CN102585950B - 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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- CN102585950B CN102585950B CN201210045745.0A CN201210045745A CN102585950B CN 102585950 B CN102585950 B CN 102585950B CN 201210045745 A CN201210045745 A CN 201210045745A CN 102585950 B CN102585950 B CN 102585950B
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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, relate to a kind of method taking cog joint Straw Gas as waste synthetic natural gas.
Background technology
Coke-oven gas is the byproduct in coke production, and China is coke production big country, and annual throughput, more than 300,000,000 tons, approximately has 400m according to every 1 ton of coke product
3coke-oven gas byproduct generates, and the annual coke-oven gas producing of China approximately has 1,200 hundred million m
3, except producing, coke is personal, heating, generating etc., approximately have 20,000,000,000 m
3rationally do not utilized.In recent years, the utilization of coke-oven gas was more and more extensive, comprised after hydrogen manufacturing, methyl alcohol processed, deep purifying or 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%, CO content and 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 small amount of benzene, naphthalene, tar and sulfide etc. simultaneously.
H in Straw Gas major ingredient
2content accounts for 45 ~ 60%, CH
4content accounts for 3 ~ 10%, CO content and 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 small amount of benzene, muriate, tar and sulfide etc. simultaneously.
In existing open source literature, also have toward the report of mending carbon in coke-oven gas, as CN101607859A " a kind of technique of employing coke-oven gas for production of methane ", in this patent by adding 100% CO
2or liquid CO
2after gasification, be added into before coke-oven gas methanation reaction, by adjusting CO
2add-on is by 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, passes through stack gas by low dividing potential drop purification CO in this patent
2the H separating with pressure-variable adsorption afterwards
2turn back to carbon-replenishing hydrogen-returning workshop section simultaneously and again carry out methanation reaction; " 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) join before methanation reaction with circulation gas, by unnecessary H
2react away.Power consumption in whole methanation reaction process process more than 90% is all used on gas compressor, the 1 volume CO supplementing
2with 4 volume H
2reaction generates 1 volume CH
4with 2 volume H
2no matter O, be therefore to circulate before the gas after methanation reaction is returned to first step methanation reaction, or by CO
2add in unstripped gas and unnecessary H
2reaction all cannot be brought up to maximum value by economic benefit.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of preparing synthetic natural gas by coke oven gas in combination with straw gas, the method is few and many features of the few carbon of hydrogen in Straw Gas according to the many carbon of hydrogen in coke(oven)gas, comprehensive utilization coke-oven gas and biological renewable energy Straw Gas are produced synthetic natural gas, make full use of exchange energy, reduce loop compression, energy-saving and emission-reduction, increase economic efficiency; And be conducive to environment protection, develop reproducible biomass new forms of energy and substitute fossil energy.
The present invention solves the problems of the technologies described above adopted technical scheme:
A method for preparing synthetic natural gas by coke oven gas in combination with straw gas, comprises the steps:
(1) adjust unstripped gas component: adjust the uninterrupted of coke-oven gas and Straw Gas, make 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: by behind purified gas heat exchange to 300 ~ 350 DEG C, add steam, then complete methanation reaction process by the reaction bed of nickel catalyst is housed; The mol ratio of steam add-on and purified gas is 0.1～0.2:1;
(4) gas-liquid separation: by the gas cooling to 30 after methanation reaction ~ 40 DEG C, water coolant in reactant gases is removed by existing method;
(5) Pressure Swing Adsorption methane: adopt pressure swing adsorption that the impurity in gas after gas-liquid separation is removed, obtain CH
4more than 90% synthetic natural gas of concentration.
Described methanation reaction adopts the reactor of two-stage different types to contact, and wherein one-level is isothermal reactor, and the second stage is adiabatic reactor.
Or described methanation reaction adopts a reactor to complete.
