CN103146447A - System for producing CH4-enriched gas and method for producing CH4-enriched gas by employing system - Google Patents
System for producing CH4-enriched gas and method for producing CH4-enriched gas by employing system Download PDFInfo
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Abstract
The invention discloses a system for producing CH4-enriched gas through synthesis gas and a method for producing CH4-enriched gas by employing the system. The system comprises a methanation reactor unit, a carbon dioxide and sulfide gas removal unit, a supplementary methanation reactor unit and a dehydration unit, wherein the synthesis gas is subjected to the direct methanation reaction in the methanation reactor unit; CO2 and sulfide gas in crude synthesized natural gas are removed in the carbon dioxide and sulfide gas removal unit, so that the concentration of the sulfide gas is less than 5ppm; the crude synthesized natural gas is subjected to the supplementary and direct methanation reaction in the supplementary methanation reactor unit; CO2, CO and H2 in the crude synthesized natural gas are converted into CH4 and H2O so as to form the synthesized natural gas; the H2O in the synthesized natural gas is removed in the dehydration unit so as to form refined synthesized natural gas; and the catalyst in the supplementary methanation reactor unit is a sulfur-resistant direct methanation catalyst and works under the atmosphere of the sulfide gas concentration of less than 5ppm.
Description
Technical field
The present invention relates to be rich in CH
4The production of gas particularly relates to producing and is rich in CH
4The system of gas and use this system to produce to be rich in CH
4The method of gas.
Background technology
Methanation is to be synthetic natural gas (or instead of natural gas, key step SNG) with solid carbon-containing material, for example coal and Wood Adhesives from Biomass.In this step, be rich in the coal of carbon monoxide, carbonic acid gas and hydrogen and gasifying biomass product stream (being commonly referred to synthetic gas) and be converted into the CH that is rich in as pipe stage quality product by following reversible reaction
4Gas:
Conventional methanation is based on reaction 1, and it requires the mol ratio of H2/CO to be about 3:1, and the direct methanation reaction is mainly based on reaction 2, and its mol ratio that requires H2/CO is 1:1.Compare with conventional methanation reaction, direct methanation reaction possesses following advantage: 1) in feed gas required H2 still less, the unstripped gas pre-treatment that therefore needs is also still less; 2) some direct methanation catalysts shows high sulfidation resistance, and therefore, in some cases, pre-desulfurization can be omitted; And 3) the catalyst carbon fouling that occurs in conventional methanation reaction can not occur, thus, catalyst life is longer.
Methanation reaction is reversible reaction.According to thermodynamic argument, the existence of CO2 will make molecular balance move to the left, thereby the direction that makes reaction carry out is unfavorable for the generation of CH4.Therefore, CO2 is the inhibitor that CH4 generates, and it has reduced speed of reaction, has also reduced the peak rate of conversion of product.In conventional commercial run, along with the accumulation of CO2 in the methanation reaction process, speed of response will slow down gradually, and the transformation efficiency of product will significantly reduce.
The CO2 that forms in the direct methanation reaction process not only brings restriction on thermodynamics to system.The CO2 that produces in the methanation reaction process is present in system together as by product and CH4, therefore must remove, and the method for removing known to persons of ordinary skill in the art comprises Rectisol, Seloxol, MDEA, lime absorption etc.This type of independently CO2 remove or CH4 purifies and also significantly increased the total cost that methanation reaction is produced.It is the part of CH4 product postprocessing that such CO2 removes, rather than the part of methanation reaction itself.
The synthetic gas that gasification produces contains the sulphur component that principal mode is H2S and COS, and this sulphur component can make the methanation reaction poisoning of catalyst, therefore must remove from pan feeding before methanation reaction carries out.Industrial, synthetic gas had passed through the deep purifying unit before entering the methanation reaction process, make sulphur content be reduced to 0.1ppm.This type of deep purifying is normally realized by one or more industrially desulfurized processes, such as Rectisol and Selexol etc.Preliminary cleaning has significantly increased capital contribution.In addition, this type of purifying method needs low temperature (room temperature or lower), so the hot synthesis gas that gasification unit is produced must lower the temperature, thereby causes reduction or the loss of energy efficiency.
