CN100596293C - Stage associating process for producing methanol and ammonia using coal and coke oven gas as material - Google Patents
Stage associating process for producing methanol and ammonia using coal and coke oven gas as material Download PDFInfo
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- CN100596293C CN100596293C CN200510056689A CN200510056689A CN100596293C CN 100596293 C CN100596293 C CN 100596293C CN 200510056689 A CN200510056689 A CN 200510056689A CN 200510056689 A CN200510056689 A CN 200510056689A CN 100596293 C CN100596293 C CN 100596293C
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- gas
- methanol
- ammonia
- synthetic
- methyl alcohol
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Abstract
The present invention is stepped process and apparatus of synthesizing methanol and ammonia with coal, petroleum, natural gas, coke oven gas and other material. Partial purified material gas is firstlow pressure synthesized to produce methanol, the rest gas is compressed to high pressure for synthesizing methanol further, and the high pressure methanol is pressure reduced, methanated to eliminateCO, CO2 and other harmful gas and synthesized to produce ammonia. The present invention has the advantages one less investment, low power consumption, high yield, etc.
Description
Technical field
The invention belongs to chemical production device and equipment, the joint production of methyl alcohol and ammonia especially is specially adapted to the occasion of hydrogeneous, nitrogen, carbon monoxide, CO 2 raw material gas synthesizing methanol and ammonia.
Background technology
Before the present invention makes, by hydrogeneous, nitrogen, carbon monoxide, the device of CO 2 raw material gas combination producing methyl alcohol and ammonia has following several: the one, and the methyl alcohol that China set up since 1967 and the joint production of ammonia (are called for short methanol unit, saw Feng Yuanqi chief editor " connection alcohol is produced " Chemical Industry Press 1989) be to seal in methanol synthesizer from five sections outlets of feed gas compressor (about pressure 11MPa), connect with copper liquid tower again the micro CO carbon in the gas behind the alcohol is removed, it is compressed to 32MPa left and right sides deammoniation synthesizer that gas advanced six sections imports of compressor after copper was washed then, this methanol unit forms for original ammonia production equipment transformation, that is presses connection alcohol in claiming.The 2nd, An Chun company in Hunan will go out to join copper behind the alcohol and washes and use the methanation method instead and replace afterwards, pressed the methyl alcohol methanation in promptly, and this method is mainly used in the purification of syngas for synthetic ammonia.The 3rd, equal the equipressure carbinol and the high pressure methyl alcohol methanations such as the joint production (Chinese invention patent ZL93105920.8) of ammonia or title of invention in 1992 by Lou Shoulin, this invention successfully puts into operation in factories such as Jiangshan of Zhejiang Province, rich happiness Linyis, Shanxi.Though but above-mentioned various alcohol method respectively has its technological and economical advantages, but all be to produce synthetic ammonia, it is secondary producing methyl alcohol, though the actual methanol output of the factory that has is near the output of synthetic ammonia, but methanol output greater than the situation of ammonia under methyl alcohol synthesize and under mesohigh, then invest greatly, and increased power consumption of compressor.
The present invention be under methanol output increase situation, provide a technology rationally, the method and the production unit of saving energy, methanol with joint production of synthetic ammonia that cost is low.
The content of invention
The present invention a kind ofly makes the method for raw material classification synthesizing methanol and ammonia with coal, oil, Sweet natural gas or coke(oven)gas, mainly is the H that contains that makes
2, CO, CO
2, N
2, CH
4That forms removes unstripped gas to the synthetic nuisance of methyl alcohol through purification, produces methyl alcohol through the synthetic unstripped gas that consumes part of low pressure methanol earlier, and remaining low pressure methanol synthesis purge gas is compressed to high pressure to carry out methyl alcohol synthetic after producing methyl alcohol; The high pressure methanol purge gas is removed CO, CO through methods such as methanations
2Synthetic to deammoniation behind the ammonia synthesis obnoxious flavour.
In the method for classification synthesizing methanol and ammonia, the pressure of low pressure methanol synthesis is 4～9MPa.
In the method for classification synthesizing methanol and ammonia, the pressure of high pressure synthesizing methanol is 10～32MPa.
In the method for classification synthesizing methanol and ammonia, methyl alcohol that low pressure methanol synthesis produces and high pressure methanol output ratio are greater than 2.
In the method for classification synthesizing methanol and ammonia, advance CO＞10% in the unstripped gas of low pressure methanol.
Description of drawings
Further specify the present invention below in conjunction with accompanying drawing.In the accompanying drawing:
Fig. 1 is with coke(oven)gas or Sweet natural gas or oily method of carrying out classification synthesizing methanol and ammonia as raw material.
Fig. 2 is to be the method that raw material carries out classification synthesizing methanol and ammonia with the coal.