Existing methanation reaction has generally been contacted by 3 ~ 6 sections of reactors, and the transformation efficiency of its CO of synthetic natural gas so obtaining after reaction could be higher, the CH after purifying of the gas mixture after its conversion
4concentration just can reach the service requirements of combustion gas; Adopt processing method of the present invention, only need to adopt 1 section of reactor or 2 sections of series windings to complete, so after methanation reaction, its CO just can reach higher transformation efficiency, the synthetic natural gas CH that the gas mixture after its conversion obtains after purifying
4concentration can reach more than 90%, in terms of existing technologies, has reduced the hop count of reactor, 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 Pressure Swing Adsorption methane is to be combined by least two or more sorbent materials in 3A molecular sieve, 4A molecular sieve, activated alumina, zeolite molecular sieve, activated carbon, silica gel, the CO under 0.5 ~ 1.5Mpa condition in separating mixed gas
2and N
2.Zeolite molecular sieve can adopt the X zeolite molecular sieve of lithium X zeolite or low Si/Al ratio.
Nickel catalyst in described step (3) comprises carrier, active constituent and auxiliary agent, and described carrier is Al
2o
3, MgO, active ingredient is NiO, auxiliary agent is La
2o
3, in this nickel catalyst, each component and mass percent thereof are: 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 nickel catalyst work in-process: the Ni (NO that placing response still in water bath with thermostatic control is 26.54 ~ 44.24g/L by concentration
3)
26H
2the O aqueous solution; Al (the NO of 50.13 ~ 83.50g/L
3)
39H
2the O aqueous solution; Mg (the NO of 17.35 ~ 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 reactor, adds precipitation agent K under agitation condition while being heated to 65 ~ 75 DEG C
2cO
3to K
2cO
3mass percent concentration be 10 ~ 12%, in whole precipitin reaction process, keep 68 ~ 70 DEG C, regulator solution pH value to 9.0 ~ 9.5; The throw out that filtration washing obtains is nickel catalyst work in-process; (2) dry: nickel catalyst work in-process are dried to 4 ~ 5 hours under 120 ~ 150 DEG C of conditions; (3) calcining: by dried nickel catalyst work in-process the temperature lower calcination of 300 ~ 450 DEG C 3 ~ 4 hours; (4) mix: nickel catalyst work in-process and graphite after calcining are added and in ball mill, grind and mix in 100:1 ~ 3 in mass ratio, and its mixture is all by 200 mesh sieves; (5) compression moulding: add 6 ~ 12% distilled water, mix rear compression moulding and obtain nickel catalyst finished product.In this preparation method, by regulating the parameters such as the concentration, pH, temperature, time of each component, can make its CO transformation efficiency of prepared catalyzer needs that can meet Industrial Catalysis such as high, active.The nickelous nitrate of step (1), aluminum nitrate, magnesium nitrate, lanthanum nitrate is all chemical reagent, the Ni (NO of 26.54 ~ 44.24g/L
3)
26H
2o represents not have Ni (NO in 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 the nitrate such as O and precipitation agent generation precipitin reaction, after calcining, form NiO, La
2o
3, Al
2o
3, MgO oxide compound and volatile volatile gases, its part by weight is through conversion, then adds a certain amount of graphite, is: NiO 30 ~ 50%, La in the catalyzer finished product finally making by the each component of oxide compound and mass percent thereof
2o
31 ~ 5%, Al
2o
330 ~ 50%, MgO 12 ~ 20%, graphite 1 ~ 3%.
