al ratio.
Nickel catalyst in the said step (3) comprises carrier, active constituent and auxiliary agent, and said carrier is Al
2O
3, MgO, active ingredient is NiO, auxiliary agent is La
2O
3, each component and mass percent thereof are in this nickel catalyst: NiO 30 ~ 50%, La
2O
31 ~ 5%, Al
2O
330 ~ 50%, MgO 12 ~ 20%, graphite 1 ~ 3%.The preparation method of this nickel catalyst comprises the steps: that (1) precipitin reaction makes the nickel catalyst work in-process: placing response still in water bath with thermostatic control is the Ni (NO of 26.54 ~ 44.24g/L with concentration
3)
26H
2The O aqueous solution; 50.13 the Al (NO of ~ 83.50g/L
3)
39H
2The O aqueous solution; 17.35 the Mg (NO of ~ 28.92g/L
3)
26H
2La (the NO of the O aqueous solution and 0.60 ~ 3.02g/L
3)
36H
2The O aqueous solution adds in the reaction kettle, adds precipitation agent K when under agitation condition, being heated to 65 ~ 75 ℃
2CO
3To K
2CO
3Mass percent concentration be 10 ~ 12%, in whole precipitin reaction process, keep 68 ~ 70 ℃, regulator solution pH value to 9.0 ~ 9.5; The resulting throw out of filtration washing is the nickel catalyst work in-process; (2) drying: with nickel catalyst work in-process under 120 ~ 150 ℃ of conditions dry 4 ~ 5 hours; (3) calcining: with dried nickel catalyst work in-process 300 ~ 450 ℃ temperature lower calcination 3 ~ 4 hours; (4) mix: the nickel catalyst work in-process after will calcine and graphite are by grinding in mass ratio 100:1 ~ 3 adding ball mills and mixing, and its mixture is all through 200 mesh sieves; (5) compression moulding: the zero(ppm) water of adding 6 ~ 12% mixes back compression moulding and promptly obtains the nickel catalyst finished product.Among this preparation method, through regulating parameters such as each component concentrations, pH value of solution value, temperature, time, can be so that its CO transformation efficiency height of prepared catalyzer, activity etc. can satisfy the needs of Industrial Catalysis.The nickelous nitrate of step (1), aluminum nitrate, magnesium nitrate, Lanthanum trinitrate is all chemical reagent, the Ni (NO of 26.54 ~ 44.24g/L
3)
26H
2O representes not have Ni (NO in the L solution
3)
26H
2The weight of O is 26.54 ~ 44.24g, Ni (NO
3)
26H
2O, Al (NO
3)
39H
2O, Mg (NO
3)
26H
2O, La (NO
3)
36H
2After nitrate salt such as O and the precipitation agent generation precipitin reaction, the calcining back forms NiO, La
2O
3, Al
2O
3, MgO oxide compound and volatile volatile gases, its part by weight adds a certain amount of graphite again through converting, and in the catalyzer finished product that finally makes by each component of oxide compound and mass percent thereof is: NiO 30 ~ 50%, La
2O
31 ~ 5%, Al
2O
330 ~ 50%, MgO 12 ~ 20%, graphite 1 ~ 3%.