US3904386 discloses a kind of Mo of employing or catalyst based coal preparing natural gas (CH4) technique of W, and its flow process is: raw coal is produced crude synthesis gas by gasification unit; Crude synthesis gas enters in methanation and water-gas shift integrated reactor, and methanation and water gas shift reaction occur; Then, remove CO in gas mixture
2And sulfide; At last, remove residue CO through conventional methanation reaction (the H2/CO mol ratio is about 3:1) in replenishing methanator, produce and be rich in CH
4Gas wherein, need to be in replenishing methanator the H2/CO mol ratio of gas be transferred to approximately 3:1, and desulfurization before need be carried out the low temperature deep desulfuration, makes sulphur content less than 0.1ppm.
GTI (The Gas Research Institute, USA) proposes the directly technique of synthetic natural gas processed (CH4) of a kind of synthetic gas, and its flow process is: produce crude synthesis gas by gasification unit; Crude synthesis gas enters and carries out the direct methanation reaction in the direct methanation reactor; Then, remove CO in gas mixture
2And sulfide; Remove residue CO through conventional methanation reaction (the H2/CO mol ratio is about 3:1) at last in replenishing methanator, produce and be rich in CH
4Gas, same, this technique also need to be in replenishing methanator transfers to approximately 3:1 with the H2/CO mol ratio of gas, and desulfurization before also need be carried out the low temperature deep desulfuration, makes sulphur content less than 0.1ppm.
There is following very important technical problem in above-mentioned prior art:
(1) deep desulfuration problem: adopt the not Ni of anti-sulphur methanation catalyst because replenish methanator, so, carry out deep desulfuration to entering the gas that replenishes methanator, with H
2S content is removed to less than 0.1ppm, and is industrial, and the sweetening processes such as employing low-temp methanol washing process realize.
(2) the cold and hot and problem of technique: this type of purifying method needs first the temperature of synthetic gas to be down to-40 ℃ from several Baidu, and the synthetic gas after purifying enter again replenish methanator before, also need temperature is risen to 250-400 ℃, therefore, there is serious cold and hot and problem, can cause energy wastage like this, the facility investment of low-temperature rectisol is huge simultaneously.
(3) dirt gas transition problem: do not regulating dirt gas H by transformationreation
2In the situation of/CO mol ratio, in dirt gas, remaining CO possibly can't be converted into CH fully in replenishing methanator
4
Above-mentioned the problems of the prior art have strengthened Operating Complexity and investment and the production cost of suitability for industrialized production synthetic natural gas, thereby have slackened the market competitiveness and the price advantage of synthetic natural gas.
The present invention is devoted to solve above-mentioned technical barrier, thereby makes the technique of production synthetic natural gas become simple and cheap, thereby strengthens the market competitiveness of synthetic natural gas.
Summary of the invention
According to first aspect present invention, provide a kind of synthetic gas preparation to be rich in the system of CH4 gas, described system comprises:
Methanator unit, synthetic gas carry out direct methanation reaction therein under catalyst action, and are converted into and comprise CH4, CO
2, CO, H
2Thick synthetic natural gas with sulfide gas;
Carbonic acid gas and sulfide gas remove the unit, the CO in thick synthetic natural gas
2Be removed therein with sulfide gas, make sulfide gas concentration in thick synthetic natural gas less than 5ppm;
Additional methanator unit, thick synthetic natural gas is replenished the direct methanation reaction therein under catalyst action, further with the CO in thick synthetic natural gas
2, CO, H
2Be converted into CH4 and H
2O, thus synthetic natural gas formed; With
Dewatering unit, synthetic natural gas are removed H therein
2O, thus refining synthetic natural gas formed,
Wherein, the catalyzer that replenishes in methanator is the direct methanation of anti-sulphur catalyzer, and it is worked under the atmosphere of sulfide gas concentration less than 5ppm.