Straw Gas of the present invention is farm crop as a kind of inflammable gas that corn cob, wheat straw, cotton straw, straw etc. produce through thermolysis, and this inflammable gas is due to gasification type of furnace difference, vaporized chemical difference and component differs greatly.The Straw Gas inflammable gas component content of wherein producing using water vapor as vaporized chemical is high, and foreign matter content is less, H in its main component
2content accounts for 45 ~ 60%, CH
4content accounts for 3 ~ 10%, CO content and 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 small amount of benzene, muriate, tar and sulfide etc. simultaneously.Coke-oven gas is similar to Straw Gas component, and maximum difference is that in coke-oven gas, the many carbon of hydrogen is few, and in Straw Gas, the few carbon of hydrogen is many; In the process of producing synthetic natural gas or compressed natural gas CNG, need first a small amount of objectionable impurities to remove as benzene, tar, sulfide etc., then carry out following (1) and (2) methanation reaction:
CO+3H
2=CH
4+H
2O （1）
CO
2+4H
2=CH
4+2H
2O （2）
Prepare in synthetic natural gas process for coke-oven gas, in the mixed gas after methanation reaction, have 20 ~ 40% H
2need to remove through separating this part H
2can not get fully effectively utilizing, economic benefit cannot be further enhanced; And prepare in synthetic natural gas process excessive CO and CO for Straw Gas
2exist, because being cannot not react completely to remain in gas product, reduce synthetic natural gas calorific value, a bit outside, excessive CO, CO
2if do not remove, also can there is disproportionation reaction (3) 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）
In prior art not by coke-oven gas and Straw Gas (biological renewable energy) both in conjunction with research and the relevant report of application, the technological process that these two kinds of difference are larger is also not easy the consideration that linked together conventionally.The present invention is few and many features of the few carbon of hydrogen in Straw Gas according to the many carbon of hydrogen in coke(oven)gas, and comprehensive utilization coke-oven gas is produced synthetic natural gas with biological renewable energy Straw Gas, makes full use of exchange energy, minimizing loop compression, and energy-saving and emission-reduction, increase economic efficiency; And be conducive to environment protection, develop reproducible biomass new forms of energy and substitute fossil energy.
The object that adds water vapor is to ascend to heaven too highly in order to control in reaction process temperature, and simultaneously at reaction gas during through one-level isothermal reactor, 10 ~ 30% heat of reaction is walked, and 85 ~ 92% CO is being converted into CH after one section of methanation reaction
4, remaining CO generates methane when through two sections of methanation reactions.
Compared with prior art, the invention has the beneficial effects as follows:
1, adopt the inventive method, make full use of the feature of coke-oven gas and Straw Gas, the many carbon of coke-oven gas hydrogen is few, and the few carbon of Straw Gas hydrogen is many, has complementary advantages; Coke-oven gas byproduct when producing coke; Straw Gas is by corps heat cracking gained (renewable resources); both can be alleviated to China's natural gas in conjunction with the synthetic natural gas of producing and use nervous situation; so that agricultural byproducts stalk is utilized effectively; protection of the environment; save the energy, develop reproducible biomass new forms of energy and substitute fossil energy technology.
2, in the method, adopt the mode of two sections of methanation reactions, saved great deal of investment, heat energy and the unstripped gas heat exchange of in logical many reaction process, emitting, without outer supplying heat source, aspect saving energy and reduce the cost, effect is especially remarkable.
3, without circulate to dilute the CO/CO in unstripped gas before being again pressed and delivered to reaction after reacted gas cooling
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, it is high, active good that this nickel catalyst has transformation efficiency, is convenient to industrial application and promotes.
Brief description of the drawings
Fig. 1 is the method process flow diagram of the embodiment of the present invention 1 with preparing synthetic natural gas by coke oven gas in combination with straw gas.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited only to following embodiment.
embodiment 1
(1), adjust unstripped gas component: coke-oven gas composition (mol%) 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 composition (mol%) is: 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;
At gas holder gas mixture composition (mol%) after mixing be: 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: the gas that (1) step is mixed arrives 2.0Mpa through compressor pressurizes, by the adsorption bed process Temp .-changing adsorption of gac is housed, absorb by hydrocracking and ZnO again, remove benzene, naphthalene, tar and sulfide in unstripped gas, reach subsequent technique requirement.
(3) thermal pretreatment and add water vapor: mixing raw material gas and two sections of methanation reaction outlet of still gas after (2) step is purified carry out heat exchange, and mixing raw material gas will be heated to 144 DEG C from 30 DEG C; Again carry out heat exchange with one section of methanation reaction outlet of still gas, after then mixing with the saturated vapor 129Kmol under 2.2Mpa condition, temperature reaches 321 DEG C.
