CN101293812A - Technique for joint production of methanol and natural gas with methyl hydride containing synthesis gas - Google Patents
Technique for joint production of methanol and natural gas with methyl hydride containing synthesis gas Download PDFInfo
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- CN101293812A CN101293812A CNA2008100552213A CN200810055221A CN101293812A CN 101293812 A CN101293812 A CN 101293812A CN A2008100552213 A CNA2008100552213 A CN A2008100552213A CN 200810055221 A CN200810055221 A CN 200810055221A CN 101293812 A CN101293812 A CN 101293812A
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- methanol
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- methane
- methyl alcohol
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Abstract
The invention belongs to the technology field of coal gasification comprehensive utilization and provides particularly a technique for preparing methanol and natural gas from methane-containing synthetic gas. The technique can overcome the shortcomings of a processing scheme of methanol in synthetic gas in the prior art; and the technique comprises the following steps: methane-containing synthetic gas is pressurized and then mixed with recycle gas from a methanol synthetic tower to synthesize methanol; the methanol-containing gas from the methanol synthetic tower is heat-exchanged with the gas mixture fed into the tower and cooled, and methanol is separated; a part of the methanol-separated gas as purged gas is introduced into a methane synthesizing device, and the other part is introduced into the methanol synthetic tower to continuously react to obtain natural gas after it is pressurized via circulator, recycled and then mixed with the methane-containing synthetic gas. The technique combines synthesis of methanol of high CH4 inert gas and production of natural gas by re-synthesizing methane from purged gas obtained from methanol synthesis. With the technique, two synthesis pressures and heat energy utilization can be combined together; thus making full use of the material and achieving the purposes of saved investment, energy and consumption and good benefit.
Description
Technical field
The invention belongs to gasification comprehensive utilization technique field, be specially a kind of methane synthetic gas combined production of methanol and Sweet natural gas technology of containing.
Background technology
At present, the solid-state ash discharge gasification of 4.0MPa (a) pure oxygen pressurization moving-bed for high volatile coal, contains methane 16～17% in the synthetic gas behind the raw gas purifying, account for 40% of caloric power of gas.Pure oxygen moving-bed slag tap gasification, CH in the synthetic gas after the purification
4Content 14～15% accounts for caloric power of gas about 37%.3MPa pure oxygen fluidized-bed pressing gasization, CH in the synthetic gas after the purification
4Content 8～9% accounts for caloric power of gas 25%.ICL for Indirect Coal Liquefaction system synthetic oil contains CH in the tail gas
442%, account for caloric power of gas 70%.CH in the coke-oven gas
4About content 26%, account for coke-oven gas calorific value 53%.
The existence of methane is synthetic unfavorable to methyl alcohol in the synthetic gas, reduces Synthesis conversion, increases to discharge the tolerance discharging, increases raw material, power consumption, increases investment etc.In order to overcome above technical problem, can adopt following scheme: scheme 1: methane conversion in the synthetic gas is become CO, H
2Produce methyl alcohol.Scheme 2: adopt deep cooling with methane liquefaction, CH
4From synthetic gas, separate, produce natural gas liquids, remaining CO, H
2Remove synthesizing methanol.Scheme 1 facts have proved its complex technical process through factory, and technical process is long, starting material power consumption height, and the product cost height should not be selected for use.Scheme 2: prove that in the factory that builds investment is big, power consumption is big, benefit influences greatly.
Summary of the invention
The present invention for solve exist in the prior art to the weak point of methane processing scheme in the synthetic gas and a kind of technology that contains methane synthetic gas combined production of methanol and Sweet natural gas is provided.
The present invention is realized by following technical scheme, and a kind of methane synthetic gas combined production of methanol and Sweet natural gas technology of containing contains the synthetic gas (H of methane
2, CO, CO
2, CH
4) be forced into 6-8MPa (a), then with go out methyl alcohol synthetic reactor after circulation gas mix, mixed gas is through heat exchange to 220～230 ℃, enter the methyl alcohol synthetic reactor synthesizing methanol, go out methyl alcohol synthetic reactor contain methyl alcohol gas with go into the heat exchange of tower gas mixture after, through air cooler, water cooler gas the most at last is chilled to 40 ℃, methyl alcohol is condensed into liquid and separates, separated the gas part behind the methyl alcohol and entered the methane synthesizer as off-gas, another part mixes with the synthetic gas that contains methane and is preheating to through the recirculation of circulator pressurization back and enters the methyl alcohol synthetic reactor continuation again after temperature required and react
From the off-gas behind methyl alcohol building-up reactions and the separation of methanol be preheated to 180～190 ℃ with enter first methanator after the circulation gas that comes out from first methanator mixes, enter the catalytic bed reaction at 240～250 ℃ and generate methane, obtain Sweet natural gas at last through second, third methane reactor.