Fig. 3 is to be that the little ammonia plant retrofit of raw material normal pressure system gas is the method for classification synthesizing methanol and ammonia with the coal.
Better embodiment
Fig. 1 is to be that raw material is implemented FB(flow block) of the present invention with coke(oven)gas or Sweet natural gas or oil, and coke(oven)gas contains about 28% the CH of having an appointment
4And C
mH
n, 4～8% N
2, all the other are H
2, CO, CO
2Deng, pressure is 4～9MPa, about 900 ℃ of temperature are carried out catalysis with steam and oxygen or oxygen-rich air in converter or on-catalytic transforms, with CH
4Deng being converted into H
2, unstripped gas such as CO.For the catalyzed conversion coke(oven)gas, need first desulfurization etc., on-catalytic is transformed then can after conversion, go purification such as smart desulfurization again and remove the catalyst for methanol nuisance.Making unstripped gas that the raw material pure oxygen gasification makes with oil also needs purification such as smart desulfurization to remove the catalyst for methanol nuisance.When being raw material with Sweet natural gas, the smart desulfurization earlier of Sweet natural gas compression back, carry out steam reforming, conversion of natural gas can adopt one-stage converter or one section conversion and two sections from thermal transition, the also available oxygen enrichment of available pure oxygen, enter the low pressure methanol synthesis loop then and consume most of unstripped gas synthesizing methanol, remaining methanol purge gas is compressed to 10～32MPa, earlier after synthetic CO, the CO of consuming of high pressure methyl alcohol
2And H
2Generate methyl alcohol, make CO+CO
2＜0.6%, enter high-pressure methanation again and obtain CO+CO
2The unstripped gas of＜20ppm also can be added pure nitrogen gas in case of necessity and make it to become and contain H
2And N
2Remove synthetic ammonia than the refinery gas that is about 3.In this law, can adopt pure oxygen to transform or oxygen enrichment transforms according to the needs of alcohol/ammonia ratio, when adopting oxygen enrichment to transform then in the reforming gas nitrogen increase, be used to reduce alcohol/ammonia ratio, improve hydrazine yield.
Fig. 2 is to be that raw material adopts FB(flow block) of the present invention with the coal, coal is a raw material preparing synthetic gas in coal gasifier earlier, coal gasifier can adopt texaco coal-water slurry gasification, or pressurized gasification such as Shell dry method powder coal gasification furnace, or vapourizing furnace such as atmospheric fixed bed vapourizing furnace, vaporized chemical also needs with pure oxygen or oxygen-rich air or air system gas according to different vapourizing furnaces and system methyl alcohol and ammonia synthesis output except that water vapor, and the synthetic gas that makes needs through purification, CO conversion and take off CO
2, smart desulfurization etc. removes the synthetic nuisance of methyl alcohol, to normal pressure system gas also need compressedly, consume the partial raw gas synthesizing methanol through the low pressure methanol synthesis loop then, remaining methanol purge gas is compressed to 10～32MPa, earlier after synthetic CO, the CO of consuming of high pressure methyl alcohol
2And H
2Generate methyl alcohol, make CO+CO
2＜0.6%, enter high-pressure methanation again and obtain CO+CO
2＜20ppm contains H
2And N
2Remove synthetic ammonia than the refinery gas that is about 3.In this law, can adopt pure oxygen to transform or oxygen enrichment transforms according to the needs of alcohol/ammonia ratio, when adopting oxygen enrichment to transform then in the reforming gas nitrogen oxygen increase, be used to reduce alcohol/ammonia ratio, improve hydrazine yield.
Fig. 3 is the schematic block follow diagram that adopts classification synthesizing methanol of the present invention and ammonia with the old factory of the middle-size and small-size synthetic ammonia of atmospheric fixed bed coal gasifier.Old device adopts water vapour, the atmospheric fixed bed gasification of air to make raw gas, transform this law as and adopt that to increase appliance arrangement newly be the normal pressure gas stove, raw gas converges through the raw gas purifying desulfurization with old gas furnace coal gas, tell a part of gas then by old multistage compressor compresses (I), another part through newly-increased multistage low pressure compressor low pressure (LP) cylinder compression (I) to about the 0.8MPa, converge old compressor gas together through the CO conversion, take off CO
2Tell a part of gas again and compress (II) to 5～6MPa through newly-increased low pressure compressor, converge again with through the gas of old compressor compresses (II) behind 5～6MPa, generate methyl alcohol through the synthetic partial raw gas that consumes of low pressure methanol again, remaining methanol purge gas compressed (III) is to 10～32MPa, earlier after synthetic CO, the CO of consuming of high pressure methyl alcohol
2And H
2Generate methyl alcohol, make CO+CO
2＜0.6%, enter high-pressure methanation again and obtain CO+CO
2＜20ppm contains H
2And N
2Remove synthetic ammonia than the refinery gas that is about 3.In this law, can adopt pure oxygen to transform or oxygen enrichment transforms according to the needs of alcohol/ammonia ratio, when adopting oxygen enrichment to transform then in the reforming gas nitrogen oxygen increase, be used to reduce alcohol/ammonia ratio, improve hydrazine yield.