(4) one sections of methanation reactions: the above-mentioned mixed gas that adds water vapor is entered into one section of methanation reaction stove that nickel catalyst is housed, bed upper temp rises to rapidly 607 DEG C, by and bed in coil pipe between after heat exchange, one section of methanation furnace temperature out is down to 527 DEG C.By can by-product 4.0Mpa superheated vapour 7.6 tons/hour with the heat exchange of one section of methanation reaction stove, now reactant gases composition (mol%) be: H
29.26, CH
456.18, CO 3.76, CO
226.00, N
24.80, pressure 1.86Mpa.
(5) two sections of methanation reactions: above-mentioned one section of methanation furnace exit gas and the mixing raw material gas of (3) step are carried out to heat exchange, temperature is down to 409 DEG C, enter two sections of methanation reaction stoves that nickel catalyst is housed and complete secondary methanation reaction, after reaction, gas temperature rises to 539 DEG C, and now reactant gases composition (mol%) is: H
20.03, CH
465.06, CO 41ppm, CO
229.37, N
25.27, pressure 1.80Mpa.
In step (4), (5), nickel catalyst used comprises carrier, active constituent and auxiliary agent, and described carrier is Al
2o
3, MgO, active ingredient is NiO, auxiliary agent is La
2o
3, in this catalyzer, each component and mass percent thereof are: NiO 30 ~ 50%, La
2o
31 ~ 5%, Al
2o
330 ~ 50%, MgO 12 ~ 20%, graphite 1 ~ 3%.
(6) gas-liquid separation: by 539 DEG C of gases after two sections of methanation reactions by with material mixed gas heat exchange after be down to 444.5 DEG C, produce after steam and water coolant heat exchange with useless pot again, be cooled to 30 ~ 40 DEG C, enter the liquid water that gas-liquid separator gets off condensation and remove, gas is discharged from gas-liquid separator top.
(7) Pressure Swing Adsorption methane: by after pressure-swing absorption apparatus, adsorption bed is loaded by activated alumina, activated carbon and X zeolite by the above-mentioned gas of separating, the product gas composition (mol%) obtaining is: H
20.39, CH
496.19, CO 45mmp, CO
20.91, N
22.46, calorific value is 33.53MJ/Nm
3, obtain altogether normal temperature condition gas product 395.9kmol pressure 1.60Mpa.
CO in stripping gas
2content 78 ~ 81, N
2with CH
4content approximately puts 7 ~ 9%, and this part gas can also further be processed.
embodiment 2
(1), adjust unstripped gas component: coke-oven gas composition (mol%) 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 composition (mol%) is: 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;
At gas holder gas mixture composition (mol%) after mixing be: 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 purifies: the gas that (1) step is mixed to 1.6Mpa, through Temp .-changing adsorption after removes benzene, naphthalene, tar and organosulfur in unstripped gas by the adsorption bed of gac is housed through compressor pressurizes, reaches subsequent technique requirement.
(3) thermal pretreatment and add water vapor: mixing raw material gas and two sections of methanation reaction outlet of still gas after (2) step is purified carry out heat exchange, and mixing raw material gas will be heated to 147 DEG C from 30 DEG C; Again carry out heat exchange with one section of methanation reaction outlet of still gas, after then mixing with the saturated vapor 179.5Kmol under 2.0Mpa condition, temperature reaches 317 DEG C.
(4) one sections of methanation reactions: above-mentioned and water vapor mixture body are entered into one section of methanation reaction stove, and bed upper temp rises to rapidly 601 DEG C, by and bed in coil pipe between after heat exchange, one section of methanation furnace temperature out is down to 517 DEG C.By can by-product 4.0Mpa superheated vapour 7.1 tons/hour with the heat exchange of one section of methanation reaction stove, now reactant gases composition (mol%) be: H
27.58, CH
457.24, CO 4.06, CO
226.54, N
24.58, pressure 1.46Mpa.
(5) two sections of methanation reactions: above-mentioned one section of methanation furnace exit gas and the mixing raw material gas of (3) step are carried out to heat exchange, temperature is down to 403 DEG C, enter two sections of methanation reaction stoves and complete secondary methanation reaction, after reaction, gas temperature rises to 527 DEG C, and now reactant gases composition (mol%) is: H
21.58, CH
463.58, CO 42ppm, CO
229.99, N
24.82, pressure 1.40Mpa.