Straw Gas of the present invention is a kind of inflammable gas that farm crop such as corn cob, wheat straw, cotton straw, straw etc. produce through thermolysis, and component differs greatly this inflammable gas because the gasification type of furnace is different, vaporized chemical is different.The Straw Gas inflammable gas component content of wherein producing as vaporized chemical with water vapor is high, and foreign matter content is less, H in its staple
2Content accounts for 45 ~ 60%, CH
4Content accounts for 3 ~ 10%, and CO content accounts for 15 ~ 25%, CO
2Content accounts for 15 ~ 25%, N
2Content accounts for 0.3 ~ 3%, C
nH
mContent accounts for 0.2 ~ 2%, O
2Content accounts for 0.1 ~ 0.8%, also contains a spot of benzene, muriate, tar and sulfide etc. simultaneously.Coke-oven gas is similar with the Straw Gas component, and maximum difference is that the many carbon of hydrogen are few in the coke-oven gas, and the few carbon of hydrogen is many in the Straw Gas; In the process of producing synthetic natural gas or compressed natural gas CNG, need earlier a small amount of objectionable impurities such as benzene, tar, sulfide etc. are removed, carry out following (1) and (2) methanation reaction again:
CO+3H
2=CH
4+H
2O （1）
CO
2+4H
2=CH
4+2H
2O （2）
Prepare in the synthetic natural gas process for coke-oven gas, 20 ~ 40% H is arranged in the mixed gas behind the methanation reaction
2Need to remove through separating, this is H partly
2Can not get fully effectively utilizing, economic benefit can't be further enhanced; And prepare in the synthetic natural gas process excessive CO and CO for Straw Gas
2Exist,, reduce the synthetic natural gas calorific value owing to be can not react to remain in the product gas, a bit outside, excessive CO, CO
2If do not remove, disproportionation reaction (3) also can take place and generate CO in unnecessary CO
2, this part CO injustice is not fully had utilization, and economic benefit is affected, and can cause and on catalyzer, analyse carbon.
2CO=C+CO
2 （3）
Both do not combine research and the relevant report used with coke-oven gas and Straw Gas (biological renewable energy) in the prior art, and the technological process that these two kinds of difference are bigger also is not easy the consideration that linked together usually.The present invention is few and many characteristics of the few carbon of hydrogen in the Straw Gas according to the many carbon of hydrogen in the coke(oven)gas, and the comprehensive utilization coke-oven gas is produced synthetic natural gas with the biological renewable energy Straw Gas, make full use of energy to exchange, and the minimizing loop compression, energy-saving and emission-reduction are increased economic efficiency; And help environment protection, develop reproducible biomass new forms of energy and substitute fossil energy.
The purpose that adds water vapor is to ascend to heaven too highly in order to control in the reaction process temperature, and simultaneously at reaction gas during through the one-level isothermal reactor, 10 ~ 30% heat of reaction is walked, and 85 ~ 92% CO is converted into CH after through one section methanation reaction
4, remaining CO generates methane through two sections methanation reactions the time.
Compared with prior art, the invention has the beneficial effects as follows:
1, adopt the inventive method, make full use of the characteristic of coke-oven gas and Straw Gas, the many carbon of coke-oven gas hydrogen are few, and the few carbon of Straw Gas hydrogen is many, has complementary advantages; Coke-oven gas sub product when producing coke; Straw Gas is by corps heat cracking gained (renewable resources); The synthetic natural gas that both combinations are produced can be alleviated the situation that China's natural gas is used anxiety, so that the agricultural byproducts stalk is utilized effectively the protection environment; Save the energy, develop reproducible biomass new forms of energy and substitute the fossil energy technology.
2, adopt the mode of two sections methanation reactions in this method, practiced thrift great deal of investment, the heat energy and the virgin gas heat exchange of emitting in logical many reaction process need not outer supplying heat source, and effect is especially remarkable aspect saving energy and reduce the cost.
3, need not before being pressed and delivered to reaction after the reacted gas cooling once more, to circulate with the CO/CO in the dilution virgin gas
2Concentration, every processing 1Nm
3The power consumption of gas can drop to 0.46Kw from 0.5 ~ 0.65Kw.
4, the nickel catalyst that provides a kind of coke(oven)gas and Straw Gas to be mixed with Sweet natural gas, this nickel catalyst have transformation efficiency height, active good, are convenient to industrial application and promote.
Description of drawings
Fig. 1 is the embodiment of the invention 1 is produced synthetic natural gas with the cog joint Straw Gas a method process flow diagram.
Embodiment
Below in conjunction with embodiment the present invention is made further detailed description, but embodiment of the present invention is not limited only to following embodiment.