The most of unstripped gas of the present invention is synthesizing methanol under low pressure, reduce the compressed synthesis gas power consumption significantly, significantly improve Catalyst Production intensity, the synthetic low-voltage equipment that adopts of methyl alcohol reduces investment, high pressure methyl alcohol is synthetic only to be produced small amount of methanol and is used for gas sweetening as the associating methanation, presses the methyl alcohol methanation to save more than 1/3 to producing same output methanol device output investment ratio in existing.
Embodiment
The above-mentioned Fig. 3 flow process of little synthetic ammonia factory the present invention that former annual output is 30,000 tons, increase gas furnace and low pressure compressor, adopt atmospheric air water vapor system to be so incensed that raw gas (1), through raw gas purifying, thick desulfurization, respectively through the old and new's compressor compresses (I) to 0.8MPa, through the CO conversion with take off CO
2Get unstripped gas (2) compressed (II) and go low pressure methanol synthetic, adopt JW low pressure homogeneous temperature type methyl alcohol synthetic reactor, 2 meters dresses of synthetic tower diameter 25m to 5.5MPa
3NC307 low pressure methanol catalyzer synthetic 90,000 tons/year of methyl alcohol, low pressure methanol off-gas (3) recompression (III) to 30MPa go high pressure methyl alcohol synthetic 10,000 tons of/year methyl alcohol, again through methanation get refinery gas (4) deammoniation synthesize 30,000 tons of/year ammonia.Data calculated is seen attached list:
After having read detailed description of the present invention, those of ordinary skill in the art can easily carry out various changes and modifications to the present invention under situation without departing from the spirit and scope of the present invention.Present invention resides in the various changes and modifications in the claims scope, the off-gas after also aforementioned low pressure methanol can being synthesized in addition adopts the low change of CO decarburization methanation to reach CO+CO
2Deammoniation synthetic method behind the＜20ppm.
Claims (3)
1. make the method for raw material classification synthesizing methanol and ammonia with coal, coke(oven)gas for one kind, it is characterized in that the H that contains that makes
2, CO, CO
2, N
2, CH
4That forms removes the unstripped gas that methyl alcohol is synthesized nuisance through purification, produce methyl alcohol through the synthetic unstripped gas that consumes part of low pressure methanol earlier, remaining low pressure methanol synthesis purge gas is compressed to high pressure to carry out methyl alcohol synthetic after producing methyl alcohol, and the high pressure methanol purge gas is removed ammonia synthesis harmful gas CO, CO through the methanation method
2Back deammoniation is synthetic; Wherein the pressure of low pressure methanol synthesis is 4～9MPa; The pressure of high pressure synthesizing methanol is 10～32MPa.
2. according to the classification synthesizing methanol of claim 1 and the method for ammonia, it is characterized in that low pressure methanol synthetic the methyl alcohol that produces and high pressure methanol output ratio greater than 2.
3. according to the classification synthesizing methanol of claim 1 and the method for ammonia, it is characterized in that into CO＞10% in the low pressure methanol synthetic raw gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510056689A CN100596293C (en) | 2005-04-14 | 2005-04-14 | Stage associating process for producing methanol and ammonia using coal and coke oven gas as material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510056689A CN100596293C (en) | 2005-04-14 | 2005-04-14 | Stage associating process for producing methanol and ammonia using coal and coke oven gas as material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1847208A CN1847208A (en) | 2006-10-18 |
| CN100596293C true CN100596293C (en) | 2010-03-31 |
Family
ID=37076983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200510056689A Expired - Fee Related CN100596293C (en) | 2005-04-14 | 2005-04-14 | Stage associating process for producing methanol and ammonia using coal and coke oven gas as material |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214922B (en) * | 2007-12-26 | 2010-06-02 | 罗庆洪 | Combined purifying technique for ammonia preparation from natural gas, ammonia preparation from coal and methanol preparation from coal |
| CN102211977A (en) * | 2011-04-07 | 2011-10-12 | 杨皓 | Process for producing synthetic ammonia and methanol by using coke oven gas and blast furnace gas |
| CN108191609A (en) * | 2018-01-13 | 2018-06-22 | 安徽金禾实业股份有限公司 | A kind of method of low middle pressure series connection production methanol |
| CN109574038A (en) * | 2018-12-09 | 2019-04-05 | 陈良明 | It is adapted to the syngas for synthetic ammonia compression method and system of small-sized nitrogenous fertilizer station-service |
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