Wherein, described synthetic gas comes from the gasification reaction product of coal and/or biomass.Described synthetic gas is removed sulfide gas before in entering the methanator unit, makes the concentration of sulfide gas in described synthetic gas less than 5ppm.
Catalyzer in described methanator unit is the direct methanation of anti-sulphur catalyzer or the direct methanation of anti-sulphur catalyzer not.Wherein, the described direct methanation of anti-sulphur catalyzer is with molybdenum, tungsten, and vanadium, cobalt is or/and nickel is active ingredient, the direct methanation catalyzer take the oxide compound of aluminium, zirconium, titanium, cerium, magnesium or hopcalite as carrier.The described direct methanation of anti-sulphur catalyzer is further the Ni/Mo base, Ni/W is basic and/or the basic direct methanation catalyzer of Ni/ (Mo+W).The described direct methanation of anti-sulphur catalyzer is further take NiO as active ingredient, with MoO
3And/or WO
3For coagent, with Al
2O
3Direct methanation catalyzer for carrier.
Wherein, described methanator unit is the methanator of three series connection, and wherein, the first and second methanators are adiabatic reactor, and the front three alkylation reactors is thermal insulation or isothermal reactor.Wherein, described first, second, and third methanator temperature of reaction is 200～700 ℃, and air speed is 2000～10000/ hours.Wherein, described additional methanator unit is a thermal insulation or isothermal reactor, and its temperature of reaction is 200～700 ℃, and air speed is 2000～10000/ hours.
Wherein, enter the H of the synthetic gas in described methanator unit
2/ CO(mol ratio)=0.70-1.67; Enter the H that replenishes the thick synthetic natural gas in the methanator unit
2/ CO(mol ratio)=0.90-3.0.Wherein, carbonic acid gas and sulfide gas in carbonic acid gas and sulfide gas remove the unit through N methyldiethanol amine (MDEA) or Polyethylene glycol dimethyl ether (SELEXOL) absorption and be removed.
According to second aspect present invention, a kind of method that is rich in CH4 gas with aforementioned system production is provided, described method comprises the following steps in order:
The synthetic gas that (1) will contain CO, CO2, H2, sulfide gas and optional water vapor is sent in the methanator unit, and synthetic gas carries out the direct methanation reaction therein under catalyst action, and is converted into and comprises CH4, CO
2, CO, H
2Thick synthetic natural gas with sulfide gas;
(2) above-mentioned thick synthetic natural gas is sent into carbonic acid gas and sulfide gas removes in the unit, the CO in thick synthetic natural gas
2Be removed therein with sulfide gas, make sulfide gas concentration in thick synthetic natural gas less than 5ppm;
(3) the thick synthetic natural gas after carbon dioxide removal and sulfide gas enters and replenishes in the methanator unit, and thick synthetic natural gas is replenished therein direct methanation and reacted under catalyst action, further with the CO in thick synthetic natural gas
2, CO, H
2Be converted into CH4 and H
2O, thus synthetic natural gas formed, wherein, the catalyzer that replenishes in methanator is the direct methanation of anti-sulphur catalyzer, it is worked under the atmosphere of sulfide gas concentration less than 5ppm;
(4) synthetic natural gas enters in dewatering unit, and described synthetic natural gas is removed H therein
2O, thus refining synthetic natural gas formed.
Wherein, thick synthetic natural gas enter replenish methanation reaction in replenishing the methanator unit before, do not need to regulate its H
2/ CO(mol ratio).Described refining synthetic natural gas meets GB GB17820-2012 Natural gas standard.
Description of drawings
Fig. 1 is the schematic diagram that the system operation principles of CH4 gas is rich in existing synthetic gas preparation of explanation
Fig. 2 is the schematic diagram that the system operation principles of CH4 gas is rich in synthetic gas preparation of the present invention of explanation.