Embodiment 1
(1), adjustment virgin gas component: coke-oven gas is formed (mol%) and is: H
256.5, CH
425.6, CO 7.6, CO
22.3, N
25.4, C
nH
m2.2, O
20.4, total sulfur 380mg/Nm
3, benzene and naphthalene trace, tar＜7mg/Nm
3, tolerance 535.7kmol/h;
Straw Gas is formed (mol%): H
248.2, CH
43.9, CO 23.6, CO
222.7, N
20.7, C
nH
m0.6, O
20.3, total sulfur 180mg/Nm
3, benzene and naphthalene trace, tar＜12mg/Nm
3, tolerance 750kmol/h;
Forming (mol%) at gas holder gas mixture after mix is: H
251.8, CH
412.9, CO 17.0, CO
214.1, N
22.6, C
mH
n1.3, O
20.3, total sulfur 261mg/Nm
3, benzene and naphthalene trace, tar＜9.9mg/Nm
3
(2), compression purifies: (1) step blended gas is arrived 2.0Mpa through compressor pressurizes; Adsorption bed through gac is housed is adsorbed through alternating temperature; Absorb through hydrocracking and ZnO again, remove benzene, naphthalene, tar and sulfide in the virgin gas, reach the subsequent technique requirement.
(3) thermal pretreatment and adding water vapor: mixing raw material gas and two sections methanation reaction outlet of still gas after the purification of (2) step are carried out heat exchange, and mixing raw material gas will be heated to 144 ℃ from 30 ℃; Carry out heat exchange with one section methanation reaction outlet of still gas once more, then with the 2.2Mpa condition under saturated vapor 129Kmol mix the back temperature reach 321 ℃.
(4) one sections methanation reactions: the mixed gas of above-mentioned adding water vapor is entered into one section methanation reaction stove that nickel catalyst is housed; The bed upper temp rises to 607 ℃ rapidly; Through and bed in coil pipe between after the heat exchange, one section methanation furnace temperature out is reduced to 527 ℃.But through with 7.6 tons/hour of one section methanation reaction stove heat exchange by-product 4.0Mpa superheated vapours, reactant gases was formed (mol%) and was this moment: H
29.26, CH
456.18, CO 3.76, CO
226.00, N
24.80, pressure 1.86Mpa.
(5) two sections methanation reactions: above-mentioned one section methanation furnace exit gas and the mixing raw material gas that (3) go on foot are carried out heat exchange; Temperature is reduced to 409 ℃; Two sections methanation reaction stoves completion secondary methanation reactions of nickel catalyst are equipped with in entering; Reaction back gas temperature rises to 539 ℃, and reactant gases composition this moment (mol%) is: H
20.03, CH
465.06, CO 41ppm, CO
229.37, N
25.27, pressure 1.80Mpa.
Used nickel catalyst comprises carrier, active constituent and auxiliary agent in step (4), (5), and said carrier is Al
2O
3, MgO, active ingredient is NiO, auxiliary agent is La
2O
3, each component and mass percent thereof are in this catalyzer: NiO 30 ~ 50%, La
2O
31 ~ 5%, Al
2O
330 ~ 50%, MgO 12 ~ 20%, graphite 1 ~ 3%.
(6) gas-liquid separation: with 539 ℃ of gases behind two sections methanation reactions through with the material mixed gas heat exchange after reduce to 444.5 ℃; After producing steam and water coolant heat exchange with useless pot again; Be cooled to 30 ~ 40 ℃; The liquid water that the entering gas-liquid separator gets off condensation is removed, and gas is discharged from the gas-liquid separator top.
(7) transformation absorption purification methane: through behind the pressure-swing absorption apparatus, adsorption bed is by activated alumina, activated carbon and the filling of X zeolite with the above-mentioned gas of separating, and the product gas that obtains is formed (mol%) and is: H
20.39, CH
496.19, CO 45mmp, CO
20.91, N
22.46 calorific value is 33.53MJ/Nm
3, obtain normal temperature condition product gas 395.9kmol pressure 1.60Mpa altogether.
CO in the stripping gas
2Content 78 ~ 81, N
2With CH
4Content puts 7 ~ 9% approximately, and this part gas can also further be handled.
