CN101812339A - Method and device for producing synthetic natural gas, and natural gas product thereof - Google Patents
Method and device for producing synthetic natural gas, and natural gas product thereof Download PDFInfo
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- CN101812339A CN101812339A CN 201010149218 CN201010149218A CN101812339A CN 101812339 A CN101812339 A CN 101812339A CN 201010149218 CN201010149218 CN 201010149218 CN 201010149218 A CN201010149218 A CN 201010149218A CN 101812339 A CN101812339 A CN 101812339A
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Abstract
The invention provides a method for producing synthetic natural gas and a device thereof. The continuous technological process of the invention is realized in a way that gasified product gas is used as the raw material for producing high methane gas containing more than 94 mol% of methane. The method can well adjust the methanation reaction temperature and avoid the problems of catalyst temperature-runaway sintering and the like due to improper material composition, excessive fluctuation or unexpected accident, thereby reducing the recycle gas amount and enhancing the energy comprehensive utilization efficiency.
Description
Technical field
The present invention relates to a kind of method of full methanation, particularly, the present invention relates to the gasification product is raw material, and the method and the device thereof of production synthetic natural gas (methane-rich gas) belong to the synthetic natural gas technical field.
Background technology
Since last century the seventies, be accompanied by oil crisis, preparing methane from coal (synthetic natural gas or instead of natural gas) is at home and abroad comparatively fast developed.The main method of preparing methane from coal comprises that coal hydrogenation gasification directly prepares methane and prepares methane indirectly through synthetic gas.
The subject matter that coal hydrogenation gasification is produced methane has: efficiency of carbon conversion is low, the methane yield is low, gas composition is complicated, methane concentration is low and can not get high-quality synthetic natural gas etc.Comparatively speaking, coal is through the technology of producing firedamp by syngas possess skills ripening degree height, carbon utilisation rate height and the high significant advantage of methane concentration.At the beginning of the eighties in last century, German LURGI has finished the exploitation of a whole set of Technology in conjunction with the methanation catalyst of BASF AG, and is successfully applied to the coal preparing natural gas factory of big plain in u.s.a factory 389 cubic meters per day; Company of Centrica has developed HICOM technology and corresponding catalyst at the synthetic gas characteristics of BGL vapourizing furnace, and has set up 2832m
3The pilot plant of/d; Rope company of Denmark Top has successfully developed 700 ℃ of pyritous wide temperature range types of the highest ability catalyzer, and has developed TREMP full methanation Technology.
In China, be purpose to utilize coal production city coal gas, set up more sophisticated coal gas part methanation technology in last century: researched and developed " water at atmospheric pressure coal gas part methanation production city coal gas " technology as Dalian Chemiclophysics Inst., Chinese Academy of Sciences; It is that the RHM-266 type nickel of unstripped gas is methanation catalyst and technology that chemical fertilizer institute of the Ministry of Chemical Industry has developed with the normal pressure semi-water gas; Coal Mining Research Institute has developed the two stage furnace water gas methanation process.
Along with the needs of Sustainable development, energy-saving and cost-reducing, raising efficiency of energy utilization becomes the direction and the trend of each technical development.For methanation, high temperature, high top pressure operation, wide temperature range type catalyzer help equipment and process intensification, and then cut down the consumption of energy, and improve hot grade of methanation reaction by-product and recovery utilization rate.In view of this, the wide temperature range type methanation catalyst, high temperature, high pressure full methanation technology have become the development trend of current methanation technology.The tame methanation commercialization of big plain in u.s.a one factory is only arranged at present in the world, and in being, the low temperature methanation technology, for high temperature, the high pressure full methanation technology of methanation development trend, still do not have the precedent of industrial applications.Domestic methanation technology only stays in the part methanation at present, and catalyzer adaptive temperature narrow range, has greatly limited the comprehensive utilization ratio of energy; The part methanation technology that carries out under the normal pressure in addition is unfavorable for reaction and equipment reinforcement, lacks the integrated optimization of reactor design and material-energy.