Embodiment
Be further explained in detail the present invention by the description below with reference to accompanying drawing, but following description only is used for making the general technical staff of the technical field of the invention can more be expressly understood principle of the present invention and marrow, and does not mean that the present invention is carried out any type of restriction.That be equal in accompanying drawing or corresponding parts or feature represent with identical reference numerals.
Compare with prior art shown in Figure 1, the present invention shown in Figure 2 has the following advantages:
(1) replenish in the methanator unit and mainly carry out the direct methanation reaction, and use catalyst for methanation in presence of sulfur, so, need not H
2S sulfides gas concentration is removed to less than 0.1ppm, only needs sulfide is removed to its concentration less than 20mg/m
3H
2S(is 5ppm approximately) get final product, namely need not to carry out the low temperature deep desulfuration, final product satisfies Sweet natural gas GB (GB17820-2012) technical requirements, like this, can reduce CO
2And/or H
2The undue harsh requirement in the acid gas removal such as S unit reduces the working load of these acid gas removals unit;
(2) minimizing is also cold and hot, adopts the sulfur removal technologies such as SELEXOL and MDEA to replace industrial low-temp methanol washing process commonly used, and acid gas removes and can operate at normal temperatures, need not the acid gas temperature is down to-40 ℃ from several Baidu, thereby, reduced energy wastage;
(3) reduce facility investment, there is no the refrigeration equipments such as ice chest in SELEXOL technique, compare with the conventional industrial technology of low-temperature rectisol, reduced facility investment;
(4) raw material of synthetic gas transforms fully, mainly carries out direct methanation and react in additional methanator unit, can fully make CO and H in raw material of synthetic gas or the rough gas of synthesis of natural
2Be converted into CH
4
(5) the C/H ratio in need not again to regulate raw material of synthetic gas or the rough gas of synthesis of natural in replenishing the methanator unit.
As shown in Figure 1, in the present invention, the conventional raw material of preparation synthetic gas comprises raw coal and/or biomass, and they form crude synthesis gas by gasification unit, after the preliminary cleaning unit removes the impurity such as dust in gas and tar, just become the stand-by synthetic gas that can carry out methanation reaction again.
As shown in Figure 1, in the present invention, contain H
2, CO, CO
2, optional H
2The synthetic gas of O and a certain amount of sulfide gas enters in the direct methanation reactor unit, and mainly carries out therein direct methanation reaction and water-gas shift reaction, with H in synthetic gas
2Change into CH with CO
4Thereby, form the rough gas of synthesis of natural that contains impurity;
The above-mentioned rough gas of synthesis of natural that contains impurity is removed most CO at thick gas clean unit
2With the sour gas such as sulfide, thereby form synthetic natural gas after purifying;
Synthetic natural gas after purification enters again replenishes in the methanator unit, will be in gas residue CO and H
2Be converted into CH
4Thereby, forming refining synthetic natural gas, described refining synthetic natural gas satisfies Sweet natural gas GB (GB17820-2012) technical specification fully.
Embodiment
Embodiment 1
By technical process shown in Figure 2, coal or biomass are vaporized in lurgi gasifier, the crude synthesis gas that forms is after removing the impurity such as dust and tar, obtain the synthetic gas of rough purification, after the synthetic gas of rough purification is preheating to 250 ℃, enter in the methanator unit, carry out direct methanation reaction and part water-gas shift reaction, wherein, reaction pressure: 3.0MPa, the synthetic gas of rough purification (butt volume) forms: H
2: 41.08%, CO:23.60%, CO
2: 26.75%, CH
4: 8.05%, H
2S+COS:0.07%, N
2+ AR:0.45%, H
2Direct methanation reaction and part water-gas shift reaction occur in/CO(mol ratio)=1.74 under Mo methylmethane catalyst action, reacted gas is cooled to room temperature after heat exchanger network reclaims heat, formed (volume) and be: H
2: 4.34%, CO:1.63%, CO
2: 55.54%, CH
4: 37.31%, H
2O:0.32%, H
2S+COS:0.14%, N
2The rough gas of the synthesis of natural of the initial reaction of+AR:0.73%.