In step (4), (5), nickel catalyst used comprises carrier, active constituent and auxiliary agent, and described carrier is Al
2o
3, MgO, active ingredient is NiO, auxiliary agent is La
2o
3, in this catalyzer, each component and mass percent thereof are: NiO 30 ~ 50%, La
2o
31 ~ 5%, Al
2o
330 ~ 50%, MgO 12 ~ 20%, graphite 1 ~ 3%.
(6) gas-liquid separation: by 527 DEG C of gases after two sections of methanation reactions by with material mixed gas heat exchange after be down to 432.7 DEG C, again with useless pot and water coolant heat exchange after, be cooled to 30 ~ 40 DEG C, enter the liquid water that gas-liquid separator gets off condensation and remove, gas is discharged from gas-liquid separator top.
(7) Pressure Swing Adsorption methane: by after pressure-swing absorption apparatus, adsorption bed is loaded by activated alumina, activated carbon and molecular sieve by the above-mentioned gas of separating, the product gas composition (mol%) obtaining is: H
22.46, CH
494.30, CO 46mmp, CO
21.2, N
22.04, calorific value is 33.12MJ/Nm
3, obtain altogether normal temperature condition gas product 358.7kmol pressure 1.20Mpa.
embodiment 3
(1), adjust unstripped gas component: coke-oven gas composition (mol%) 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 composition (mol%) is: 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;
At gas holder gas mixture composition (mol%) after mixing be: 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 purifies: the gas that (1) step is mixed to 0.5Mpa, through Temp .-changing adsorption after removes benzene, naphthalene, tar and organosulfur in unstripped gas by the adsorption bed of gac is housed through compressor pressurizes, reaches subsequent technique requirement.
(3) thermal pretreatment and add water vapor: mixing raw material gas and two sections of methanation reaction outlet of still gas after (2) step is purified carry out heat exchange, and mixing raw material gas will be heated to 146 DEG C from 30 DEG C; Again carry out heat exchange with one section of methanation reaction outlet of still gas, after then mixing with the saturated vapor 220Kmol under 1.0Mpa condition, temperature reaches 308 DEG C.
(4) one sections of methanation reactions: above-mentioned and water vapor mixture body are entered into one section of methanation reaction stove, and bed upper temp rises to rapidly 587 DEG C, by and bed in coil pipe between after heat exchange, one section of methanation furnace temperature out is down to 507 DEG C.By can by-product 4.0Mpa superheated vapour 6.0 tons/hour with the heat exchange of one section of methanation reaction stove, now reactant gases composition (mol%) be: H
29.11, CH
457.99, CO 3.84, CO
225.33, N
23.72, pressure 0.4Mpa.
(5) two sections of methanation reactions: above-mentioned one section of methanation furnace exit gas and the mixing raw material gas of (3) step are carried out to heat exchange, temperature is down to 400 DEG C, enter two sections of methanation reaction stoves and complete secondary methanation reaction, after reaction, gas temperature rises to 510 DEG C, and now reactant gases composition (mol%) is: H
22.33, CH
465.07, CO 41ppm, CO
228.81, N
26.0, pressure 0.28Mpa.
In step (4), (5), nickel catalyst used comprises carrier, active constituent and auxiliary agent, and described carrier is Al
2o
3, MgO, active ingredient is NiO, auxiliary agent is La
2o
3, in this catalyzer, each component and mass percent thereof are: NiO 30 ~ 50%, La
2o
31 ~ 5%, Al
2o
330 ~ 50%, MgO 12 ~ 20%, graphite 1 ~ 3%.
(6) gas-liquid separation: by 510 DEG C of gases after two sections of methanation reactions by with material mixed gas heat exchange after be down to 422.7 DEG C, again with useless pot and water coolant heat exchange after, be cooled to 30 ~ 40 DEG C, enter the liquid water that gas-liquid separator gets off condensation and remove, gas is discharged from gas-liquid separator top.