Methanation reaction is quick, strong exothermal reaction, and carbon monoxide content is too high in the unstripped gas will cause a large amount of heat releases, causes beds phenomenons such as " temperature runaways " to occur easily and causes catalyst deactivation, even jeopardize the safety of reactor.In present full methanation technology, default converter unit before the methanation unit by the content of carbon monoxide in the transformationreation reduction unstripped gas, perhaps adds extra steam with saturated unstripped gas in unstripped gas usually.
Methanation reaction can carry out in all kinds of reactors, comprises insulation fix bed reactor, cooling type shell and tube reactor even fluidized-bed reactor.What use was more in the prior art is insulation fix bed reactor.The cooling type shell and tube reactor is made of many reaction tubes parallel connections, (or between pipe) loading catalyst in its pipe, (or in pipe) carries out heat exchange between the thermophore flowing pipe, caliber is usually between 25～50mm, the pipe number can reach up to ten thousand, and the cooling type shell and tube reactor also is applicable to the reaction that reaction heat effect is bigger.
Summary of the invention
The objective of the invention is to, a kind of production synthetic natural gas (Synthetic Natural Gas, method SNG) are provided.
Another object of the present invention is, the device of implementing aforesaid method is provided.
The present invention realizes by the following technical solutions.On the one hand, the invention provides a kind of is the method for unstripped gas production synthetic natural gas with the gasification product, the methane mol ratio that contains in the described synthetic natural gas is more than 94%, described method comprises the steps a) to d), and by delivery of steam system independently with external steam and/or step b), c) and/or d) in the steam that produces feed step b), c) and/or d) described in first section insulation fix bed reactor and/or second section insulation fix bed reactor and/or the 3rd section insulation fix bed reactor in:
A) unstripped gas is divided into first strand of unstripped gas (4) and second strand of unstripped gas (5) after heating;
B) carry out methanation reaction in the first section insulation fix bed reactor (7) with the feeding of the first strand of unstripped gas (4) in step a) filling methanation catalyst, wherein the temperature of inlet gas is 230-400 ℃; It is 450-700 ℃ the first product gas (8) that reaction obtains temperature, and this first product gas (8) obtains temperature and be 150-350 ℃ the refrigerative first product gas (10) after cooling; While by-product saturation steam and/or superheated vapour.
C) second strand of unstripped gas (5) in the step a) and the mixed gas (11) that obtains after the resulting refrigerative first product gas (10) in the step b) mixes are fed in second section insulation fix bed reactor (12) of filling methanation catalyst and carry out methanation reaction, wherein the temperature of inlet gas is 230-400 ℃; It is 450-700 ℃ the second product gas (13) that reaction obtains temperature, and this second product gas (13) obtains temperature and be 150-350 ℃ the refrigerative second product gas (15), simultaneously by-product saturation steam and/or superheated vapour after cooling.