Then, the rough gas of above-mentioned synthesis of natural is entered in thick gas clean unit, comprise CO in order to remove the overwhelming majority
2And/or H
2The sour gas of S, thereby, formed (butt volume) and be: H
2: 9.86%, CO:3.69%, CO
2: 0.13%, CH
4: 84.67%, H
2O:0.01%, H
2S+COS:4ppm, and N
2The rough gas of synthesis of natural after the purification of+AR:1.65%, then after heat exchange is warmed up to 260 ℃ with it enters and replenishes in the methanator unit, at Ni/Mo/Al
2O
3Under the effect of base catalyst for methanation in presence of sulfur, the rough gas of above-mentioned synthesis of natural carries out the direct methanation reaction, will wherein remain H
2, CO and CO
2Change CH into
4And H
2O, reaction product is cooled to room temperature, then obtains refining synthetic natural gas through dehydration, and described refining synthetic natural gas satisfies Sweet natural gas GB (GB17820-2012) technical specification, and its composition (volume) is: H
2: 1.85%, CO:0.06%, CO
2: 0.88%, CH
4: 95.40%, H
2S+COS:4ppm, N
2+ AR:1.80%, then, compressed the entering of described refining synthetic natural gas is transported to user side in pipeline.
In the present embodiment 1, the chemical constitution of raw material of synthetic gas, each stage work in-process (thick gas) and the finished product (refining synthetic natural gas) represents in the following Table 1.
Table 1
Embodiment 2
By technical process shown in Figure 2, coal or biomass are vaporized in the E-Gas vapourizing furnace, the crude synthesis gas that forms is after removing the impurity such as dust and tar, obtain the synthetic gas of rough purification, after the synthetic gas of rough purification is preheating to 250 ℃, enter in the methanator unit, carry out direct methanation reaction and part water-gas shift reaction, wherein, reaction pressure: 4.1MPa, the synthesis gas composition of rough purification (butt volume): H
2: 41.95%, CO:38.96%, CO
2: 18.01%, CH
4: 0.11%, H
2S+COS:0.09%, N
2+ AR:0.87%, H
2/ CO(mol ratio)=1.07, add a certain amount of water vapor, carry out direct methanation reaction and part water-gas shift reaction under (Mo+W) methylmethane catalyst action, reacted gas is after heat exchanger network reclaims heat, be cooled to room temperature, formed (volume) and be: H
2: 2.32%, CO:0.92%, CO
2: 61.48%,
CH
4: 33.35%, H
2O:0.32%, H
2S+COS:0.15%, N
2The rough gas of the synthesis of natural of the initial reaction of+AR:1.46%.
Then, the rough gas of above-mentioned synthesis of natural is entered in thick gas clean unit, comprise CO in order to remove the overwhelming majority
2And/or H
2The sour gas of S, thereby, formed (butt volume) and be: H
2: 6.09%, CO:2.41%, CO
2: 0.16%, CH
4: 87.49%, H
2O:0.01%, H
2S+COS:2ppm, N
2The rough gas of synthesis of natural after the purification of+AR:3.84%, then after heat exchange is warmed up to 280 ℃ with it enters and replenishes in the methanator unit, at Ni/ (Mo+W)/Al
2O
3Under the effect of base catalyst for methanation in presence of sulfur, carry out the direct methanation reaction, will wherein remain H
2, CO and CO
2Change CH into
4And H
2O, reaction product is cooled to room temperature, then obtains refining synthetic natural gas through dehydration, and described refining synthetic natural gas satisfies Sweet natural gas GB (GB17820-2012) technical specification, its composition (volume): H
2: 0.87%, CO:0.02%, CO
2: 0.67%, CH
4: 94.38%, H
2S+COS:2ppm, N
2+ AR:4.05%, then, compressed the entering of described refining synthetic natural gas is transported to user side in pipeline.
