CN102531819A - Method for preparing methane and methanol by using synthesis gas - Google Patents
Method for preparing methane and methanol by using synthesis gas Download PDFInfo
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- CN102531819A CN102531819A CN2010106134482A CN201010613448A CN102531819A CN 102531819 A CN102531819 A CN 102531819A CN 2010106134482 A CN2010106134482 A CN 2010106134482A CN 201010613448 A CN201010613448 A CN 201010613448A CN 102531819 A CN102531819 A CN 102531819A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a method for preparing methane and methanol by using synthesis gas. The method mainly comprises that: the synthesis gas is converted into the methane, and the methanol and an oil product are produced at the same time. The catalyst is a zinc-chromium catalyst or a copper-based catalyst; the reaction for preparing the methane and the methanol by using the synthesis gas comprises that: the reaction temperature is 250 to 500 DEG C, the reaction pressure is 2.0 to 50.0MPa, the gas hourly space velocity (GHSV) is 500 to 50,000, and the ratio of hydrogen (H2) to carbon monoxide (CO) is 2-15; and the product is subjected to gas-liquid separation, the gas enters a natural gas pipeline, and the liquid contains the methanol and the oil product. The synthesis gas is used as a raw material, is wide in source, and can be obtained from coal or biomass. The catalyst is a mature methanol catalyst, the product can be regulated as required, and the method is suitable for continuous large-scale production.
Description
Technical field
The invention belongs to the catalytic chemistry field, relate to synthetic gas and transform system methane, and combined production of methanol, a kind of catalysis novel process and application that is used for preparing methane by synthetic gas and combined production of methanol is provided.
Background technology
Enforcement along with policies such as the domestic strategy of sustainable development and reinforcement environmental protection; Domestic demand to Sweet natural gas increases substantially; Domestic gas production can not be met the need of market fully; Imbalance between supply and demand is outstanding, therefore must be by all kinds of means, multimode enlarges resource provision, satisfies the growing market requirement.Be based on the rich coal energy structure of China's oil starvation weak breath characteristics simultaneously, development coal preparing natural gas is one of feasible mode.In the process that coal transforms, the energy efficiency of coal preparing natural gas is the highest coal utilization mode, reaches 53%, not only can significantly reduce the consumption of coal, has also reduced SO simultaneously
2, CO
2Discharging, the pollution that alleviates environment.In addition, the coal preparing natural gas can be carried through pipeline on a large scale, has increased its transportation and the security of using.
With gas reforming is that methane (synthetic natural gas) is a mature technology, and 1 ton of coal can be converted into 400m
3Synthetic natural gas, present sophisticated technology have Top's rope methanation circulation technology (TREMPTM) technology, DAVY company methanation technology (CRG).Also there are sophisticated methanation technology in BASF AG and LURGI.Domestic comparatively familiar to methanation technology.
Whether at present, carrying out preparing methane from coal on a large scale has good economic benefit, is still waiting the actual production checking.The preparing methane from coal industry has characteristics such as investment has a big risk greatly.If can realize that coal preparing natural gas and other are raw material with coal,, can increase the ability to ward off risks of coal preparing natural gas project through the coproduction of the multiple Coal Chemical Industry product of synthetic gas system.Realize coal preparing natural gas and coal system methyl alcohol, coal system alkene, coal system oil, the coproduction of multiple coal-based product such as synthetic ammonia will realize that multiple coal-based product advantage is complementary, effectively improves the economic benefit and whole opposing risk ability of coal preparing natural gas project.In addition, China's gas very unbalanced with gas, northern area consumption in winter is big, and it is few that non-heating season is saved gas, and peaking problem is very serious.Except adopting peak regulation means such as underground natural gas storage, gas peak regulation generating or LNG, also can carry out peak regulation with coal preparing natural gas factory, that is to say that coal preparing natural gas factory produces Sweet natural gas winter; Other seasons can coproduction part methyl alcohol; Oil, alkene, products such as synthetic ammonia.
Through synthetic gas system methane, and the research and development of coproduction alcohol, oil, alkene, catalyst of synthetic ammonia and technology have very big practicality and application prospect to coal.
Summary of the invention
The object of the present invention is to provide the catalysis novel process and the application of a kind of preparing methane by synthetic gas and combined production of methanol.