D) the resulting refrigerative second product gas (15) in the step c) is selected from one of following processing:
The resulting refrigerative second product gas (15) in the step c) fed in the 3rd section insulation fix bed reactor of filling methanation catalyst or the cooling type shell and tube reactor (17) carry out methanation reaction, obtain temperature and be 350-600 ℃ three products gas (18), this three products gas (18) is after cooling, obtain refrigerative three products gas (20), simultaneously by-product saturation steam and/or superheated vapour; And resulting a part of three products gas as circulation gas (22), is fed in the first section insulation fix bed reactor and/or second section insulation fix bed reactor in the step c) in the step b) again; Another part three products gas feeds in the latter end insulation fix bed reactor of loading catalyst or the cooling type shell and tube reactor (26) as product gas (21) and carries out methanation reaction, obtain latter end product gas (24), this latter end product gas (24) obtains synthetic natural gas (26) after cooling, gas-liquid separation; Wherein said circulation gas (22) and product gas (21) volume ratio are preferably 0-5.0: 1, and 0.3-3.0 more preferably: 1;
Perhaps
Resulting a part of refrigerative second product gas in the step c) is fed in the first section insulation fix bed reactor and/or second section insulation fix bed reactor in the step c) in the step b) again as circulation gas (22 '); Another part refrigerative second product gas feeds in the latter end insulation fix bed reactor of loading catalyst or the cooling type shell and tube reactor as product gas (21 ') and carries out methanation reaction, obtain latter end product gas (24), this latter end product gas (24) obtains synthetic natural gas (26) after cooling, gas-liquid separation; Wherein said circulation gas (22 ') and product gas (21 ') volume ratio are preferably 0-5.0: 1, and 0.3-3.0 more preferably: 1;
Perhaps
Resulting a part of refrigerative second product gas in the step c) is fed in the first section insulation fix bed reactor and/or second section insulation fix bed reactor in the step c) in the step b) again as circulation gas (22 '); Another part refrigerative second product gas feeds in the 3rd section insulation fix bed reactor of filling methanation catalyst or the cooling type shell and tube reactor as product gas (21 ') and carries out methanation reaction, obtain three products gas (18), this three products gas (18) is after cooling, obtain refrigerative three products gas (20), by-product saturation steam and/or superheated vapour; This refrigerative three products gas (20) are fed in the latter end insulation fix bed reactor of filling methanation catalyst or the cooling type shell and tube reactor carry out methanation reaction, obtain latter end product gas (24), this latter end product gas (24) obtains synthetic natural gas (26) after cooling, gas-liquid separation; Wherein said circulation gas (22 ') and product gas (21 ') volume ratio are preferably 0-5.0: 1, and 0.3-3.0 more preferably: 1;
In one embodiment of the invention, the saturation steam in described step b), step c) and/or the step d) generates superheated vapour through heat exchange, and the heat of described heat exchange preferably derives from the first product gas, second product gas and/or the three products gas to small part; Preferably, described saturation steam and/or superheated vapour originating to small part steam as described independently delivery of steam system.
Preferably, described unstripped gas purifies earlier before heating, to remove the small amount of impurities that wherein contains.
Preferably, the gas mole in the described unstripped gas is composed as follows: carbon monoxide 5-45%, carbonic acid gas 0-30% and hydrogen 20-80%.
Preferably, the methanation catalyst that is loaded in the methanation catalyst that is loaded in described first section insulation fix bed reactor, second section insulation fix bed reactor and/or the 3rd section insulation fix bed reactor or the cooling type shell and tube reactor and latter end insulation fix bed reactor or the cooling type shell and tube reactor is different.
In a preferred embodiment, the methanation catalyst that is loaded in first section insulation fix bed reactor, second section insulation fix bed reactor and/or the 3rd section insulation fix bed reactor or the cooling type shell and tube reactor is that the main active ingredient of the methanation catalyst of high temperature high voltage resistant is the oxide compound of metal, described metal comprises aluminium, nickel and rare earth element, and in strontium, vanadium and the chromium one or more, preferably, wherein said rare earth element comprises one or more in lanthanum, cerium, praseodymium, europium and the ytterbium.Preferably, described catalyzer is a benchmark with the catalyzer of 100 weight parts, and in metallic element, the content of nickel is the 1-10 weight part, and the content of rare earth element is the 1-6 weight part, and the total content of strontium, vanadium and chromium is the 0.5-5 weight part, and surplus is an aluminum oxide.
In a preferred embodiment, the methanation catalyst that is loaded in latter end insulation fix bed reactor or the cooling type shell and tube reactor is middle Catalyst for Low-Temperature Methanation, can be any middle Catalyst for Low-Temperature Methanation known in the art, for example commercially available methanation catalyst.