(7) Pressure Swing Adsorption methane: by after pressure-swing absorption apparatus, adsorption bed is loaded by molecular sieve, activated carbon and X zeolite by the above-mentioned gas of separating, the product gas composition (mol%) obtaining is: H
23.54, CH
493.74, CO 43mmp, CO
20.87, N
21.81, calorific value is 33.06MJ/Nm
3, obtain altogether normal temperature condition gas product 338.7kmol pressure 0.2Mpa.
In prior art, H in Straw Gas major ingredient
2content accounts for 45 ~ 60%, CO content accounts for 15 ~ 25%, be characterized in that the few carbon of hydrogen is many, adopt separately Straw Gas as unstripped gas synthetic natural gas, even if hydrogen all after methanation reaction all participate in methanation reaction, still can remain 20% left and right that a large amount of CO(accounts for CO total amount), CO is in methanation reaction process, and the in the situation that of hydrogen deficient, reaction generates CO
2, cause the waste of resource; And H in coke-oven gas (being coke(oven)gas) major ingredient in prior art
2content accounts for 50 ~ 60%, CO content accounts for 5 ~ 8%, be characterized in that the many carbon of hydrogen is few, even the transformation efficiency of CO very high (more than 99%) in methanation reaction, or CO all transforms, the residual content of its hydrogen is very large (accounting for 50% left and right of hydrogen total amount) still, causes the waste of resource or increased the cost of hydrogen recovery; Embodiment 1-3 all synthesizes with reference to the operational path shown in Fig. 1, adopt synthesis technique of the present invention, in embodiment 1-3, prepare respectively normal temperature condition gas product 395.9kmol pressure 1.60Mpa, normal temperature condition gas product 358.7kmol pressure 1.20Mpa, normal temperature condition gas product 338.7kmol pressure 0.2Mpa; Owing to having optimized the component proportions of unstripped gas, select the gas mixture of Straw Gas and coke(oven)gas and regulate wherein CO and H
2ratio, CO is when methanation reaction transformation efficiency higher (more than 99%) under the effect of catalyzer to make gas mixture, the residual content of hydrogen is only 2% left and right, makes CO and H
2do not have very large residue and waste, saved resource.
embodiment 4:
Catalyzer 1:
Placing response still in water bath with thermostatic control, by 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 reactor, stirs, and adds 10% K while being heated to 68 DEG C
2cO
3solution, keeps this temperature to carry out precipitin reaction and the final pH of adjusting value is 9.2.The throw out that filtration washing obtains is catalyzer work in-process.Catalyzer work in-process are dried to 5 hours in 120 DEG C in loft drier, in retort furnace, at 380 DEG C, calcine 4 hours, burnt material (catalyzer work in-process) and graphite are put into according to material: graphite=100:2 (mass ratio) to ball mill grinds and batch mixing, its mixture is all by 200 mesh sieves, add 8% distilled water, after mixing, make ￠ 5x5mm with tabletting forming machine cylindric.In catalyzer prepared by the present embodiment, each component and mass percent thereof are: NiO30%, La
2o
31%, Al
2o
348.1%, MgO 18.9%, graphite 2%.
Catalyzer 2:
Placing response still in water bath with thermostatic control, by 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 reactor, stirs, and adds 12% K while being heated to 72 DEG C
2cO
3solution, keeps this temperature to carry out precipitin reaction and the final pH of adjusting value is 9.5.The throw out that filtration washing obtains is catalyzer work in-process.Catalyzer work in-process are dried to 4 hours in 150 DEG C in loft drier, in retort furnace, at 450 DEG C, calcine 3 hours, burnt material and graphite are put into according to material: graphite=100:3 (mass ratio) to ball mill grinds and batch mixing, its mixture is all by 200 mesh sieves, add 10% distilled water, after mixing, make ￠ 5x5mm with tabletting forming machine cylindric.In catalyzer prepared by the present embodiment, each component and mass percent thereof are: NiO50%, La
2o
35%, Al
2o
329.8%, MgO12.2%, graphite 3%.