Compared with prior art, technology of the present invention has been initiated high CH
4Rare gas element methyl alcohol synthesizes and methyl alcohol is synthesized H in the middle off-gas that produces
2, CO, CO
2Resynthesis methane obtains the joint process technology of Sweet natural gas, and two kinds of synthesis pressures, heat energy utilizations are combined, accomplish to make the best use of everything, reached reduced investment, energy-conservation, consume low, profitable purpose.
Particularly compare with the scheme 2 described in the background technology, the synthesic gas compressor of the present invention because of using, system for methanol synthesis are compared capacity of equipment with the comparatively ideal synthetic gas composition of same scale and are increased, and investment increases, the circulator power consumption increases, but increases very limited.By calculating as can be known:
(1) produce 1,500,000 t/a methyl alcohol equally, power consumption of the present invention (comprising synthesic gas compressor, synthesis cycle machine, synthetic natural gas circulator power consumption) only increases by 36% than scheme 2.
(2) the present invention does not consume steam, but by-product 188t/h 2.6MPa (a) saturation steam (methyl alcohol synthesizes by-product) also, but 450 ℃ of superheated vapour 125.8t/h of synthetic natural gas by-product 4.0MPa (a), and scheme 2 is except that by-product 188t/h 2.6MPa (a) saturation steam, also to consume 535 ℃ of superheated vapour 284t/h of 8.8MPa (a), 3.4MPa (a), 435 ℃ of superheated vapour 44t/h, 0.5MPa (g), 158 ℃ of saturation steam 5.6t/h.
(3) scheme 2 needs water coolant 35446t/h (water coolant does not comprise that methyl alcohol is synthetic), and the present invention only needs 1221t/h.
(4) only 900,000,000 yuans (technology, key equipment import) of low temperature separation process production LNG need of capital project 2, and the present invention includes synthetic gas compression, system for methanol synthesis because the tolerance increase causes investment to increase by 1.87 hundred million yuan, synthetic natural gas is invested 1.5 hundred million yuan, amount to about 300,000,000 yuan, therefore investment of the present invention only is 33% of scheme 2 investments.
(5) scheme 2 has the about 22500Nm of methanol purge gas
3/ h, the off-gas system that emits increases starting material, power consumption and raises the cost.The advantage of the technology of the present invention is not have the off-gas discharging, and gas pressure has about 6MPa (a), can carry at a distance.
By above-mentioned comparative analysis, the synthetic gas production methyl alcohol co-producing natural gas that contains methane can reach reduced investment, low, the profitable purpose of cost.
Description of drawings
Fig. 1 is a process flow sheet of the present invention
1-methyl alcohol synthetic reactor, 2-gas-gas heat exchanger, 3-air cooler, 4-water cooler, 5-methanol separator, 6-circulator, 7-interchanger, 8-first methanator, 9-vapor superheater, 10-primary waste heat boiler, 11-second methanator, 12-secondary waste heat boiler, 13-de-salted water preheater, 14-methane synthesis cycle machine, 15-front three alkylation reactors, the useless pot of 16-base pressure, 17-methane discharge preheater, 18-water cooler, 19-water separator among the figure
Embodiment
Below in conjunction with Fig. 1 the present invention is done further to specify, a kind of methane synthetic gas combined production of methanol and Sweet natural gas technology of containing contains the synthetic gas (H of methane
2, CO, CO
2, CH
4) be forced into about 7MPa (a) with synthesic gas compressor, then with go out methyl alcohol synthetic reactor 1 after circulation gas mix, mixed gas process gas-gas heat exchanger 2 heat exchange to 220～230 ℃, enter methyl alcohol synthetic reactor 1 synthesizing methanol, go out containing methyl alcohol gas and going into the tower gas mixture after gas-gas heat exchanger 2 heat exchange of methyl alcohol synthetic reactor 1, through air cooler 3, water cooler 4 gas the most at last is chilled to 40 ℃, methyl alcohol is condensed into liquid and separates in methanol separator 5, separated the gas part behind the methyl alcohol and entered the methane synthesizer as off-gas, another part mixes with the synthetic gas that contains methane through circulator 6 pressurization back and is preheating to and enters methyl alcohol synthetic reactor 1 continuation again after temperature required and react
From the off-gas behind methyl alcohol building-up reactions and the separation of methanol be preheated to 180～190 ℃ with enter first methanator after the circulation gas that comes out from first methanator mixes, enter the catalytic bed reaction at 240～250 ℃ and generate methane, obtain Sweet natural gas at last through second, third methane reactor.