The present invention goes back combined production of methanol and oil product except synthetic gas changes into methane, all synthetic gas are not to be converted into methane or methyl alcohol fully, and prior art then is converted into methane to synthetic gas fully, and perhaps to be converted into methyl alcohol fully be purpose to synthetic gas.Compare with full methanation technology, the present invention can reduce the industry risk, operates more flexibly, can realize bigger economic and social benefit.This is the maximum difference that precipitated iron-based catalyst provided by the invention and existing full methanation technology exist.
The present invention carries out methanation reaction with synthetic gas through the reactor drum that catalyst for methanol is housed, preparation methane and combined production of methanol and oil product.
Catalyzer according to the invention can be zinc chrome ZnO/Cr
2O
3Catalyzer.
The molar ratio ZnO/Cr of zinc oxide and chromic oxide in the catalyzer according to the invention
2O
3=0.2-1.5
Catalyzer according to the invention can be zinc chrome Cu-A-B-O catalyzer.Wherein:
Active ingredient Cu, in metallic element, the weight percentage in catalyzer is 10.0-50.0wt%;
Auxiliary agent A is Zn, Cr, and Mn, Al, the mixing of any one or a few in the Fe oxide compound, in metallic element, the content in catalyzer is 0.0-50.0wt%;
Auxiliary agent B is Zr, B, Ce, Si, and the mixing of any one or a few in the Ti oxide compound, in metallic element, the content in catalyzer is 0.0-50.0wt%.
The temperature of reaction of preparing methane by synthetic gas according to the invention and combined production of methanol and oil product is 250～500 ℃, and reaction pressure is 2.0～50.0MPa, and air speed GHSV is 500～50000, and the ratio of hydrogen and carbon monoxide is H
2/ CO=2～15.
The selectivity of methyl alcohol is 1.0-20.0% in the product of the present invention; The selectivity of oil product is 0.0-20.0% in the product.
The carbon number n=3-15 of oil product according to the invention.
ZnO/Cr according to the invention
2The O3 catalyst preparation step is following: be mixed with the nitrate mixed solution of zinc and chromium by the mol ratio of said zinc oxide and chromic oxide, the nitrate soln of zinc and chromium is used alkali precipitation, make catalyzer through washing, dry aftershaping.
Cu-A-B-O catalyst preparation step according to the invention is following: in the ratio of each component in the Cu-A-B-O catalyzer, with the nitrate mixed solution and the precipitation agent anhydrous Na of Cu, adjuvant component A and the described metals ion of B
2CO
3Solution; Under constant pH, constant agitation speed, carry out coprecipitation reaction, throw out behind deionized water thorough washing, suction filtration, at 80～150 ℃ (in air) dry 1～10 hour; Respectively 400～1000 ℃ of roasting temperatures 1～20 hour, obtain said catalyzer again.
With the hydrogen of hydrogen or inert gas dilution, react then by or synthetic gas reduction before reaction for the catalyzer of preparing methane by synthetic gas according to the invention and combined production of methanol and oil product.
Description of drawings
Fig. 1 be copper-based catalysts copper zinc-aluminium Cu-Zn-Al under different temperature of reaction to H
2/ CO=3: the catalytic performance of 1 synthetic gas methanation and combined production of methanol.(catalyst quality: 1g Cu-Zn-Al catalyzer; Virgin gas is formed: H
2/ CO/Ar=64/32/4; Synthetic gas flow velocity: Syngas=120ml/min; Reaction pressure: P=3.0MPa; Activation condition: 350 ℃ of following 5h)
Fig. 2 be copper-based catalysts copper zinc-aluminium Cu-Zn-Al under different temperature of reaction to H
2/ CO=8: the catalytic performance of 1 synthetic gas methanation and combined production of methanol.(catalyst quality: 1g Cu-Zn-Al catalyzer; Virgin gas is formed: H
2/ CO/Ar=85.5/10.5/4; Synthetic gas flow velocity: Syngas=120ml/min; Reaction pressure: P=3.0MPa; Activation condition: 350 ℃ of following 6h)
Fig. 3 be copper-based catalysts Cu-Zn-Al under different reaction pressures to H
2/ CO=3: the catalytic performance of 1 synthetic gas methanation and combined production of methanol.(catalyst quality: 1g Cu-Zn-Al; Virgin gas is formed: H
2/ CO/Ar=72/24/4; Synthetic gas flow velocity: Syngas=120ml/min; Temperature of reaction: T=280 ℃; Activation condition: 350 ℃ of following 5h)
Fig. 4 be copper-based catalysts Cu-Zn-Al under different reaction pressures to H
