CN101550052B - Process for producing methanol and coproducing methane by using synthesis gas containing methane - Google Patents

Process for producing methanol and coproducing methane by using synthesis gas containing methane Download PDF

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CN101550052B
CN101550052B CN 200810226890 CN200810226890A CN101550052B CN 101550052 B CN101550052 B CN 101550052B CN 200810226890 CN200810226890 CN 200810226890 CN 200810226890 A CN200810226890 A CN 200810226890A CN 101550052 B CN101550052 B CN 101550052B
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methane
gas
methanol
synthetic
temperature
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CN 200810226890
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Chinese (zh)
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CN101550052A (en
Inventor
常俊石
田文堂
蒋建明
张梅香
孟令龙
史立杰
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新奥新能(北京)科技有限公司
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Abstract

A technology for producing methanol and coproducing methane by using synthesis gas containing methane is characterized in that the synthesis gas is synthesized into methanol by purification, and the remaining active ingredients of purge gas of the synthesized methanol such as H2, CO and CO2 are used to be synthesized into methane. An internal heating cooling pipe heat exchange type reactor is adopted for synthesizing methane by an advanced methane catalyst, and simultaneously the methane in the raw gas is recycled to realize the technology for synthesizing methanol and coproducing methane.

Description

Contain methane synthetic gas methanol coproduction methane technology
Technical field
The present invention relates to contain the novel process of methane synthetic gas methanol, methane, particularly utilize the method for effective ingredient synthesizing methane remaining in the relief gas of synthetic methanol.
Background technology
The technique of synthetic gas methanol mainly contains four kinds according to raw material sources: gasification, Sweet natural gas, coke-oven gas, oil product at present.Industrial methanol synthetizing technology flow process mainly contain high-pressure process and in, low-pressure process.No matter adopt which kind of technique, roughly can be divided into following operation, see accompanying drawing 1.
In the process of synthetic gas direct production methyl alcohol, there is following inferior position:
1, hydrogen-carbon ratio is 2.05~2.1/1, CO 2Content is 1~3%, and this will changes persuing change with the decarbonizing section processing condition harsh;
2, the CH that is rich in of unstripped gas 4Discharged as rare gas element, caused energy dissipation and financial loss;
3, do not have that the synthetic gas of complete reaction is burned to be fallen or discharged, reduced the utilization ratio of unstripped gas.
Methanation technology is applied in the ammonia synthesis process the earliest to remove CO and the CO in the unstripped gas 2, the forties is just attached great importance to the research that qualified Sweet natural gas and town gas technology are produced in methanation abroad, makes most of CO and H in the coal gas by some or all of methanation 2Reaction is converted into the methane of high heating value, thereby generates SNG (instead of natural gas), can reduce the content of CO in the synthetic gas, and then reduce its toxicity, and improve the calorific value of gas.Methanation process is divided into not anti-sulphur and anti-sulphur technique, and its typical process flow is seen accompanying drawing 2.
In the process of synthetic gas direct production methane, there is following inferior position:
1, methanation reaction is strong exothermal reaction, and the problem that the synthetic gas of high CO content carries out methanation reaction liberated heat organic efficiency also is a difficult problem of not capturing fully up till now;
2, in the reaction by synthetic gas direct production methane, can generate a large amount of water, raw material H 2Utilization ratio just reduced, so just increased the requirement to conversion section.
Summary of the invention
At present, by containing CH 4The technique of synthetic gas direct production methyl alcohol, synthetic gas direct production methane very ripe, but the problem such as they all exist and do not take full advantage of resource, cause certain financial loss, and cost is high, processing condition are harsh.