In the present embodiment 2, the chemical constitution of raw material of synthetic gas, each stage work in-process (thick gas) and the finished product (refining synthetic natural gas) represents in the following Table 2.
Table 2
Embodiment 3
By technical process shown in Figure 2, coal or biomass are vaporized in the Texaco vapourizing furnace, the crude synthesis gas that forms obtains the synthetic gas of rough purification, after the synthetic gas of rough purification is preheating to 250 ℃ after removing the impurity such as dust and tar, enter in the methanator unit, carry out direct methanation reaction and part water-gas shift reaction, wherein, reaction pressure: 4.1MPa, crude synthesis gas (butt volume) consists of: H
2: 36.19%, CO:49.55%, CO
2: 12.87%, CH
4: 0.40%, H
2S+COS:0.09%, N
2+ AR:0.90%, add a certain amount of water vapor, direct methanation reaction and part water-gas shift reaction occur under W methylmethane catalyst action, reacted gas is after heat exchanger network reclaims heat, be cooled to room temperature, formed (butt volume) and be: H
2: 2.40%, CO:0.83%, CO
2: 62.42%, CH
4: 32.52%, H
2S+COS:0.14%, N
2The rough gas of the synthesis of natural of the initial reaction of+AR:1.37%.
Then, the rough gas of above-mentioned synthesis of natural is entered in thick gas clean unit,, comprise CO in order to remove the overwhelming majority
2And/or H
2The sour gas of S, thereby, formed (butt volume) and be: H
2: 6.46%, CO:2.22%, CO
2: 0.17%, CH
4: 87.45%, H
2S+COS:5ppm, N
2The rough gas of synthesis of natural after the purification of+AR:3.70%, then after heat exchange is warmed up to 280 ℃ with it enters and replenishes in the methanator unit, at Ni/W/Al
2O
3Under the effect of base catalyst for methanation in presence of sulfur, carry out the direct methanation reaction, will wherein remain H
2, CO and CO
2Change CH into
4And H
2O, reaction product is cooled to room temperature, then obtains refining synthetic natural gas through dehydration, and described refining synthetic natural gas satisfies Sweet natural gas GB (GB17820-2012) technical specification, its composition (butt volume): H
2: 1.01%, CO:0.02%, CO
2: 0.47%, CH
4: 94.59%, H
2S+COS:5ppm, N
2+ AR:3.91%, then, compressed the entering of described refining synthetic natural gas is transported to user side in pipeline.
In the present embodiment 3, the chemical constitution of raw material of synthetic gas, each stage work in-process (thick gas) and the finished product (refining synthetic natural gas) represents in the following Table 3.
Table 3
Test case 1
Measure all technical of the synthetic natural gas product (refining synthetic natural gas) that obtains in embodiment 1-3 according to Sweet natural gas GB (GB17820-2012) technical specifications, and compare with the numerical value of Sweet natural gas GB (GB17820-2012) technical specifications regulation.
Table 4
A: in GB GB17820-2012, the standard reference condition of gas volume is 101.325KPa, 20 ℃;
B: in GB GB17820-2012, under transport condition, when the buried temperature in pipeline pipe top was 0 ℃, water dew point should be higher than-5 ℃;
C: in GB GB17820-2012, enter the Sweet natural gas of gas pipe line, the pressure of water dew point should be the highest transfer pressure.
The term that this specification sheets is used and form of presentation only are used as descriptive and nonrestrictive term and form of presentation, the feature that will represent and describe unintentionally when using these terms and form of presentation or any equivalent exclusion of its integral part.
Although represented and described several embodiment of the present invention, the present invention is not restricted to described embodiment.On the contrary; those skilled in the art should recognize that in the situation that do not break away from principle of the present invention and spirit can be carried out any accommodation and improvement to these embodiments, protection scope of the present invention is determined by appended claim and equivalent thereof.