Embodiment 2
(1), adjustment virgin gas component: coke-oven gas is formed (mol%) and is: H
256.5, CH
425.6, CO 7.6, CO
22.3, N
25.4, C
mH
n2.2, O
20.4, organosulfur 380mg/Nm
3, benzene and naphthalene trace, tar＜7mg/Nm
3, tolerance 446.5kmol/h;
Straw Gas is formed (mol%): H
250.0, CH
43.6, CO 24.1, CO
220.7, N
20.6, C
mH
n0.7, O
20.3, organosulfur 184mg/Nm
3, benzene and naphthalene trace, tar＜12mg/Nm
3, tolerance 750kmol/h;
Forming (mol%) at gas holder gas mixture after mix is: H
252.6, CH
411.8, CO 17.7, CO
213.9, N
22.4, C
mH
n1.3, O
20.3, total sulfur 263mg/Nm
3, benzene and naphthalene trace, tar＜10.1mg/Nm
3
(2), compression purification: (1) step blended gas is arrived 1.6Mpa through compressor pressurizes, remove benzene, naphthalene, tar and the organosulfur in the virgin gas after adsorbing through alternating temperature through the adsorption bed that gac is housed, reach the subsequent technique requirement.
(3) thermal pretreatment and adding water vapor: mixing raw material gas and two sections methanation reaction outlet of still gas after the purification of (2) step are carried out heat exchange, and mixing raw material gas will be heated to 147 ℃ from 30 ℃; Carry out heat exchange with one section methanation reaction outlet of still gas once more, then with the 2.0Mpa condition under saturated vapor 179.5Kmol mix the back temperature reach 317 ℃.
(4) one sections methanation reactions: above-mentioned and water vapor mixture body are entered into one section methanation reaction stove, and the bed upper temp rises to 601 ℃ rapidly, through and bed in coil pipe between after the heat exchange, one section methanation furnace temperature out is reduced to 517 ℃.But through with 7.1 tons/hour of one section methanation reaction stove heat exchange by-product 4.0Mpa superheated vapours, reactant gases was formed (mol%) and was this moment: H
27.58, CH
457.24, CO 4.06, CO
226.54, N
24.58, pressure 1.46Mpa.
(5) two sections methanation reactions: above-mentioned one section methanation furnace exit gas and the mixing raw material gas that (3) go on foot are carried out heat exchange; Temperature is reduced to 403 ℃; Get into two sections methanation reaction stoves and accomplish the secondary methanation reaction; Reaction back gas temperature rises to 527 ℃, and reactant gases composition this moment (mol%) is: H
21.58, CH
463.58, CO 42ppm, CO
229.99, N
24.82, pressure 1.40Mpa.
Used nickel catalyst comprises carrier, active constituent and auxiliary agent in step (4), (5), and said carrier is Al
2O
3, MgO, active ingredient is NiO, auxiliary agent is La
2O
3, each component and mass percent thereof are in this catalyzer: NiO 30 ~ 50%, La
2O
31 ~ 5%, Al
2O
330 ~ 50%, MgO 12 ~ 20%, graphite 1 ~ 3%.
(6) gas-liquid separation: with 527 ℃ of gases behind two sections methanation reactions through with the material mixed gas heat exchange after reduce to 432.7 ℃; Again with useless pot and water coolant heat exchange after; Be cooled to 30 ~ 40 ℃, the liquid water that the entering gas-liquid separator gets off condensation is removed, and gas is discharged from the gas-liquid separator top.
(7) transformation absorption purification methane: through behind the pressure-swing absorption apparatus, adsorption bed is by activated alumina, activated carbon and molecular sieve filling with the above-mentioned gas of separating, and the product gas that obtains is formed (mol%) and is: H
22.46, CH
494.30, CO 46mmp, CO
21.2, N
22.04 calorific value is 33.12MJ/Nm
3, obtain normal temperature condition product gas 358.7kmol pressure 1.20Mpa altogether.