Preferably, described methanation catalyst has multiple configuration, layering or the mixed packing different positions in reactor;
Preferably, described methanation catalyst also comprises prereduction process, is to be 300-600 ℃ with synthetic gas (its main component is hydrogen and carbon monoxide) or hydrogen in temperature, and air speed is 100～2000h
-1Condition under directly realize that by methanation catalyst described synthetic gas or hydrogen are preferably through nitrogen dilution;
Preferably, the working pressure of described methanation catalyst is 1-10MPa, preferred 2-4MPa; The operation air speed is 2000-60000h
-1, preferred 3000-40000h
-1
On the other hand, the invention provides the device of implementing aforesaid method, it comprises following equipment:
Methanator is used for unstripped gas is implemented methanation reaction;
Heat-exchange equipment links to each other with the outlet of methanator respectively, is used to cool off the product gas that methanation reaction generates, and by-product saturation steam and/or superheated vapour; And
Steam input system links to each other with the inlet of methanator respectively, is used for importing steam to described methanator.
In one embodiment of the invention, described methanator is selected from insulation fix bed reactor and cooling type shell and tube reactor; Wherein said methanator is divided into three sections or four sections, its type is respectively: first section methanator and second section methanator comprise at least one insulation fix bed reactor, and the 3rd section methanator and/or latter end methanator comprise at least one insulation fix bed reactor and/or cooling type shell and tube reactor.
Preferably, described device also comprises the tubing system that connects outlet of back segment methanator and leading portion methanator inlet, is used for the portioned product conductance that the back segment methanator is generated is gone into the leading portion methanator; Preferably, described tubing system also comprises compressor.
Preferably, described device also comprises treating plant, is used for unstripped gas is carried out deep purifying, removes the small amount of impurities that wherein contains; Preferably, described device also comprises heating installation, is used to heat the unstripped gas that enters first section methanator and/or second section methanator.
The synthetic natural gas that the present invention also provides aforesaid method to produce, the methane mol ratio that contains in the described synthetic natural gas is more than 94%.
In sum, the invention provides a kind of is the continuous processing flow process and the relative unit of the raw material production methane-rich gas that comprises methane 94% or above mol ratio with gasification product gas.Carbon monoxide content is 5-45% in the unstripped gas, and carbon dioxide content is that 0%-30% and hydrogen content are 20%-80%.Technical process provided by the present invention is as follows: unstripped gas is divided into two strands, feeds first, second section insulation fix bed reactor respectively; First section reactor outlet gas mixes second section insulation fix bed reactor of feeding with second strand of unstripped gas; Then second section reactor product gas feeds the 3rd section reactor; The 3rd section reactor outlet portioned product gas as circulation gas feed first section and or second section reactor, another part product gas then feeds the latter end methanator and further reacts and finally make desired product synthetic natural gas SNG.
More than one methanation catalysts of filling in the methanator in the technology of the present invention,, and in different reactor, select different catalyzer and catalyst configuration for use.
Contain independent steam system in the technology of the present invention, vapor stream is mixed into corresponding methanator with unstripped gas or product gas respectively, preferably the controlling reactor temperature out.But the flow modulation of this vapor stream; mix with unstripped gas on the one hand; reduce CO content in the unstripped gas; the temperature of control reaction reduces the circulation gas scale of construction according to practical situation on the other hand, reduces the methanation energy consumption; improve system energy efficiency; also can be under the condition that unstripped gas fluctuates widely, temperature in the controlling reactor, guard catalyst.Steam at least a portion derives from the steam of heat-exchange equipment by-product.
The present invention can determine the saturation steam of by-product different grades according to actual needs, also can produce superheated vapour through further heat exchange.The superheated vapour of by-product and saturation steam can be used for conditioned reaction device feed composition, control reaction temperature on the one hand; Can optimize technology on the other hand, reduce the circulation gas scale of construction, reduce system energy consumption, improve energy utilization efficiency.
If still contain a spot of carbon monoxide or carbonic acid gas, the further reaction of gas can be obtained the finished product in the product of the present invention.