Claims (15)
1. a synthetic gas prepares the system that is rich in CH4 gas, and described system comprises:
Methanator unit, synthetic gas carry out direct methanation reaction therein under catalyst action, and are converted into and comprise CH4, CO
2, CO, H
2Thick synthetic natural gas with sulfide gas;
Carbonic acid gas and sulfide gas remove the unit, the CO in thick synthetic natural gas
2Be removed therein with sulfide gas, make sulfide gas concentration in thick synthetic natural gas less than 5ppm;
Additional methanator unit, thick synthetic natural gas is replenished the direct methanation reaction therein under catalyst action, further with the CO in thick synthetic natural gas
2, CO, H
2Be converted into CH4 and H
2O, thus synthetic natural gas formed; With
Dewatering unit, synthetic natural gas are removed H therein
2O, thus refining synthetic natural gas formed,
Wherein, the catalyzer that replenishes in methanator is the direct methanation of anti-sulphur catalyzer, and it is worked under the atmosphere of sulfide gas concentration less than 5ppm.
2. system according to claim 1, wherein, described synthetic gas comes from the gasification reaction product of coal and/or biomass.
3. system according to claim 1, wherein, described synthetic gas is removed sulfide gas before in entering the methanator unit, makes the concentration of sulfide gas in described synthetic gas less than 5ppm.
4. system according to claim 1, wherein, the catalyzer in described methanator unit is the direct methanation of anti-sulphur catalyzer or the direct methanation of anti-sulphur catalyzer not.
5. according to claim 1 or 4 described systems, wherein, the described direct methanation of anti-sulphur catalyzer is with molybdenum, tungsten, vanadium, cobalt is or/and nickel is active ingredient, the direct methanation catalyzer take the oxide compound of aluminium, zirconium, titanium, cerium, magnesium or hopcalite as carrier.
6. system according to claim 5, wherein, the described direct methanation of anti-sulphur catalyzer is further the Ni/Mo base, Ni/W is basic and/or the basic direct methanation catalyzer of Ni/ (Mo+W).
7. system according to claim 5, wherein, the described direct methanation of anti-sulphur catalyzer is further take NiO as active ingredient, with MoO
3And/or WO
3For coagent, with Al
2O
3Direct methanation catalyzer for carrier.
8. system according to claim 1, wherein, described methanator unit is the methanator of three series connection, and wherein, the first and second methanators are adiabatic reactor, and the front three alkylation reactors is thermal insulation or isothermal reactor.
9. system according to claim 8, wherein, described first, second, and third methanator temperature of reaction is 200～700 ℃, air speed is 2000～10000/ hours.
10. system according to claim 1, wherein, described additional methanator unit is a thermal insulation or isothermal reactor, and its temperature of reaction is 200～700 ℃, and air speed is 2000～10000/ hours.
11. system according to claim 1 wherein, enters the H of the synthetic gas in described methanator unit
2/ CO(mol ratio)=0.70-1.67; Enter the H that replenishes the thick synthetic natural gas in the methanator unit
2/ CO(mol ratio)=0.90-3.0.
12. system according to claim 1, wherein, carbonic acid gas and sulfide gas in carbonic acid gas and sulfide gas remove the unit through N methyldiethanol amine (MDEA) or Polyethylene glycol dimethyl ether (SELEXOL) absorption and be removed.