If these two kinds of techniques are combined, utilize to contain methane synthetic gas methanol, and then utilize effective constituent H remaining in the relief gas of synthetic methanol 2, CO, CO 2Synthesizing methane.Can increase the utilization ratio of unstripped gas, and with unstripped gas in the methane that contains together reclaim, can be used as the raw material of producing clean energy CNG (compressed natural gas), LNG (natural gas liquids).
This technique yet there are no report at home and abroad at present, the ratio of methyl alcohol and two kinds of products of methane can be regulated and control according to the composition of synthetic gas and the market requirement or product price, the method of regulate and control method available adjustment hydrogen-carbon ratio makes synthetic gas be suitable for methanol or methane, has very large handiness.
Material synthesis gas derives from gasification, Sweet natural gas, coke-oven gas or oil product.Because the oil and natural gas resource is day by day in short supply, so coal based synthetic gas becomes the focus of concern, gasification mode can be traditional gasification, underground gasification, catalytic gasification, coke(oven)gas, texaco gasification etc., each component concentration scope:
Off-gas for synthesizing methanol needs only H 2/ CO just can synthesize satisfactory product methane than suitable, so just less demanding to conversion section.
If take methane as the main purpose product, because CO 2Also can carry out methanation reaction, thus less demanding to decarbonizing section, CO 2Content range can expand 1~20% to, as long as H 2/ CO 2Than suiting just can synthesize satisfactory product methane.
Adopt this processing technology routine, both can increase economic efficiency, can reduce discharging again, realize energy-saving and emission-reduction, have very strong competitive edge.
The purpose of this invention is to provide a kind of methane synthetic gas methanol that contains and join methanogenic novel process.
Being described below of technical process of the present invention:
The coarse raw materials gas that will contain first a certain amount of methane passes through the dedusting decoking, utilizes the Cobalt Phthalocyanine method to carry out the thick desulfurization of wet type, and the synthetic gas after the desulfurization enters the sulfur-resisting transformation operation through pressurization, interpolation steam, according to product methyl alcohol and methane production requirement, suitably regulates H 2With CO or (CO+CO 2) and ratio, in theory H 2/ CO is transferred to 2/1 methanol, is transferred to 3/1 and produces methane, and reality is selected suitable proportional range, H according to the ratio of two product requirements between the two 2/ CO enters decarbonization process 2/1~3/1.Usually the decarbonization methods such as the propylene carbonate of operation technique comparative maturity, low-temperature rectisol carry out decarburization, isolate sour gas CO 2And H 2S etc.Purified gas further is converted into inorganic sulfur to organosulfur through catalysis at 200~350 ℃, and catalyzer is selected Co-Mo/ γ-Al usually 2O 3Then catalyzer carries out smart desulfurization, usually selects the ZnO desulfurizing agent.
Pass through pressurization through refining purified gas, enter the methyl alcohol synthesis procedure by the catalyst for methanol synthesizing methanol, catalyst for methanol can adopt common commercial methanol catalyzer, the thick methanol product of extraction, obtain the refined methanol product through rectifying, react the remaining gas that discharges and enter the methanation operation.