Compared with prior art, the present invention has realized the synthetic gas full methanation of gasification product after purifying come the production synthetic natural gas, have technical process rationally, possess operability; Save energy; Advantage such as environmentally friendly.
Description of drawings
Below, describe embodiment of the present invention in conjunction with the accompanying drawings in detail, wherein:
Fig. 1 is a full methanation reaction process schematic flow sheet in the embodiment of the invention 1;
Fig. 2 is a full methanation reaction process schematic flow sheet in the embodiment of the invention 2.
Reference numeral part description pairing with it is as follows:
1/4/5: unstripped gas 2: clean unit
3/9/14/19/25: interchanger 6/11/16: gas mixture
7/12/17/23: methanator 8/13/18/24: product gas
10/15/20: chilled product gas 21/21 ': product gas
22/22 '/28/29: circulation gas 26: end product SNG
27: compressor 30/31/32: steam
Embodiment
Below in conjunction with embodiment this invention is described in further detail, but this should be interpreted as that scope of the present invention only limits to following embodiment.
Figure 1 shows that a kind of preferred implementation of the production method of synthetic natural gas provided by the present invention.Describe the particular case of each workshop section's methanation reaction of the present invention in detail in conjunction with Fig. 1 at this.
Main material synthesis gas is produced by vapourizing furnace, through conventional steps such as over-quenchings, removes impurity such as tar, oil, phenol, ammonia and dust wherein, and removes petroleum naphtha, sulfide and the partial CO 2 etc. that wherein contain by the acid gas removal unit.Enter deep purifying unit 2 through acid gas removal unitary unstripped gas 1, further remove the impurity such as sulfur-bearing, oxygen and chlorine, arsenic of the trace that wherein contains.Unstripped gas is divided into two strands of air-flows after by interchanger 3 preheatings, i.e. first strand of unstripped gas 4 and second strand of unstripped gas 5.First strand of unstripped gas 4 mixes with back segment circulation gas 28 and steam 30, the temperature of the gas mixture 6 that obtains is 230-400 ℃, with its feeding be filled with the high temperature high voltage resistant methanation catalyst (employed catalyzer for example can adopt the preparation of following method: use strong aqua to regulate 0.3 to rub/liter the pH of ammonium bicarbonate soln be 9, then under agitation condition, with 31.20 gram Ni (NO
3)
2With 9.36 gram La (NO
3)
2Slowly join in the above-mentioned solution; Under agitation condition, with the solution that obtains with contain 272.54 gram Al
2(SO
4)
3The aqueous solution slowly splash in the reactor simultaneously, with 1 rub/liter NaOH solution the pH value of solution in the reactor is adjusted to 9.5, temperature of reaction is 40 ℃, stir speed (S.S.) is 600rpm, reacts 9 hours.Filter the precipitation (Ni-La-Al complex hydroxide) that to obtain then and separate,, use deionized water wash then,, 500 ℃ of following roastings 4 hours, make catalyst precursor afterwards 100 ℃ of dryings 12 hours 60 ℃ of following ageings 4 hours; With 1.56 gram Sr (NO
3)
2With 2.29 gram Cr (NO
3)
3Water-soluble catalyst precursor is carried out supersaturation dipping, flood after 12 hours,, obtain catalyst powder at last then 400 ℃ of following roastings 4 hours at 120 ℃ times dry 8-12 hour; Press the polyvinyl alcohol of mass ratio interpolation 3% as binding agent to catalyst powder, add 3.5% graphite and play the sheet moulding after as lubricant, obtain preformed catalyst) first section insulation fix bed reactor 7 in carry out methanation reaction, the temperature of the first product gas 8 that obtains of reaction is 450-700 ℃.The first product gas 8 is cooled to 150-350 ℃ by 9 heat exchange of the useless pot of high pressure steam, simultaneously the by-product saturation steam.The refrigerative first product gas 10 mixes with second strand of unstripped gas 5, back segment circulation gas 29 and