Catalyzer 3
Placing response still in water bath with thermostatic control, by 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 reactor, stirs, and adds 10% K while being heated to 70 DEG C
2cO
3solution, keeps this temperature to carry out precipitin reaction and the final pH of adjusting value is 9.2.The throw out that filtration washing obtains is catalyzer work in-process.Catalyzer work in-process are dried to 4 hours in 120 DEG C in loft drier, in retort furnace, at 400 DEG C, calcine 4 hours, burnt material and graphite are put into according to material: graphite=100:2 (mass ratio) to ball mill grinds and batch mixing, its mixture is all by 200 mesh sieves, add 10% distilled water, after mixing, make ￠ 5x5mm with tabletting forming machine cylindric.In catalyzer prepared by the present embodiment, each component and mass percent thereof are: 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 Function of graphite and water is to make the easier moulding of catalyzer, and bonding tight, appearance has the features such as metalluster.
Catalyzer 1-3 is crushed to respectively to the small-particle of 1 ~ 2mm, gets respectively 10ml and pack the reaction tubes that internal diameter is 17mm into, catalyst bed layer height 35mm, carries out determination of activity to catalyzer.
Analysis about Selection instrument: chemical industry plant and instrument dawn company limited of gas chromatograph GC-1690(Hangzhou section)
Unstripped gas: adopt coke(oven)gas and Straw Gas mixing gas component to carry out distribution, its mixed gas composition is 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
At 350 DEG C of temperature, use hydrogen pressure-raising to 0.6Mpa, reductase 12 hour, reduction air speed 2000h
-1, after finishing, reduction passes into water vapor and unstripped gas, then disconnect hydrogen, and pressure-raising is to 1.5Mpa gradually, and temperature rises to 520 DEG C of beds outlets, unstripped gas air speed 10000 h
-1, steam-to-gas ratio 0.2 carries out methanation reaction, records reaction result 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 from table, the gas mixture methanation catalyst of coke(oven)gas of the present invention and Straw Gas has the function also in methanation reaction function with transformationreation between bed, is good polyfunctional catalyst, after running, the catalyst surface unloading is totally without carbon distribution.
The disclosed a kind of catalyzer for coal preparing natural gas methanator of prior art CN201110188574.2, this catalyst environment Raw atmospheric pressure is 3.5MPa, the unstripped gas of its catalysis 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 in coke(oven)gas and Straw Gas gas mixture methanation reaction, the transformation efficiency of CO is greater than 92%, and the selectivity of methane is greater than 94%.In the present embodiment, catalyst environment Raw atmospheric pressure is 1.5Mpa, for existing catalyst environment Raw atmospheric pressure 3.5MPa, the requirement of its catalytic reaction environment is much lower, thereby also much lower to the requirement of conversion unit, and the production security of reactor can further be ensured, catalyzer of the present invention requires under lower pressure condition at catalytic environment Raw gas, can ensure equally the transformation efficiency of CO in unstripped gas, and the transformation efficiency of CO is far above the transformation efficiency that adopts its CO when existing catalyzer, therefore adopt catalyzer of the present invention, its activity is good, CO transformation efficiency is significantly increased with respect to prior art, more be conducive to industrial applications.
As mentioned above, just can realize preferably the present invention.