Methanol purge gas enters in the cold pipe heat exchange type of the interior heat-obtaining reactor of fill depth methane synthesizing catalyst, and the methane building-up reactions is carried out in a reactor.Methane synthesizing catalyst selects that CN2007101460337 is described to be consisted of: Al 2O 3: 70~80%; NiO:12~20%; La:0.5~5%; Ce:0.1~5%; Ca:0.1~3%; Na:0.1~1%; The catalyzer of Ba:0.01~1%.Reacting system pressure is 1.0~31.4MPa, and temperature is 200~700 ℃, and air speed is 6000~12500h -1, carry out methanation reaction, the CO+CO of reactor outlet 2Concentration is controlled at below 0.5%.The synthetic rear product gas of methane is compressible to be 1.0~31.4MPa methane product.Reactor product is lowered the temperature through vapour generator, the while byproduct steam, and the methane product of preliminary cooling is further lowered the temperature through the superheated water superheater again, simultaneously the overheated hot water of by-product.Cooled gas carries out heat exchange through circulating gas preheater and cold circulation gas again, and the methanation product that then is cooled passes through final cooler again and lowers the temperature at last.Product temperature reaches about 40 ℃, through water separator, and the production sharing two portions behind the removal water, a part can be directly as the raw material of producing clean energy CNG, LNG, and another part circulates, to alleviate the temperature rise in the methanation reaction.
Description of drawings
Fig. 1 is prior art synthetic gas methanol schema;
Wherein 1---thionizer; 2---the conversion tower; 3---decarbonizing tower; 4---compressor; 5---methanol reactor; 6---rectifying tower.
Fig. 2 is prior art producing firedamp by syngas schema;
Wherein 1---the sulfur-resisting transformation tower; 2,5---acid gas removal body tower; 3---methanator; 4---the methanation in presence of sulfur reactor.
Fig. 3 is for containing methane synthetic gas methanol coproduction methane technology schema;
Wherein 1---efficient desulfurizing tower; 2---the conversion tower; 3---decarbonizing tower; 4---smart thionizer; 5---methanol reactor; 6---water condenser; 7---pure separator; 8---rectifying tower; 9---methanator; 10---vapour generator; 11---the hot water superheater; 12---circulating gas preheater; 13---final cooler; 14---water separator; 15---recycle pump; 16---water-and-oil separator.
Wherein, Fig. 3 is Figure of abstract.
Embodiment
The present invention will be further described below in conjunction with Figure of description, below only is preferred embodiment of the present invention, can not limit scope of the present invention with this.Be every variation and modification of doing according to the present patent application claim, all should still belong in the scope that patent of the present invention contains.
Embodiment 1
Produce the methyl alcohol of 60,000 ton/years of scales, contain methane 4.5% in the gasification coal mining raw gas composition, use and add a certain amount of Cobalt Phthalocyanine and contain 0.5mol/LNa 2CO 3Carry out desulfurization in the basic solution, with the H in the gas 2S takes off to 40ppm.Complete low shift conversion step through 0.8MPa is regulated hydrogen-carbon ratio, and the decarbonization system that then enters pressure and be 2.70MPa carries out decarburization, and purified gas is further through Co-Mo/ γ-Al 2O 3It is synthetic that the smart desulfurization of catalyst hydrogenation conversion and zinc oxide enters methyl alcohol, and 200 tons of daily output methyl alcohol produce 4800Nm 3/ h discharges gas.
Gasification coal mining raw gas consists of:
Discharging gas consists of:
Methyl alcohol is synthetic discharges gas, and by the methanation system, pressure is 5.0MPa, and temperature is 200~300 ℃, and air speed is 6000~10000h -1, make CO and H 2Synthesizing methane, product gas pressure was 5.0MPa after methane was synthetic.According to describing gross calorific value 〉=31.4MJ/m of CNG among the GB GB/T18047-2000 3, this product meets GB GB/T18047-2000, and this gas can CNG produces dress As its raw material, every day, production contained 93.01%CH 4CNG63000Nm 3
Embodiment 2
Produce the methyl alcohol of 200,000 ton/years of scales, be rich in methane 20.0% in the low-temperature catalysis gasification raw gas composition, use and add a certain amount of Cobalt Phthalocyanine and contain 0.5mol/LNa 2CO 3Carry out desulfurization in the basic solution, with the H in the gas 2S takes off to 40ppm.Complete low shift conversion step through 0.8MPa is regulated hydrogen-carbon ratio, and the decarbonization system that then enters pressure and be 2.70MPa carries out decarburization, and purified gas is further through Co-Mo/ γ-Al 2O 3It is synthetic that the smart desulfurization of catalyst hydrogenation conversion and zinc oxide enters methyl alcohol, and 667 tons of daily output methyl alcohol produce 16,000Nm 3/ h discharges gas.
The low-temperature catalysis gasification raw gas forms