2/ CO=8: the catalytic performance of 1 synthetic gas methanation and combined production of methanol.(catalyst quality: 1g Cu-Zn-Al; Virgin gas is formed: H
2/ CO/Ar=85.5/10.5/4; Synthetic gas flow velocity: Syngas=100ml/min; Temperature of reaction: T=280 ℃; Activation condition: 350 ℃ of following 5h)
Fig. 5 is that copper-based catalysts Cu-Zn-Al is at different H
2Under/the CO to the catalytic performance of synthetic gas methanation and combined production of methanol.(catalyst quality: 1.0g Cu-Zn-Al; Reaction pressure: P=3.0MPa; Temperature of reaction: T=330 ℃; Activation condition: 350 ℃ of following 5h, reaction velocity GHSV=7000hr
-1)
Fig. 6 is zinc chrome catalyzer catalytic performance to synthetic gas methanation and combined production of methanol under different temperature.(catalyst quality: 1.0g ZnO/Cr
2O3; Virgin gas is formed: H
2/ CO/Ar=72/24/4, temperature of reaction: T=380 ℃, reaction pressure: P=6.0MPa; Activation condition: 450 ℃ of following 5h, reaction velocity GHSV=7000hr
-1)
Embodiment
Embodiment 1 method for preparing catalyst
Cu-Zn-Al-O catalyst preparation step according to the invention is following: with the nitrate mixed solution of Copper nitrate hexahydrate, zinc nitrate hexahydrate, nine water aluminum nitrates; Vigorous stirring at room temperature; Precipitation agent Na2CO3 solution is slowly dripped to wherein, under constant pH to 9.0, constant agitation speed, carry out coprecipitation reaction.Continue to stir after the 150min, will precipitate age overnight.The precipitate with deionized water washing is extremely neutral, spinning.Gained is deposited in dry 12h in 120 ℃ of baking ovens, and dry back sample places retort furnace, is warmed up to 400 ℃ with the temperature rise rate of 2 ℃/min, and roasting 2h obtains the sample after the roasting.
The analytical procedure of embodiment 2 products
Products obtained therefrom is analyzed with Agilent 7890A.Chromatogram is furnished with dual-detector FID and TCD, and a ten-way valve is arranged, can be so that product gets into packed column and capillary column simultaneously respectively.Data are with the Chemstation software processes of Agilent.
The concrete chromatographic condition of Agilent is following:
Chromatogram: Agilent 7890A
FID chromatographic column: HP-PONA 19091S-001,50mx0.2mm (internal diameter), 0.5 μ m thickness
Carrier gas: helium, 2.5ml/min
Post oven temperature, degree: 35 ℃ keep 5min
35-150℃，5℃/min
150 ℃ keep 10min
Injection port: shunting (100: 1) temperature: 170 ℃
250 ℃ of detector: FID
TCD chromatographic column: carbonaceous molecular sieve post, TDX-01 2mx2mm (internal diameter)
Carrier gas: helium, 20ml/min
Post oven temperature, degree: 35 ℃ keep 5min
35-150℃，5℃/min
150 ℃ keep 10min
Injection port: temperature: 170 ℃
200 ℃ of detector: TCD
The catalytic perfomance of embodiment 3 preparing methane by synthetic gas and combined production of methanol
In tubular fixed-bed reactor, prepared catalyzer has been carried out the catalytic perfomance test evaluation of preparing methane by synthetic gas and combined production of methanol.According to requirement of the present invention, the technique initialization of preparing methane by synthetic gas and combined production of methanol as follows:
Raw material is formed: H2/CO/Ar argon gas (Ar) is interior mark
Reaction pressure: 0.1-6.0MPa
The volume space velocity GHSV:7000hr of raw material
-1
The weight of catalyzer: 1.0g
The granularity of catalyzer: 40-60 order
The height of beds :～10mm
When beginning to investigate, at first that embodiment 1,2 is prepared catalyzer is at 350 ℃, and pure hydrogen, or add carrier gas, or reduction 5 hours under the condition of synthetic gas drop to specified temperature to the temperature of bed then, feed synthetic gas and react.Being heated by electrical heater of reactor drum, the control of temperature of reaction is confirmed by the thermocouple that inserts beds.Virgin gas and product gas are formed through the Angilent7890 gas chromatographic detection, and this chromatogram has two detectors: hydrogen flame detector and thermal conductivity detector.The hydrocarbon polymer that hydrogen flame detector detects in the product distributes, and thermal conductivity detector detects the hydrogen in raw material and the product, carbon monoxide, carbonic acid gas with, methane and interior mark argon gas.The composition of two detectors is integrated as intermediary with methane.Only if other explanation is arranged, the instance below the present invention all carries out under above-mentioned experiment condition.