Embodiment 3
(1), adjustment virgin gas component: coke-oven gas is formed (mol%) and is: H
254.2, CH
426.2, CO 6.3, CO
22.7, N
24.1, C
mH
n3.0, O
20.4, total sulfur 376mg/Nm
3, benzene and naphthalene trace, tar＜8mg/Nm
3, tolerance 446.5kmol/h;
Straw Gas is formed (mol%): H
250.0, CH
43.6, CO 24.1, CO
220.7, N
20.6, C
mH
n0.7, O
20.3, total sulfur 184mg/Nm
3, benzene and naphthalene trace, tar＜13mg/Nm
3, tolerance 669.6kmol/h;
Forming (mol%) at gas holder gas mixture after mix is: H
252.5, CH
412.8, CO 17.2, CO
213.6, N
22.0, C
mH
n1.6, O
20.3, total sulfur 264mg/Nm
3, benzene and naphthalene trace, tar＜10.0mg/Nm
3
(2), compression purification: (1) step blended gas is arrived 0.5Mpa through compressor pressurizes, remove benzene, naphthalene, tar and the organosulfur in the virgin gas after adsorbing through alternating temperature through the adsorption bed that gac is housed, reach the subsequent technique requirement.
(3) thermal pretreatment and adding water vapor: mixing raw material gas and two sections methanation reaction outlet of still gas after the purification of (2) step are carried out heat exchange, and mixing raw material gas will be heated to 146 ℃ from 30 ℃; Carry out heat exchange with one section methanation reaction outlet of still gas once more, then with the 1.0Mpa condition under saturated vapor 220Kmol mix the back temperature reach 308 ℃.
(4) one sections methanation reactions: above-mentioned and water vapor mixture body are entered into one section methanation reaction stove, and the bed upper temp rises to 587 ℃ rapidly, through and bed in coil pipe between after the heat exchange, one section methanation furnace temperature out is reduced to 507 ℃.But through with 6.0 tons/hour of one section methanation reaction stove heat exchange by-product 4.0Mpa superheated vapours, reactant gases was formed (mol%) and was this moment: H
29.11, CH
457.99, CO 3.84, CO
225.33, N
23.72, pressure 0.4Mpa.
(5) two sections methanation reactions: above-mentioned one section methanation furnace exit gas and the mixing raw material gas that (3) go on foot are carried out heat exchange; Temperature is reduced to 400 ℃; Get into two sections methanation reaction stoves and accomplish the secondary methanation reaction; Reaction back gas temperature rises to 510 ℃, and reactant gases composition this moment (mol%) is: H
22.33, CH
465.07, CO 41ppm, CO
228.81, N
26.0, pressure 0.28Mpa.
Used nickel catalyst comprises carrier, active constituent and auxiliary agent in step (4), (5), and said carrier is Al
2O
3, MgO, active ingredient is NiO, auxiliary agent is La
2O
3, each component and mass percent thereof are in this catalyzer: NiO 30 ~ 50%, La
2O
31 ~ 5%, Al
2O
330 ~ 50%, MgO 12 ~ 20%, graphite 1 ~ 3%.
(6) gas-liquid separation: with 510 ℃ of gases behind two sections methanation reactions through with the material mixed gas heat exchange after reduce to 422.7 ℃; Again with useless pot and water coolant heat exchange after; Be cooled to 30 ~ 40 ℃, the liquid water that the entering gas-liquid separator gets off condensation is removed, and gas is discharged from the gas-liquid separator top.
(7) transformation absorption purification methane: through behind the pressure-swing absorption apparatus, adsorption bed is by molecular sieve, activated carbon and the filling of X zeolite with the above-mentioned gas of separating, and the product gas that obtains is formed (mol%) and is: H
23.54, CH
493.74, CO 43mmp, CO
20.87, N
21.81 calorific value is 33.06MJ/Nm
3, obtain normal temperature condition product gas 338.7kmol pressure 0.2Mpa altogether.