steam 31, the temperature of resulting gas mixture 11 is 230-400 ℃, its feeding is filled with in second section insulation fix bed reactor 12 of high temperature high voltage resistant methanation catalyst (the same) and carries out methanation reaction, reaction obtains the second product gas 13, its temperature is 450-700 ℃, the heat exchange in useless pot 14 of the second product gas 13 is cooled to 150-350 ℃, simultaneously the by-product saturation steam.The refrigerative second product gas 15 mixes with steam 32, resulting gas mixture 16 temperature are 230-400 ℃, its feeding is filled with in the 3rd section insulation fix bed reactor of high temperature high voltage resistant methanation catalyst (the same) or the cooling type shell and tube reactor 17 carries out methanation reaction, reaction obtains three products gas 18, and its temperature is 450-700 ℃.Three products gas 18 is cooled to 150-350 ℃ by 19 heat exchange of useless pot, and the by-product saturation steam.Refrigerative three products gas 20 is divided into two strands, and one loops back first section insulation fix bed reactor and second section insulation fix bed reactor as circulation gas 28 and 29 as circulation gas 22 respectively via compressor 27; Another strand enters as product gas 21 and is filled with middle Catalyst for Low-Temperature Methanation, can be any middle Catalyst for Low-Temperature Methanation known in the art, for example commercially available J105 or CJ106 type methanation catalyst.Latter end insulation fix bed reactor or cooling type shell and tube reactor 23 carry out methanation reaction, the reaction four-product gas that obtains 24 obtains end product SNG26 by after interchanger 25 heat exchange.
Below by the gas composition parameter of each logistics in the table 1, a situation arises to have described the reality of each workshop section's methanation reaction in Fig. 1 technical process intuitively.
The parameter of each methanator turnover implication of table 1 and unstripped gas, circulation gas and SNG
Figure 2 shows that the another kind of preferred implementation of the production method of synthetic natural gas provided by the present invention.The difference of embodiment shown in Figure 2 and embodiment shown in Figure 1 only is, changes the 3rd section insulation fix bed reactor exit gas round-robin flow process in the embodiment shown in Figure 1 into second section insulation fix bed reactor exit gas circulation; In this embodiment the 3rd section and latter end reactor all can use insulation fix bed reactor or cooling type shell and tube reactor simultaneously.
Below by the gas composition parameter of each logistics in the table 2, a situation arises to have described the reality of each workshop section's methanation reaction in Fig. 2 technical process intuitively, by-product 5MPa saturation steam 1066kmol/h.
The parameter of each methanator turnover implication of table 2 and unstripped gas, circulation gas and product gas
Below by the gas composition parameter of each logistics in the table 3, a situation arises to have described the reality of each workshop section's methanation reaction in Fig. 2 technical process intuitively.Be with the difference of table 2, in first section methanator 7, add 5MPa saturated vapor 50mol/h.
Below by the gas composition parameter of each logistics in the table 3, a situation arises to have described the reality of each workshop section's methanation reaction in Fig. 2 technical process intuitively.
The condition of each workshop section of table 3 methanation reaction and the gas composition parameter of different workshop sections
Compare with table 2, by in first section methanator, adding a small amount of saturated vapor (5MPa, 50kmol/h, account for first section methanator inlet gas 4.5%), by-product saturation steam 1066kmol/h (not containing the saturated vapor that in first section methanator, adds), circulating flow rate reduces by 10.33% (reducing to 625kmol/h from 697kmol/h), and the recycle compressor power consumption reduces by 9.64% (being reduced to 50.87kw from 56.30kw).
