CN101775319B - Method for producing synthetic natural gas SNG from coal and processing installation thereof - Google Patents
Method for producing synthetic natural gas SNG from coal and processing installation thereof Download PDFInfo
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- CN101775319B CN101775319B CN 201010128165 CN201010128165A CN101775319B CN 101775319 B CN101775319 B CN 101775319B CN 201010128165 CN201010128165 CN 201010128165 CN 201010128165 A CN201010128165 A CN 201010128165A CN 101775319 B CN101775319 B CN 101775319B
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- natural gas
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Abstract
The invention relates to a method for producing synthetic natural gas SNG from coal and a processing installation thereof. The method includes the following steps that: coal is gasified and goes through sulfur-tolerant shift, the proportion between CO, CO2 and H2 in the gas is regulated, organic sulfur is converted into inorganic sulfur, the gas is then purified to remove the sulfur and part of the CO2 in the gas, and after the components of the gas meet the following formula: the ratio of(H2-3CO)to CO2 is about 4, the gas is sent into a methanation reactor, so that the H2, the CO and the CO2 are methanated to synthesize the SNG (synthetic natural gas). The installation consists of a coal gasification process, a sulfur-tolerant shift process, a purification process and a methanation process, in particular, the methanation reactor in the methanation process adopts a water-cooled tube array structure, which can quickly take away reaction heat, so that the overheat of catalyst can be prevented, the high-pressure steam in the removed heat by-product serves as power for equipment such as a compressor and a pump, consequently, the reaction heat is rationally utilized, and the produced synthetic natural gas can be directly used as fuel for urban residents or further processed into SNG and LNG. Compared with the prior reactor methanation process, the method has the advantages of short process, investment saving and high heat energy utilization rate.
Description
Technical field
A kind ofly produce the method for SNG (synthetic natural gas) by coal, namely by with gasification through conversion and purification, then by methanation reaction, make H
2, CO and CO
2Synthetic natural gas SNG.Specially refer to a cover and realize the chemical technique device of aforesaid method.The field that belongs to chemical technique technology and energy development.
Background technology
China is oil, vapour shortage of resources, the coal resource more rich country that compares.Moderately the Development of Coal chemical industry both can obtain the transport fuel oil product (synthetic oil) of petroleum replacing, also can obtain basic oil (ethene, the propylene) industrial chemicals of petroleum replacing, can also obtain the synthetic Sweet natural gas of instead of natural gas.This is significant to the Sustainable development that guarantees Chinese energy safety and economy.
Along with the enforcement of the policies such as the domestic strategy of sustainable development and reinforcement environmental protection, domestic demand to Sweet natural gas will grow with each passing day.Estimate that China's natural gas demand in 2010 will reach 1000～1,100 hundred million m
3, the same period, gas production can only reach 900～95,000,000,000 m
3, expect the year two thousand twenty China's natural gas demand and will reach 2,000 hundred million m
3, the gas production of the same period can only reach 1400-1600 hundred million m
3, so the imbalance between supply and demand solution of problem of a few years from now on Sweet natural gas must be by all kinds of means, multimode supply, can satisfy growing market demand, it is exactly a kind of mode that obtains Sweet natural gas that coal is produced synthetic SNG.The large moulded coal preparing natural gas of the U.S.'s several covers under construction project has also been ratified the Inner Mongol 4,000,000,000 m in China National Development and Reform Committee recently
3With 1,600,000,000 m
3Two cover coal preparing natural gas projects are carried out previous work.The gasification process of selecting in these projects at present is most to be the lurgi pressure gasification technology, working pressure 3.0MPa, and the raw gas component is about:
Component CO
2CO H
2CH
4N
2∑
VOL％ 26.4 23.48 39.48 8.48 1.96 100
Produce in the technology of Sweet natural gas at coal, because synthetic CH
4Reaction be a strong exothermal reaction, reaction heat is untimely to be removed, and usually can cause catalyst overheating and inactivation.In order to remove fast reaction heat, used technique is the multi-stage fixed-bed adiabatic reactor of design at present, service temperature 250-670 ℃, in the intersegmental method that interchanger is set, removes heat in the reactor, byproduct steam.The shortcomings such as long flow path, investment is high, heat energy recovery rate is low are arranged.The present invention utilizes the residential district of contemporary frontier science and technology material, and the inside heat exchange type that new technology is made is water cooled reactor, and service temperature is in 250-450 ℃ of scope, and it is short to have flow process, the characteristics that heat recovery rate is high.
In recent years, have been introduced for the domestic more existing patents of the method for coal to SNG (synthetic natural gas), the patent No. is: CN101338231A, introduced take coal as raw material in the patent of its title " coal preparing natural gas or hydrogen ", the gasification process of coal hydrogenation in gas processed, produce class natural gas, it consists of: CH
4Content: 50～100%, hydrogen content: 0～50%, also have a small amount of C
mH
n, CO
2, H
2, N
2With CO etc.Calorific value of gas during its calorific value approaches, in order to be different from the Sweet natural gas of methane rich high heating value, name and be class natural gas, during with class natural gas hydrogen manufacturing, be through purifying, after the steam reforming again with pressure-variable adsorption or membrane sepn making pure hydrogen, this patent can only purify for class natural gas or with class natural gas outward, and pressure-variable adsorption or membrane sepn just can obtain Sweet natural gas, and there is complex process in it, long flow path is invested high problem.