Form according to the mole that synthetic gas is different, determine H in the virgin gas
2, CO, CO
2, CH
4Mole form, guarantee methanol quality, quality of natural gas, a complete set of technology does not have the off-gas discharging, the methyl alcohol synthesis cycle than 3.5～4.5 and circulation gas in the mole composition 25～35% of rare gas element.
Form according to the methanol purge gas mole, determine that according to the characteristic of methanation catalyst the synthetic natural gas circulator is the position of the methane synthesis cycle machine 14 illustrated among Fig. 1, determine that methane synthetic cyclic gas and virgin gas are than, reactor progression and CO, H at different levels
2, CO
2Transformation efficiency.
As schematically shown in Figure 1, methanator has used three, be respectively first methanator 8, second methanator 11, front three alkylation reactors 15, from methyl alcohol synthetic off-gas successively through first methanator, 8, the second methanators, 11, the front three alkylation reactors, 15 synthesizing methanes.The methane synthesis cycle machine 14 and first methanator 8 form circulation loop, and are positioned at after the primary waste heat boiler 10.
From 40 ℃ of methyl alcohol synthetic off-gas, 6.5MPa (a) mixes laggard first methanator, 8 chucks through being preheated to 180～190 ℃ with 180～190 ℃, the circulation gas of 6.5MPa (a), and 240～250 ℃ enter catalytic bed, H
2, CO, CO
2Following reaction takes place:
The gas temperature that goes out first methanator 8 enters vapor superheater 9 for 550 ℃, and 4.0MPa (a) saturation steam is superheated to 450 ℃, goes into primary waste heat boiler 10 then and produces 4.0MPa (a) saturation steam.Go out primary waste heat boiler 10 contain methane gas one and the heat exchange of circulator exit gas after, gas temperature is reduced to 180 ℃ and is advanced 14 superchargings of methane synthesis cycle machine, and with mix from methyl alcohol synthetic off-gas, advance first methane synthesis reactor, 8 chucks again, temperature rises to 240～250 ℃.
Another strand that goes out primary waste heat boiler 10 contains methane gas behind feedwater preheater, reduce to 180 ℃ of chucks of going into second methane reactor 11, about 240～250 ℃ are advanced beds, go out about 360 ℃ of second methanator, 11 gas temperatures and enter secondary waste heat boiler 12 production 4.0MPa (a) saturation steams, then with the methanol purge gas heat exchange after about 230 ℃ advance leucoaurin and be combined to reactor 15, the synthetic natural gas of coming out through with methanol purge gas preheater 17 and heat exchange after produce 0.5MPa (a) saturation steams through feedwater preheater or the useless pot 16 of low pressure again.
Second and third methane synthesis reactor mainly contains following chemical reaction.
Nearly 100% through the synthetic CO transformation efficiency of three reactor, H
2Transformation efficiency reaches 99%, CO
2Transformation efficiency reaches 91%.The Sweet natural gas low heat value reaches 30982kJ/Nm
3(7400kcal/Nm
3).
Claims (3)
1, a kind of methane synthetic gas combined production of methanol and Sweet natural gas technology of containing, it is characterized in that: the synthetic gas that contains methane is forced into 6-8MPa, then with go out methyl alcohol synthetic reactor after circulation gas mix, mixed gas is through heat exchange to 220～230 ℃, enter the methyl alcohol synthetic reactor synthesizing methanol, go out methyl alcohol synthetic reactor contain methyl alcohol gas with go into the heat exchange of tower gas mixture after, through air cooler, water cooler gas the most at last is chilled to 40 ℃, methyl alcohol is condensed into liquid and separates, separated the gas part behind the methyl alcohol and entered the methane synthesizer as off-gas, another part mixes with the synthetic gas that contains methane and is preheating to through the recirculation of circulator pressurization back and enters the methyl alcohol synthetic reactor continuation again after temperature required and react
Be preheated to from the off-gas behind methyl alcohol building-up reactions and the separation of methanol and enter methanator after 180～190 ℃ of circulation gas with 170 ℃ of the water vapor temperature of saturation of coming out from methanator mix, enter the catalytic bed reaction at 240～250 ℃ and generate methane.