In the prior art, H in the Straw Gas major ingredient
2Content accounts for 45 ~ 60%; CO content accounts for 15 ~ 25%, is characterized in that the few carbon of hydrogen is many, adopts Straw Gas as the virgin gas synthetic natural gas separately; Even hydrogen all behind methanation reaction are all participated in methanation reaction; Still can remain a large amount of CO (account for CO total amount about 20%), CO is in the methanation reaction process, and reaction generates CO under the situation of hydrogen deficient
2, cause the waste of resource; And H in coke-oven gas (the being coke(oven)gas) major ingredient in the prior art
2Content accounts for 50 ~ 60%; CO content accounts for 5 ~ 8%; Be characterized in that the many carbon of hydrogen are few, though in methanation reaction the transformation efficiency of CO very high (more than 99%), perhaps CO all transforms; The residual content of its hydrogen still very big (account for hydrogen total amount about 50%) causes the waste of resource or has increased the cost of hydrogen recovery; Embodiment 1-3 all synthesizes with reference to operational path shown in Figure 1; Adopt synthesis technique of the present invention; In embodiment 1-3, prepare normal temperature condition product gas 395.9kmol pressure 1.60Mpa, normal temperature condition product gas 358.7kmol pressure 1.20Mpa, normal temperature condition product gas 338.7kmol pressure 0.2Mpa respectively; Owing to optimized the component proportions of virgin gas, selected the gas mixture of Straw Gas and coke(oven)gas for use and regulate wherein CO and H
2Ratio, make gas mixture at CO under the effect of catalyzer when methanation reaction transformation efficiency higher (more than 99%), the residual content of hydrogen is merely about 2%, makes CO and H
2Do not have very big residue and waste, practiced thrift resource.
Embodiment 4:
Catalyzer 1:
Placing response still in water bath with thermostatic control is with 26.54gNi (NO
3)
26H
2O; 83.50gAl (NO
3)
39H
2O; 28.92gMg (NO
3)
26H
2O; 0.60gLa (NO
3)
36H
2O is mixed with 1L solution and adds in the reaction kettle, stirs, and adds 10% K when being heated to 68 ℃
2CO
3Solution keeps this temperature to carry out precipitin reaction and the final pH of adjusting value is 9.2.The resulting throw out of filtration washing is the catalyzer work in-process.With the catalyzer work in-process in loft drier in 120 ℃ of dryings 5 hours; In retort furnace, calcined 4 hours down in 380 ℃; Burnt material (catalyzer work in-process) and graphite put into according to material: graphite=100:2 (mass ratio) ball mill grinds and batch mixing, its mixture is all through 200 mesh sieves, the zero(ppm) water of adding 8%; After mixing, it is cylindric to process ￠ 5x5mm with the compression molding machine.Each component and mass percent thereof are in the catalyzer of present embodiment preparation: NiO30%, La
2O
31%, Al
2O
348.1%, MgO 18.9%, graphite 2%.
Catalyzer 2:
Placing response still in water bath with thermostatic control is with 44.24gNi (NO
3)
26H
2O; 50.13gAl (NO
3)
39H
2O; 17.35gMg (NO
3)
26H
2O; 3.02gLa (NO
3)
36H
2O is mixed with 1L solution and adds in the reaction kettle, stirs, and adds 12% K when being heated to 72 ℃
2CO
3Solution keeps this temperature to carry out precipitin reaction and the final pH of adjusting value is 9.5.The resulting throw out of filtration washing is the catalyzer work in-process.With the catalyzer work in-process in loft drier in 150 ℃ of dryings 4 hours; In retort furnace, calcined 3 hours down in 450 ℃; Burnt material and graphite put into according to material: graphite=100:3 (mass ratio) ball mill grinds and batch mixing, its mixture adds 10% zero(ppm) water all through 200 mesh sieves; After mixing, it is cylindric to process ￠ 5x5mm with the compression molding machine.Each component and mass percent thereof are in the catalyzer of present embodiment preparation: NiO50%, La
2O
35%, Al
2O
329.8%, MgO12.2%, graphite 3%.