Because experiment is carried out under different reaction conditions, resulting methyl alcohol selectivity is also different, and product can be regulated on demand.
Claims (7)
1. the method for preparing methane by synthetic gas and combined production of methanol is carried out methanation reaction with synthetic gas through the reactor drum that the synthesising gas systeming carbinol catalyzer is housed, and preparation methane and combined production of methanol is characterized in that said catalyzer is zinc chrome ZnO/Cr
2O
3Catalyzer or Cu-A-B-O catalyzer;
Said preparing methane by synthetic gas and combined production of methanol reaction are: temperature of reaction is 250～500 ℃, and reaction pressure is 2.0～50.0MPa, and air speed GHSV is 500～50000, and the ratio of hydrogen and carbon monoxide is H
2/ CO=2～15.
2. according to the described method of claim 1, it is characterized in that said zinc chrome ZnO/Cr
2O
3The molar ratio ZnO/Cr of zinc oxide and chromic oxide in the catalyzer
2O
3=0.2-1.5.
3. according to the described method of claim 1, it is characterized in that, in the said zinc chrome Cu-A-B-O catalyzer:
Active ingredient Cu, in metallic element, the weight percentage in catalyzer is 10.0-50.0wt%;
Auxiliary agent A is Zn, Cr, and Mn, Al, the mixing of any one or a few in the Fe oxide compound, in metallic element, the content in catalyzer is 0.0-50.0wt%;
Auxiliary agent B is Zr, B, Ce, Si, and the mixing of any one or a few in the Ti oxide compound, in metallic element, the content in catalyzer is 0.0-50.0wt%.
4. according to the described method of claim 1, it is characterized in that said temperature of reaction is 150～350 ℃, reaction pressure is 0.5～8.0MPa, and air speed GHSV is 500～50000, and the ratio of hydrogen and carbon monoxide is H
2/ CO=2～15.
5. according to the described method of claim 1, it is characterized in that with the hydrogen of hydrogen or inert gas dilution, react then by or synthetic gas reduction before reaction for said catalyzer.
6. according to the described method of claim 2, it is characterized in that said ZnO/Cr
2O
3Catalyst preparation step is following: be mixed with the nitrate mixed solution of zinc and chromium by the mol ratio of said zinc oxide and chromic oxide, the nitrate soln of zinc and chromium is used alkali precipitation, make catalyzer through washing, dry aftershaping.
7. according to the described method of claim 3; It is characterized in that; Said Cu-A-B-O catalyst preparation step is following: in the ratio of each component in the Cu-A-B-O catalyzer, with the nitrate mixed solution and the precipitation agent anhydrous Na of Cu, adjuvant component A and the described metals ion of B
2CO
3Solution; Under constant pH, constant agitation speed, carry out coprecipitation reaction, throw out behind deionized water thorough washing, suction filtration, at 80～150 ℃ (in air) dry 1～10 hour; Respectively 400～1000 ℃ of roasting temperatures 1～20 hour, obtain said catalyzer again.
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| CN2010106134482A CN102531819A (en) | 2010-12-30 | 2010-12-30 | Method for preparing methane and methanol by using synthesis gas |
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|---|---|---|---|
| CN2010106134482A CN102531819A (en) | 2010-12-30 | 2010-12-30 | Method for preparing methane and methanol by using synthesis gas |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230621A (en) * | 2013-06-07 | 2014-12-24 | 中国海洋石油总公司 | Method for producing methane and co-producing low carbon alcohol from carbonaceous material |
| CN107971026A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | Combination catalyst for producing light olefins |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230621A (en) * | 2013-06-07 | 2014-12-24 | 中国海洋石油总公司 | Method for producing methane and co-producing low carbon alcohol from carbonaceous material |
| CN104230621B (en) * | 2013-06-07 | 2016-12-28 | 中国海洋石油总公司 | A kind of method being produced methane coproduction low-carbon alcohols by carbonaceous material |
| CN107971026A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | Combination catalyst for producing light olefins |
| CN107971026B (en) * | 2016-10-21 | 2020-11-27 | 中国石油化工股份有限公司 | Combined catalyst for preparing low-carbon olefin |
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Application publication date: 20120704 |