2, methane synthetic gas combined production of methanol and the Sweet natural gas technology of containing according to claim 1, it is characterized in that: methanator has used three, be respectively first methanator, second methanator, the front three alkylation reactors, from methyl alcohol synthetic off-gas successively through a methanator, second methanator, the front three alkylation reactors has finally been synthesized Sweet natural gas, the heat energy classification utilization that building-up reactions is emitted, and its effective rate of utilization reaches 98%.
3, methane synthetic gas combined production of methanol and the Sweet natural gas technology of containing according to claim 1 is characterized in that: the methyl alcohol synthesis cycle is than 3.5～4.5, the mole 25～35% of rare gas element in the circulation gas.
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|---|---|---|---|
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| CN101293812A true CN101293812A (en) | 2008-10-29 |
| CN101293812B CN101293812B (en) | 2011-03-30 |
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| CN101892104A (en) * | 2010-06-30 | 2010-11-24 | 西南化工研究设计院 | Method for preparing liquefied natural gas by utilizing relief gas of methanol |
| CN102585951A (en) * | 2012-03-07 | 2012-07-18 | 四川天一科技股份有限公司 | Novel process for co-production of liquefied synthesis gas, pure hydrogen and methanol from coke-oven gas |
| CN102977958A (en) * | 2012-12-03 | 2013-03-20 | 华东理工大学 | Preparation method for peak regulation of coal-based natural gas through methyl alcohol synthesis |
| CN103013598A (en) * | 2013-01-04 | 2013-04-03 | 大唐国际化工技术研究院有限公司 | Method and device for producing synthesized 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 |
| 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 |
| CN103288593A (en) * | 2013-06-04 | 2013-09-11 | 江苏乐科热力科技有限公司 | Device and method for producing sodium methoxide through recompression of mechanical steam |
| CN103553861A (en) * | 2013-10-29 | 2014-02-05 | 西南化工研究设计院有限公司 | System and technology for synthesis of methanol and co-production of methane by using synthesis gas |
| CN104164263A (en) * | 2014-08-19 | 2014-11-26 | 赛鼎工程有限公司 | Method for preparing liquefied natural gas (LNG) through sulphur-tolerant methanation of coke-oven gas |
| CN104788285A (en) * | 2015-03-26 | 2015-07-22 | 七台河宝泰隆煤化工股份有限公司 | Methanol synthesis system |
| CN104788286A (en) * | 2015-03-26 | 2015-07-22 | 七台河宝泰隆煤化工股份有限公司 | Process method for synthesizing methanol |
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| CN105175223A (en) * | 2015-08-31 | 2015-12-23 | 四川天一科技股份有限公司 | Methanol pre-rectifying tower heating system utilizing methanol synthesis reaction gas |
| WO2017178769A1 (en) * | 2016-04-15 | 2017-10-19 | Engie | Device and method for the cogeneration of methanol and synthesis methane |
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| CN104910985A (en) * | 2009-01-06 | 2015-09-16 | 通用电气公司 | Heat integration in coal gasification and methanation reaction process |
| 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 |
| 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 |
| CN101892104B (en) * | 2010-06-30 | 2012-10-17 | 西南化工研究设计院 | Method for preparing liquefied natural gas by utilizing relief gas of methanol |
| CN101892104A (en) * | 2010-06-30 | 2010-11-24 | 西南化工研究设计院 | Method for preparing liquefied natural gas by utilizing relief gas of methanol |
| CN102585951A (en) * | 2012-03-07 | 2012-07-18 | 四川天一科技股份有限公司 | Novel process for co-production of liquefied synthesis gas, pure hydrogen and methanol from coke-oven gas |
| CN102977958B (en) * | 2012-12-03 | 2014-04-09 | 华东理工大学 | Preparation method for peak regulation of coal-based natural gas through methyl alcohol synthesis |
| CN102977958A (en) * | 2012-12-03 | 2013-03-20 | 华东理工大学 | Preparation method for peak regulation of coal-based natural gas through methyl alcohol synthesis |
| CN103013598B (en) * | 2013-01-04 | 2014-07-16 | 大唐国际化工技术研究院有限公司 | Method and device for producing synthesized natural gas |
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| CN103553861A (en) * | 2013-10-29 | 2014-02-05 | 西南化工研究设计院有限公司 | System and technology for synthesis of methanol and co-production of methane by using synthesis gas |
| CN104164263A (en) * | 2014-08-19 | 2014-11-26 | 赛鼎工程有限公司 | Method for preparing liquefied natural gas (LNG) through sulphur-tolerant methanation of coke-oven gas |
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| WO2017178769A1 (en) * | 2016-04-15 | 2017-10-19 | Engie | Device and method for the cogeneration of methanol and synthesis methane |
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