Catalyzer 3
Placing response still in water bath with thermostatic control is with 35.39gNi (NO
3)
26H
2O; 66.85gAl (NO
3)
39H
2O; 23.14gMg (NO
3)
26H
2O; 1.8gLa (NO
3)
36H
2O is mixed with 1L solution and adds in the reaction kettle, stirs, and adds 10% K when being heated to 70 ℃
2CO
3Solution keeps this temperature to carry out precipitin reaction and the final pH of adjusting value is 9.2.The resulting throw out of filtration washing is the catalyzer work in-process.With the catalyzer work in-process in loft drier in 120 ℃ of dryings 4 hours; In retort furnace, calcined 4 hours down in 400 ℃; Burnt material and graphite put into according to material: graphite=100:2 (mass ratio) ball mill grinds and batch mixing, its mixture adds 10% zero(ppm) water all through 200 mesh sieves; After mixing, it is cylindric to process ￠ 5x5mm with the compression molding machine.Each component and mass percent thereof are in the catalyzer of present embodiment preparation: NiO39.8%, La
2O
33%, Al
2O
339.2%, MgO 16%, graphite 2%.
In catalyzer 1-3, K
2CO
3Effect be regulator solution pH value; The main effect of graphite and water is to make catalyzer moulding more easily, and bonding tight, appearance has characteristics such as metalluster.
Catalyzer 1-3 is crushed to the small-particle of 1 ~ 2mm respectively, and getting the 10ml internal diameter of packing into respectively is the reaction tubes of 17mm, and catalyst bed layer height 35mm carries out determination of activity to catalyzer.
Select analyser for use: gas chromatograph GC-1690 (chemical industry plant and instrument dawn ltd of Hangzhou section)
Virgin gas: adopt coke(oven)gas and Straw Gas mixing gas component to carry out distribution, its mixed gas is formed as shown in table 1
Table 1 coke(oven)gas and Straw Gas mixing gas component (V%)
Title CO CH
4CO
2H
2N
2
Content 16.58 9.99 19.97 50.35 3.11
Under 350 ℃ of temperature, with the hydrogen pressure-raising to 0.6Mpa, reductase 12 hour, reduction air speed 2000h
-1, reduction finishes the back and feeds water vapor and virgin gas, breaks off hydrogen then, and pressure-raising is to 1.5Mpa gradually, and temperature rises to 520 ℃ of beds outlets, virgin gas air speed 10000 h
-1, steam-to-gas ratio 0.2 carries out methanation reaction, record reaction result such as table 2:
Table 2 coke(oven)gas and Straw Gas gas mixture methanation reaction result (V%)
CO CH
4CO
2N
2CO transformation efficiency % CH
4Selectivity
Embodiment 1 0.15 47.90 39.09 5.76 92.29 94.65
Embodiment 2 0.12 48.43 38.97 5.64 92.12 94.73
Embodiment 3 0.12 48.49 38.85 5.74 92.12 94.74
Data are visible from table; The gas mixture methanation catalyst of coke(oven)gas of the present invention and Straw Gas has the function that also has transformationreation in the methanation reaction function between bed, be good polyfunctional catalyst; After the running, the catalyst surface that unloads does not totally have carbon distribution.
The disclosed a kind of catalyzer that is used for coal preparing natural gas methanator of prior art CN201110188574.2, raw gas pressure is 3.5MPa in this catalyst environment, its catalytic virgin gas consists of: H
2, CO, N
2, CO
2, CH4; Its CO transformation efficiency is between 69.4 ~ 77.0%.
Catalyzer of the present invention is in embodiment 4, and the transformation efficiency of CO is greater than 92% in coke(oven)gas and the Straw Gas gas mixture methanation reaction, and the selectivity of methane is greater than 94%.In the present embodiment, raw gas pressure is 1.5Mpa in the catalyst environment, for raw gas pressure 3.5MPa in the existing catalyst environment; Its catalytic reaction environment requirement is much lower; Thereby the requirement to conversion unit is also much lower, and the production security of reactor drum can be ensured further that catalyzer of the present invention virgin gas in catalytic environment requires under the lower pressure condition; Can guarantee the transformation efficiency of CO in the virgin gas equally; And therefore the transformation efficiency of its CO adopted catalyzer of the present invention when the transformation efficiency of CO had catalyzer now far above employing, and its activity is good; The CO transformation efficiency is significantly increased with respect to prior art, more helps industrial applications.