The patent No. is: CN101434879A, in the patent of its title " method take coke(oven)gas and coal as raw material methyl methanol syngas processed and compressed natural gas ", described compressed natural gas be directly from coke(oven)gas (methane content 24～26% (vol%) in the coke(oven)gas) separate by pressure-variable adsorption and obtain, be not the coal preparing natural gas in essence.The difference of the present invention and above two patents is that this patent is the method for directly producing specially SNG (synthetic natural gas) with the coal raw material.
Summary of the invention
One of aim of the present invention is that gasification is regulated H by conversion
2, CO and CO
2Ratio, when gas sweetening, remove wherein sulphur and part CO
2, make H in the gas
2, CO and CO
2Stoichiometry reach
This gas is synthetic SNG (synthetic natural gas) through methanator the time, and liberated heat is produced mesohigh steam in the reaction, and as the power of compressor, heat energy recovery rate is high and efficiently utilized.
The technical scheme that the present invention solves technological problems is: a kind of coal is produced the method for synthetic natural gas SNG, and its technological process is as follows:
1, coal, steam and pure oxygen are gasified in pressurized-gasification furnace, generate raw gas, vapor pressure is selected 3.0MPa or 4.0MPa etc. usually.
2, raw gas is through sulfur-resisting transformation the time, through transformationreation CO+H
2O → H
2+ CO
2, H in the adjustments of gas
2, CO and CO
2Ratio, simultaneously most organosulfurs in the gas are converted into inorganic sulfur.
3, the gas after the conversion (can be selected low-temperature rectisol or NHD method+smart desulfurization) when the gas sweetening operation, removes sulphur wherein, reaches total sulfur≤0.1ppm, removes part CO wherein
2, satisfy stoichiometric ratio
Requirement.
4, purified gas is through methanator the time, under the effect of Ni series catalysts, and H
2, CO and CO
2Carry out methanation reaction, generate synthetic natural gas SNG, the reaction heat of meanwhile emitting heating tube side water is produced high pressure steam, as the power of compressor or pump.
Gasification and methanation are all finished with under the pressure rating in present method, and the methanation operation do not establish circulation loop, once by reaching technic index.
In present method: gasification, sulfur-resisting transformation, gas purification technique are mature technology, just according to advancing the front index of methanation reaction;
Requirement, process operation parameter such as interconversion rate, degree of purification have difference.
Methanator is water cooled reactor (vertical or horizontal) in present method, and the carrier of Ni catalyzer is Al
2O
3, catalyzer is contained in shell side in the reactor, 250～450 ℃ of service temperatures.
Two of aim of the present invention is to select to realize a cover process unit of aforesaid method.
The present invention is by the method for following cover process unit realization coal synthetic natural gas SNG processed, comprising gasification operation, sulfur-resisting transformation operation, gasification cleaning section and methanation operation.It is characterized in that: the gasification operation is pressurized gasification, and methanation process operations pressure is a little less than vapor pressure.Whole device flow process is short, reduced investment, and energy-conservation.
One of advantage of the present invention, it is characterized in that: methanator is water-cooled structure, working pressure and gas pressure approach, 250～450 ℃ of temperature are equipped with water pump at the water pipe that advances methanator, by accelerating the water flow mode, strengthen heat-transfer intensity, the temperature of reaction of control beds maintains in the scope it, prevents catalyst overheating.
Two of advantage of the present invention is characterized in that: be provided with sulfur-resisting transformation and gas cleaning section in the process unit, guarantee total sulfur≤0.1ppm in the gas of methanation operation, stoichiometric ratio:
These two measures can make the catalyzer long service life, and synthetic productive rate is high.
Three of advantage of the present invention is characterized in that: heat energy recovery rate high (〉=90%), can produce the mesohigh steam of GOOD TASTE, and be used for rotating machinery (compressor, pump etc.) as power.
Description of drawings
Fig. 1 is the technique block flow diagram of one of the specific embodiment of the present invention.
Fig. 2 is two the technique block flow diagram of the specific embodiment of the present invention.
Embodiment:
Can introduce in more detail the present invention by drawings and Examples, but be not restriction to protection scope of the present invention.
Embodiment 1
As shown in Figure 1, coal, steam and O
2Make raw gas in pressurized-gasification furnace (usually pressure, 3.0Mpa, 4.0Mpa), raw gas can be regulated H when sulfur-resisting transformation
2, CO and CO
2Ratio is converted into inorganic sulfur with most organosulfurs in the gas simultaneously, and conversion gas removes organic and inorganic sulfur wherein when the gas sweetening operation, make total sulfur≤0.1ppm in the gas, also removes part CO
2, make to reach stoichiometric ratio in the purified gas:
Purified gas is in the methanation operation, because the effect of Ni series catalysts finishes methanation reaction, namely generates SNG (synthetic natural gas), goes out CO in the gas of methanation
2And H
2Content all≤0.1% (VOL), CO content does not measure.Reaction heat is taken away by strong flowing water and is produced mesohigh steam.