Claims (10)
1. one kind is the method for unstripped gas production synthetic natural gas with the gasification product, the methane mol ratio that contains in the described synthetic natural gas is more than 94%, described method comprises the steps a) to d), and by delivery of steam system independently with external steam and/or step b), c) and/or d) in the steam that produces feed step b), c) and/or d) described in first section insulation fix bed reactor, second section insulation fix bed reactor and/or the 3rd section insulation fix bed reactor in:
A) unstripped gas is divided into first strand of unstripped gas (4) and second strand of unstripped gas (5) after heating;
B) carry out methanation reaction in the first section insulation fix bed reactor (7) with the feeding of the first strand of unstripped gas (4) in step a) filling methanation catalyst, wherein the temperature of inlet gas is 230-400 ℃; It is 450-700 ℃ the first product gas (8) that reaction obtains temperature, and this first product gas (8) obtains temperature and be 150-350 ℃ the refrigerative first product gas (10), simultaneously by-product saturation steam and/or superheated vapour after cooling;
C) second strand of unstripped gas (5) in the step a) and the mixed gas (11) that obtains after the resulting refrigerative first product gas (10) in the step b) mixes are fed in second section insulation fix bed reactor (12) of filling methanation catalyst and carry out methanation reaction, wherein the temperature of inlet gas is 230-400 ℃; It is 450-700 ℃ the second product gas (13) that reaction obtains temperature, and this second product gas (13) obtains temperature and be 150-350 ℃ the refrigerative second product gas (15), simultaneously by-product saturation steam and/or superheated vapour after cooling;
D) the resulting refrigerative second product gas (15) in the step c) is selected from one of following processing:
The resulting refrigerative second product gas (15) in the step c) fed in the 3rd section insulation fix bed reactor of filling methanation catalyst or the cooling type shell and tube reactor (17) carry out methanation reaction, obtain temperature and be 350-600 ℃ three products gas (18), this three products gas (18) is after cooling, obtain refrigerative three products gas (20), simultaneously by-product saturation steam and/or superheated vapour; And resulting a part of three products gas as circulation gas (22), is fed in the first section insulation fix bed reactor and/or second section insulation fix bed reactor in the step c) in the step b) again; Another part three products gas feeds in the latter end insulation fix bed reactor of filling methanation catalyst or the cooling type shell and tube reactor (26) as product gas (21) and carries out methanation reaction, obtain latter end product gas (24), this latter end product gas (24) obtains synthetic natural gas (26) after cooling, gas-liquid separation; The volume ratio of wherein said circulation gas (22) and product gas (21) is preferably 0-5.0: 1, and 0.3-3.0 more preferably: 1;
Perhaps
Resulting a part of refrigerative second product gas in the step c) is fed in the first section insulation fix bed reactor and/or second section insulation fix bed reactor in the step c) in the step b) again as circulation gas (22 '); Another part refrigerative second product gas feeds in the latter end insulation fix bed reactor of filling methanation catalyst or the cooling type shell and tube reactor as product gas (21 ') and carries out methanation reaction, obtain latter end product gas (24), this latter end product gas (24) obtains synthetic natural gas (26) after cooling, gas-liquid separation; Wherein said circulation gas (22 ') and product gas (21 ') volume ratio are preferably 0-5.0: 1, and 0.3-3.0 more preferably: 1;
Perhaps
Resulting a part of refrigerative second product gas in the step c) is fed in the first section insulation fix bed reactor and/or second section insulation fix bed reactor in the step c) in the step b) again as circulation gas (22 '); Another part refrigerative second product gas feeds in the 3rd section insulation fix bed reactor of filling methanation catalyst or the cooling type shell and tube reactor as product gas (21 ') and carries out methanation reaction, obtain three products gas (18), this three products gas (18) is after cooling, obtain refrigerative three products gas (20), simultaneously by-product saturation steam and/or superheated vapour; This refrigerative three products gas (20) are fed in the latter end insulation fix bed reactor of filling methanation catalyst or the cooling type shell and tube reactor carry out methanation reaction, obtain latter end product gas (24), this latter end product gas obtains synthetic natural gas (26) after cooling, gas-liquid separation; Wherein said circulation gas (22 ') and product gas (21 ') volume ratio are preferably 0-5.0: 1, and 0.3-3.0 more preferably: 1.