Discharging gas consists of:
Methyl alcohol is synthetic discharges gas, and by the methanation system, pressure is 10.0MPa, and temperature is 300~350 ℃, and air speed is 7000~11000h -1, make CO and H 2Synthesizing methane, product gas pressure was 10.0MPa after methane was synthetic.According to describing among the GB GB/T19204-2003, the content of methane is higher than 75% among the LNG, and this product meets GB GB/T19204-2003, and this gas can LNG produces dress As its raw material, every day, production contained 92.54%CH 4LNG320,000Nm 3
Embodiment 3
The texaco gasification synthesis gas yield is 100,000Nm 3/ d, each component content such as following table are used and are added a certain amount of Cobalt Phthalocyanine and contain 0.5mol/LNa 2CO 3Basic solution carry out thick desulfurization, with the H in the gas 2S takes off to 40ppm.Through the complete low shift conversion step of 0.8MPa, regulate hydrogen-carbon ratio, the decarbonization system that then enters pressure and be 2.70MPa carries out decarburization, removes sour gas, and purified gas is further through Co-Mo/ γ-Al 2O 3It is synthetic that the smart desulfurization of catalyst hydrogenation conversion and zinc oxide enters methyl alcohol, consumes 15290Nm 3CO reaction methanol amount is 21.84 tons, and methanol purge gas enters the methanation system, and pressure is 20.0MPa, and temperature is 350~400 ℃, and air speed is 8500~12000h -1, make CO and H 2Synthesizing methane, product gas pressure was 20.0MPa after methane was synthetic.According to describing among the GB GB/T19204-2003, the content of methane is higher than 75% among the LNG, and this product meets GB GB/T19204-2003, and this gas can LNG produces dress As its raw material, every day, production contained 93.3%CH 4LNG5359.06Nm 3
Texaco's gas consists of:
Discharging gas consists of:
Embodiment 4
The texaco gasification synthesis gas yield is 100,000Nm 3/ d, each component content such as Texaco's gas form table, use and add a certain amount of Cobalt Phthalocyanine and contain 0.5mol/LNa 2CO 3Basic solution in carry out thick desulfurization, with the H in the gas 2S takes off to 40ppm.Through the complete low shift conversion step of 0.8MPa, regulate hydrogen-carbon ratio, the decarbonization system that then enters pressure and be 2.70MPa carries out decarburization, removes sour gas, and purified gas is further through Co-Mo/ γ-Al 2O 3It is synthetic that the smart desulfurization of catalyst hydrogenation conversion and zinc oxide enters methyl alcohol, consumes 20000Nm 3CO reaction methanol amount is 28.57 tons, and methanol purge gas enters the methanation system, and pressure is 30.0MPa, and temperature is 400~500 ℃, and air speed is 8000~12000h -1, make CO and H 2Synthesizing methane, product gas pressure was 30.0MPa after methane was synthetic.According to describing gross calorific value 〉=31.4MJ/m of CNG among the GB GB/T18047-2000 3, this product meets GB GB/T18047-2000, and this gas can CNG produces dress As its raw material, every day, generation contained methane 90%CNG3568.42Nm 3Methane.
Discharging gas consists of:
Embodiment 5
The texaco gasification synthesis gas yield is 100,000Nm 3/ d, each component content such as Texaco's gas form table, use and add a certain amount of Cobalt Phthalocyanine and contain 0.5mol/LNa 2CO 3Basic solution carry out thick desulfurization, with the H in the gas 2S takes off to 40ppm.Through the complete low shift conversion step of 0.8MPa, regulate hydrogen-carbon ratio, the decarbonization system that then enters pressure and be 2.70MPa carries out decarburization, removes sour gas, and purified gas is further through Co-Mo/ γ-Al 2O 3It is synthetic that the refining smart desulfurization of catalyst hydrogenation conversion and zinc oxide enters methyl alcohol, consumes 22000Nm 3CO reaction methanol amount is 31.42 tons, and methanol purge gas enters the methanation system, and pressure is 31.4MPa, and temperature is 500~700 ℃, and air speed is 8500~12000h -1, make CO and CO 2With H 2Synthesizing methane, product gas pressure was 31.4MPa after methane was synthetic.According to describing among the GB GB/T19204-2003, the content of methane is higher than 75% among the LNG, and this product meets GB GB/T19204-2003, and this gas can LNG produces dress As its raw material, every day, production contained 93.3%CH 4LNG2272.24Nm 3
Discharging gas consists of:

Claims (4)

1. one kind contains methane synthetic gas methanol coproduction methane technology, it is characterized in that processing step is: utilize to contain methane synthetic gas methanol, then utilize effective constituent H remaining in the relief gas of synthetic methanol 2, CO, CO 2Synthesizing methane, methane is removed the production sharing two portions behind the water, and a part is directly as the raw material of producing clean energy CNG, LNG; Another part circulates, to alleviate the temperature rise in the methanation reaction; Material synthesis gas derives from gasification, Sweet natural gas, coke-oven gas or oil product; Methane synthesizing catalyst consists of: Al 2O 3: 70~80%; NiO:12~20%; La:0.5~5%; Ce:0.1~5%; Ca:0.1~3%; Na:0.1~1%; Ba:0.01~1%; The methanation reaction system pressure is 1.0~31.4MPa, and temperature is 200~700 ℃, and air speed is 6000 ~ 12500h -1The CO+CO of methanator outlet 2Concentration is controlled at below 0.5%.
2. technique according to claim 1 is characterized in that: methanol purge gas enters in the cold pipe heat exchange type of the interior heat-obtaining reactor of filling methane synthesizing catalyst and reacts.
3. technique according to claim 1 is characterized in that: product gas pressure was processed as 1.0~31.4MPa according to market demands after methane was synthetic.
4. described any one technique is characterized in that: utilize effective constituent H remaining in the relief gas of synthetic methanol according to claim 1~3 2, CO, CO 2After the synthesizing methane, methane is lowered the temperature through vapour generator, simultaneously byproduct steam; The methane of preliminary cooling is further lowered the temperature through the superheated water superheater again, simultaneously the overheated hot water of by-product; Cooled gas carries out heat exchange through circulating gas preheater and cold circulation gas again, and the methanation product that then is cooled passes through final cooler again and lowers the temperature at last; Product is removed water finally by crossing water separator.
CN 200810226890 2008-11-19 2008-11-19 Process for producing methanol and coproducing methane by using synthesis gas containing methane CN101550052B (en)

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CN101735009B (en) * 2009-12-07 2013-08-14 中国科学院山西煤炭化学研究所 Sulfur tolerant catalyzing process for preparing low carbon alcohol from synthesis gas and co-producing natural gas
CN101735008B (en) * 2009-12-07 2013-08-14 中国科学院山西煤炭化学研究所 Technology for co-producing low-carbon alcohol and natural gas by coal synthesis gas
CN103212344B (en) * 2012-01-19 2016-12-14 杭州林达化工技术工程有限公司 The anti-surge compression circulating device of a kind of scalable synthesis loop recycle ratio and technique
CN102585951B (en) * 2012-03-07 2014-03-12 四川天一科技股份有限公司 Process for co-production of liquefied synthesis gas, pure hydrogen and methanol from coke-oven gas
CN103524299B (en) * 2012-07-06 2017-08-25 杭州林达化工技术工程有限公司 A kind of synthesizing methanol and synthesizing methane cogeneration facility
CN104232195B (en) * 2013-06-18 2017-02-08 中国石油化工股份有限公司 Method for jointly producing methanol and synthetic natural gas by utilizing coke oven 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
CN104474871A (en) * 2014-12-09 2015-04-01 呼伦贝尔东能化工有限公司 Method for preparing LNG (Liquefied Natural Gas) by recycling methanol tail gas
CN104774663B (en) * 2015-04-27 2017-08-29 中国五环工程有限公司 One-step method coal synthetic natural gas and its system
FR3050206B1 (en) * 2016-04-15 2018-05-11 Engie Hydrogenation device and method for producing methanol and device and method for cogeneration of methanol and synthetic methane

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1561320A (en) * 2000-09-28 2005-01-05 埃克森美孚化学专利公司 A methanol, olefin, and hydrocarbon synthesis process
CN101284761A (en) * 2008-06-06 2008-10-15 西北化工研究院 Process for combined preparing methylic alcohol, natural gas for automobile and synthesis ammonia form industrial end gas rich in carbon and hydrogen

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1561320A (en) * 2000-09-28 2005-01-05 埃克森美孚化学专利公司 A methanol, olefin, and hydrocarbon synthesis process
CN101284761A (en) * 2008-06-06 2008-10-15 西北化工研究院 Process for combined preparing methylic alcohol, natural gas for automobile and synthesis ammonia form industrial end gas rich in carbon and hydrogen

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