As stated, just can realize the present invention preferably.
Claims (5)
1. a cog joint Straw Gas is produced the method for synthetic natural gas, it is characterized in that: comprise the steps:
(1) adjustment virgin gas component: the flow size of adjustment coke-oven gas and Straw Gas makes H in the mixed gas mixture component of coke-oven gas and Straw Gas
2Mol ratio 3.0～4.0:1.0 with CO;
(2) adopt existing pressurization, purification, preconditioning technique, remove benzene, naphthalene, tar, heavy hydrocarbon compounds and sulfide;
(3) methanation reaction: with behind purified gas heat exchange to 300～350 ℃, add steam, accomplish the methanation reaction process through the reaction bed that nickel catalyst is housed again; The mol ratio of steam add-on and purified gas is 0.1～0.2:1;
(4) gas-liquid separation:, water coolant in the reactant gases is removed with existing method with the gas cooling to 30 behind the methanation reaction～40 ℃;
(5) transformation absorption purification methane: IMPURITIES IN is removed after adopting pressure swing adsorption with gas-liquid separation, obtains CH
4The synthetic natural gas of concentration more than 90%.
2. a kind of cog joint Straw Gas according to claim 1 is produced the method for synthetic natural gas; It is characterized in that: described methanation reaction adopts the reactor drum polyphone of two-stage different types to accomplish; Wherein one-level is an isothermal reactor, and the second stage is adiabatic reactor.
3. a kind of cog joint Straw Gas according to claim 1 is produced the method for synthetic natural gas, it is characterized in that: described methanation reaction adopts a reactor drum to accomplish.
4. produce the method for synthetic natural gas according to each described a kind of cog joint Straw Gas of claim 1 to 3; It is characterized in that: the adsorption bed of described transformation absorption purification methane is to combine the CO under 0.5～1.5Mpa condition in the separating mixed gas by two or more sorbent materials at least in 3A molecular sieve, 4A molecular sieve, activated alumina, zeolite molecular sieve, activated carbon, the silica gel
2And N
2
5. produce the method for synthetic natural gas according to each described a kind of cog joint Straw Gas of claim 1 to 3, it is characterized in that: the nickel catalyst in the said step (3) comprises carrier, active constituent and auxiliary agent, and said carrier is Al
2O
3, MgO, active ingredient is NiO, auxiliary agent is La
2O
3, each component and mass percent thereof are in this nickel catalyst: NiO 30～50%, La
2O
31～5%, Al
2O
330～50%, MgO 12～20%, graphite 1～3%.
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| CN102942972A (en) * | 2012-11-14 | 2013-02-27 | 中国电子工程设计院 | Method for producing liquefied natural gas by coke oven gas |
| CN103113010A (en) * | 2013-02-01 | 2013-05-22 | 同济大学 | Method for synchronous implementation of methanation of coke oven gas and in-situ purification of marsh gas |
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| CN105080591B (en) * | 2014-05-08 | 2017-09-15 | 中国石油化工股份有限公司 | A kind of preparation method of coke-oven gas methanation catalyst |
| CN105080591A (en) * | 2014-05-08 | 2015-11-25 | 中国石油化工股份有限公司 | Preparation method of catalyst through methanation of coke oven gas |
| CN104194850A (en) * | 2014-05-27 | 2014-12-10 | 顾君尧 | Method of producing natural gas by coupling coke oven gas and producer gas and production device |
| CN104152198A (en) * | 2014-07-21 | 2014-11-19 | 中国五环工程有限公司 | Methanation reaction process |
| CN104745257B (en) * | 2015-03-10 | 2017-10-20 | 华南理工大学 | A kind of system and technique of coal and oven gas alliance preparing natural gas |
| CN104745257A (en) * | 2015-03-10 | 2015-07-01 | 华南理工大学 | System and process for producing natural gas through combined supply of coal and coke-oven gas |
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| CN111232920B (en) * | 2020-03-17 | 2023-03-14 | 昆明理工大学 | Method for producing hydrogen by coke oven coal chemical looping |
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