2. method according to claim 1 is characterized in that the saturation steam in described step b), step c) and/or the step d) generates superheated vapour through heat exchange;
Preferably, the heat of described heat exchange to small part derives from the first product gas, second product gas and/or the three products gas;
Preferably, described saturation steam and/or superheated vapour originating to small part steam as described independently delivery of steam system.
3. method according to claim 1 and 2 is characterized in that, described method also comprises the step of the product gas that obtains in latter end insulation fix bed reactor or the cooling type shell and tube reactor being carried out degree of depth methanation or carbonization treatment.
4. according to each described method in the claim 1 to 3, it is characterized in that described unstripped gas purifies earlier before heating, to remove the impurity that wherein contains.
5. according to each described method in the claim 1 to 4, it is characterized in that the gas mole in the described unstripped gas is composed as follows: carbon monoxide 5-45%, carbonic acid gas 0-30% and hydrogen 20-80%.
6. according to each described method in the claim 1 to 5, it is characterized in that the methanation catalyst that is loaded in the methanation catalyst that is loaded in described first section insulation fix bed reactor, second section insulation fix bed reactor and/or the 3rd section insulation fix bed reactor or the cooling type shell and tube reactor and latter end insulation fix bed reactor or the cooling type shell and tube reactor is different;
Preferably, described methanation catalyst has multiple configuration, layering or the mixed packing different positions in reactor;
More preferably, described methanation catalyst also comprises prereduction process, is to be 300-600 ℃ with synthetic gas or hydrogen in temperature, and air speed is 100～2000h
-1Condition under directly realize that by the methanation catalyst bed described synthetic gas or hydrogen are preferably through nitrogen dilution;
Further preferably, the working pressure of described methanation catalyst is 1-10MPa, preferred 2-4MPa; The operation air speed is 2000-60000h
-1, preferred 3000-40000h
-1
7. be used for implementing the device of each described method of claim 1 to 6, it is characterized in that, described device comprises following equipment:
Methanator is used for unstripped gas is implemented methanation reaction;
Heat-exchange equipment links to each other with the outlet of methanator respectively, is used to cool off the product gas that methanation reaction generates, and by-product saturation steam and/or superheated vapour; And
Steam input system links to each other with the inlet of methanator respectively, is used for importing steam to described methanator.
8. device according to claim 7 is characterized in that, described methanator is selected from insulation fix bed reactor and cooling type shell and tube reactor;
Preferably, wherein said methanator is divided into three sections or four sections, its type is respectively: first section methanator and second section methanator comprise at least one insulation fix bed reactor, and the 3rd section methanator and/or latter end methanator comprise at least one insulation fix bed reactor and/or cooling type shell and tube reactor.
9. according to claim 7 or 8 described devices, it is characterized in that, described device also comprises the tubing system that connects outlet of back segment methanator and leading portion methanator inlet, is used for the portioned product conductance that the back segment methanator is generated is gone into the leading portion methanator; Described tubing system preferably also comprises compressor;
Preferably, described device also comprises treating plant, is used for unstripped gas is carried out deep purifying, removes the small amount of impurities that wherein contains;
More preferably, described device also comprises heating installation, is used to heat the unstripped gas that enters first section methanator and/or second section methanator.
10. the synthetic natural gas that each described method is produced in the claim 1 to 6 is characterized in that the methane mol ratio that contains in the described synthetic natural gas is more than 94%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010149218 CN101812339A (en) | 2010-04-15 | 2010-04-15 | Method and device for producing synthetic natural gas, and natural gas product thereof |
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| CN101880559A (en) * | 2010-06-18 | 2010-11-10 | 大唐国际化工技术研究院有限公司 | Method and device for producing synthetic natural gas |
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| CN102329671A (en) * | 2011-09-13 | 2012-01-25 | 西南化工研究设计院 | Methanation process of synthetic natural gas prepared from coal |
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| CN103740425A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Method of producing substitute natural gas from synthesis gas |
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