13. one kind with according to aforementioned claim 1-12 any one described system production be rich in the method for CH4 gas, described method comprises the following steps in order:
The synthetic gas that (1) will contain CO, CO2, H2, sulfide gas and optional water vapor is sent in the methanator unit, and synthetic gas carries out the direct methanation reaction therein under catalyst action, and is converted into and comprises CH4, CO
2, CO, H
2Thick synthetic natural gas with sulfide gas;
(2) above-mentioned thick synthetic natural gas is sent into carbonic acid gas and sulfide gas removes in the unit, the CO in thick synthetic natural gas
2Be removed therein with sulfide gas, make sulfide gas concentration in thick synthetic natural gas less than 5ppm;
(3) the thick synthetic natural gas after carbon dioxide removal and sulfide gas enters and replenishes in the methanator unit, and thick synthetic natural gas is replenished therein direct methanation and reacted under catalyst action, further with the CO in thick synthetic natural gas
2, CO, H
2Be converted into CH
4And H
2O, thus synthetic natural gas formed, wherein, the catalyzer that replenishes in methanator is the direct methanation of anti-sulphur catalyzer, it is worked under the atmosphere of sulfide gas concentration less than 5ppm;
(4) synthetic natural gas enters in dewatering unit, and described synthetic natural gas is removed H therein
2O, thus refining synthetic natural gas formed.
14. a method according to claim 13, wherein, thick synthetic natural gas enter replenish methanation reaction in replenishing the methanator unit before, do not need to regulate its H
2/ CO(mol ratio).
15. a method according to claim 13, wherein, described refining synthetic natural gas meets GB GB17820-2012 Natural gas standard.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602357A (en) * | 2013-11-28 | 2014-02-26 | 青岛联信催化材料有限公司 | Production process of liquefied natural gas |
| CN104152199A (en) * | 2014-08-19 | 2014-11-19 | 赛鼎工程有限公司 | Technology for preparing natural gas through sulfur resistant methanation by coal-prepared synthesis gases |
| CN104164262A (en) * | 2014-08-19 | 2014-11-26 | 赛鼎工程有限公司 | Process for preparing substitute natural gas through sulphur-tolerant methanation of coal synthesis gas |
| CN104862017A (en) * | 2015-05-07 | 2015-08-26 | 新奥科技发展有限公司 | Purification system and method for coal gas quality improvement |
| CN111003690A (en) * | 2019-11-27 | 2020-04-14 | 浙江天禄环境科技有限公司 | Decarburization process of synthesis gas |
| CN111330589A (en) * | 2020-04-15 | 2020-06-26 | 太原理工大学 | Ordered mesoporous MgNi/WO3Preparation method of methanation catalyst |
| CN113272410A (en) * | 2018-10-11 | 2021-08-17 | 内斯特化学股份公司 | Method and apparatus for producing biomethane from waste |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602357A (en) * | 2013-11-28 | 2014-02-26 | 青岛联信催化材料有限公司 | Production process of liquefied natural gas |
| CN103602357B (en) * | 2013-11-28 | 2015-02-25 | 青岛联信催化材料有限公司 | Production process of liquefied natural gas |
| CN104152199A (en) * | 2014-08-19 | 2014-11-19 | 赛鼎工程有限公司 | Technology for preparing natural gas through sulfur resistant methanation by coal-prepared synthesis gases |
| CN104164262A (en) * | 2014-08-19 | 2014-11-26 | 赛鼎工程有限公司 | Process for preparing substitute natural gas through sulphur-tolerant methanation of coal synthesis gas |
| CN104152199B (en) * | 2014-08-19 | 2017-01-25 | 赛鼎工程有限公司 | Technology for preparing natural gas through sulfur resistant methanation by coal-prepared synthesis gases |
| CN104862017A (en) * | 2015-05-07 | 2015-08-26 | 新奥科技发展有限公司 | Purification system and method for coal gas quality improvement |
| CN113272410A (en) * | 2018-10-11 | 2021-08-17 | 内斯特化学股份公司 | Method and apparatus for producing biomethane from waste |
| CN113272410B (en) * | 2018-10-11 | 2024-05-28 | 内斯特化学技术股份公司 | Method and apparatus for producing biomethane from waste |
| CN111003690A (en) * | 2019-11-27 | 2020-04-14 | 浙江天禄环境科技有限公司 | Decarburization process of synthesis gas |
| CN111330589A (en) * | 2020-04-15 | 2020-06-26 | 太原理工大学 | Ordered mesoporous MgNi/WO3Preparation method of methanation catalyst |
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