Claims (4)
1. a method for preparing synthetic natural gas by coke oven gas in combination with straw gas, is characterized in that: comprise the steps:
(1) adjust unstripped gas component: adjust the uninterrupted of coke-oven gas and Straw Gas, make 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: by behind purified gas heat exchange to 300～350 DEG C, add steam, then complete methanation reaction process by the reaction bed of nickel catalyst is housed; The mol ratio of steam add-on and purified gas is 0.1～0.2:1; Described nickel catalyst comprises carrier, active constituent and auxiliary agent, and described carrier is Al
2o
3, MgO, active ingredient is NiO, auxiliary agent is La
2o
3, in this nickel catalyst, each component and mass percent thereof are: 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 nickel catalyst work in-process: the Ni (NO that placing response still in water bath with thermostatic control is 26.54 ~ 44.24g/L by concentration
3)
26H
2the O aqueous solution; Al (the NO of 50.13 ~ 83.50g/L
3)
39H
2the O aqueous solution; Mg (the NO of 17.35 ~ 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 reactor, adds precipitation agent K under agitation condition while being heated to 65 ~ 75 DEG C
2cO
3to K
2cO
3mass percent concentration be 10 ~ 12%, in whole precipitin reaction process, keep 68 ~ 70 DEG C, regulator solution pH value to 9.0 ~ 9.5; The throw out that filtration washing obtains is nickel catalyst work in-process; (2) dry: nickel catalyst work in-process are dried to 4 ~ 5 hours under 120 ~ 150 DEG C of conditions; (3) calcining: by dried nickel catalyst work in-process the temperature lower calcination of 300 ~ 450 DEG C 3 ~ 4 hours; (4) mix: nickel catalyst work in-process and graphite after calcining are added and in ball mill, grind and mix in 100:1 ~ 3 in mass ratio, and its mixture is all by 200 mesh sieves; (5) compression moulding: add 6 ~ 12% distilled water, mix rear compression moulding and obtain nickel catalyst finished product;
(4) gas-liquid separation: by the gas cooling to 30 after methanation reaction～40 DEG C, water coolant in reactant gases is removed by existing method;
(5) Pressure Swing Adsorption methane: adopt pressure swing adsorption that the impurity in gas after gas-liquid separation is removed, obtain CH
4more than 90% synthetic natural gas of concentration.
2. the method for a kind of preparing synthetic natural gas by coke oven gas in combination with straw gas according to claim 1, it is characterized in that: described methanation reaction adopts the reactor of two-stage different types to contact, wherein one-level is isothermal reactor, and the second stage is adiabatic reactor.
3. the method for a kind of preparing synthetic natural gas by coke oven gas in combination with straw gas according to claim 1, is characterized in that: described methanation reaction adopts a reactor to complete.
4. according to the method for a kind of preparing synthetic natural gas by coke oven gas in combination with straw gas described in claims 1 to 3 any one, it is characterized in that: the adsorption bed of described Pressure Swing Adsorption methane is to be combined by least two or more sorbent materials in 3A molecular sieve, 4A molecular sieve, activated alumina, zeolite molecular sieve, activated carbon, silica gel, the CO under 0.5～1.5Mpa condition in separating mixed gas
2and N
2.
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| CN102942972B (en) * | 2012-11-14 | 2014-10-15 | 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 |
| CN103351894B (en) * | 2013-07-07 | 2015-06-17 | 开封天宸能源化工机械有限公司 | Natural gas synthesizing technology adopting coke oven gas and coal gasifier gas |
| CN104804787B (en) * | 2014-01-29 | 2022-09-13 | 杭州林达化工技术工程有限公司 | Methanation method and device for preparing synthetic natural gas |
| 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 |
| 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 |
| CN104152198B (en) * | 2014-07-21 | 2017-05-17 | 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 |
| CN108315357A (en) * | 2018-04-10 | 2018-07-24 | 中国华能集团清洁能源技术研究院有限公司 | The method and system of combustible are coupled using regenerative resource and biomass |
| 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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| CN101993748A (en) * | 2010-11-05 | 2011-03-30 | 四川亚连科技有限责任公司 | Method for preparing and synthesizing natural gas by utilizing straw gas |
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|---|---|---|---|---|
| US4873214A (en) * | 1984-12-24 | 1989-10-10 | Trw Inc. | Carbonaceous material for production of hydrogen from low heating value fuel gases |
| CN101391935A (en) * | 2008-10-31 | 2009-03-25 | 西南化工研究设计院 | Method for synthesizing methane by using coke-oven gas |
| CN101851537A (en) * | 2010-06-21 | 2010-10-06 | 上海浦景化工技术有限公司 | Method and device for preparing synthetic natural gas |
| CN101993748A (en) * | 2010-11-05 | 2011-03-30 | 四川亚连科技有限责任公司 | Method for preparing and synthesizing natural gas by utilizing straw gas |
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