Embodiment 2
As shown in Figure 2, coal, steam and O
2In pressurized-gasification furnace (usually pressure, 3.0Mpa, 4.0Mpa), make raw gas, raw gas and external rich H
2Gas (can be coke-oven gas or other H
2The gas that content is high) mix, mixed gas will satisfy stoichiometric ratio:
Requirement.Gas mixture when purifying with gas in H
2S and organosulfur are deviate from, and the gas that goes out to purify will reach the requirement of its total sulfur content≤0.1PP.Purified gas is in the methanation operation, because the effect of Ni series catalysts makes CO
2, CO and H
2Carry out methanation reaction and synthetic CNG (synthetic natural gas), go out CO in the CNG gas of methanation operation
2And H
2Content respectively all≤0.1% (VOL), CO content does not measure.Reaction heat is taken away by strong flowing water and is produced mesohigh steam.
SNG in the present embodiment can send into gas distributing system as combustion gas in addition, can directly make if necessary high-quality CNG (natural gas used for automobile) and LNG (natural gas liquids).
Claims (5)
1. produce the method for synthetic natural gas SNG by coal for one kind, it is characterized in that: first with gasification, again by sulfur-resisting transformation, H in the adjustments of gas
2, CO and CO
2Ratio, then conversion gas is carried out gas sweetening, remove part CO
2Behind whole inorganic sulfur and organosulfur, under the effect of catalyzer, in methanator, carry out methanation reaction, reacted gas is synthetic natural gas SNG; Wherein:
Described methanator is water-cooled structure, and water is at tube side, and catalyzer is contained in shell side, and reaction gas is through shell side, and synthesis pressure is decided by the pressure of selected gasification, synthesis temperature 250-450 ℃;
Described methanator will be produced the mesohigh steam of 4.0-10.0Mpa, is added by drum on the water pipe of reactor to be provided with water pump, and it is compulsory making mobile in water pipe of water.
2. as claimed in claim 1ly produce the method for synthetic natural gas SNG by coal, it is characterized in that: it is the method that adopts low-temperature rectisol or NHD method+smart desulfurization that conversion gas carries out gas sweetening.
3. as claimed in claim 1ly produce the method for synthetic natural gas SNG by coal, it is characterized in that: described catalyzer is the NI series catalysts, and air speed is 3000Nm
3/ m
3H.
4. as claimed in claim 1ly produce the method for synthetic natural gas SNG by coal, it is characterized in that: total sulfur≤0.1ppm in the purified gas, stoichiometric ratio:
5. describedly produce the method for synthetic natural gas SNG by coal such as claim 1,2,3 or 4, it is characterized in that: purified gas once by in the methane reactor afterreaction gas by volume per-cent be H
2≤ 0.1%, CO
2≤ 0.1%, CO does not measure.
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| CN 201010128165 CN101775319B (en) | 2010-02-11 | 2010-02-11 | Method for producing synthetic natural gas SNG from coal and processing installation thereof |
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| CN101775319B true CN101775319B (en) | 2013-04-24 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086146B (en) * | 2010-12-15 | 2012-10-17 | 西南化工研究设计院 | Process for preparing glycol by oxalate hydrogenation in heat insulation reaction system |
| CN103242920B (en) * | 2012-02-09 | 2015-02-04 | 中国科学院大连化学物理研究所 | Technology for preparing natural gas from coal-gasification synthetic gas |
| CN102827657A (en) * | 2012-08-27 | 2012-12-19 | 东华工程科技股份有限公司 | Isothermal methanation process method for coal to substitute natural gas |
| CN103740428B (en) * | 2012-10-17 | 2016-07-13 | 中国石油化工股份有限公司 | Synthesis gas methanation substitutes the method for natural gas |
| CN104031703B (en) * | 2013-03-06 | 2016-05-11 | 中国石油天然气股份有限公司 | A kind of coal is prepared the method and apparatus of natural gas synthesis gas |
| CN104651004B (en) * | 2015-01-05 | 2017-04-12 | 华南理工大学 | Energy-saving coal-based natural gas process |
| CN104649859A (en) * | 2015-01-27 | 2015-05-27 | 新奥气化采煤有限公司 | Methane synthetic method and methane synthetic system |
| 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245262A (en) * | 2008-01-23 | 2008-08-20 | 清华大学 | Gas-steam combined cycle system and technique based on coal gasification and methanation |
| CN101597527A (en) * | 2009-07-07 | 2009-12-09 | 山西科灵环境工程设计技术有限公司 | A kind of method of utilizing coke(oven)gas to produce synthetic natural gas |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245262A (en) * | 2008-01-23 | 2008-08-20 | 清华大学 | Gas-steam combined cycle system and technique based on coal gasification and methanation |
| CN101597527A (en) * | 2009-07-07 | 2009-12-09 | 山西科灵环境工程设计技术有限公司 | A kind of method of utilizing coke(oven)gas to produce synthetic natural gas |
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