CN1847208A - Material gas stage associating process and apparatus for producing methanol and ammonia - Google Patents
Material gas stage associating process and apparatus for producing methanol and ammonia Download PDFInfo
- Publication number
- CN1847208A CN1847208A CN 200510056689 CN200510056689A CN1847208A CN 1847208 A CN1847208 A CN 1847208A CN 200510056689 CN200510056689 CN 200510056689 CN 200510056689 A CN200510056689 A CN 200510056689A CN 1847208 A CN1847208 A CN 1847208A
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- China
- Prior art keywords
- gas
- ammonia
- methanol
- methyl alcohol
- synthetic
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 283
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000008569 process Effects 0.000 title abstract description 3
- 239000000463 material Substances 0.000 title abstract 2
- 239000007789 gas Substances 0.000 claims abstract description 69
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003245 coal Substances 0.000 claims abstract description 11
- 239000003345 natural gas Substances 0.000 claims abstract description 8
- 239000000571 coke Substances 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 238000010926 purge Methods 0.000 claims description 8
- 235000009508 confectionery Nutrition 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 5
- 239000000796 flavoring agent Substances 0.000 claims description 2
- 235000019634 flavors Nutrition 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 abstract 1
- 239000013014 purified material Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 230000023556 desulfurization Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 238000002309 gasification Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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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 first low 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 eliminate CO, 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 and apparatus of raw material classification synthesizing methanol and ammonia with coal, oil, Sweet natural gas, coke(oven)gas etc., mainly is the H that contains that makes
2, CO, CO
2, N
2, CH
4Remove unstripped gas to the synthetic nuisance of methyl alcohol Deng what form 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; The high pressure methanol purge gas is removed CO, CO through methods such as methanations
2Synthetic Deng 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:
| Mol％ | Tolerance (Nm 3/h) | |||||||||
| H 2 | CO | CO 2 | N 2 | CH 4 | O 2 | H 2S | H 2O | CH 3OH | ||
| (1) raw gas | 47.90 | 37.90 | 6.90 | 6.50 | 0.40 | 0.20 | 0.20 | 0 | 0 | 42084 |
| (2) unstripped gas | 69.77 | 22.34 | 0.50 | 6.96 | 0.43 | 39216 | ||||
| (3) methanol purge gas | 73.69 | 6.01 | 0.33 | 17.83 | 1.09 | 0.14 | 0.64 | 15243 | ||
| (4) refinery gas | 76.27 | 22.29 | 1.44 | 12124.5 | ||||||
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 (5)
1. make the method and apparatus of raw material classification synthesizing methanol and ammonia with coal, oil, Sweet natural gas, coke(oven)gas etc. for one kind, it is characterized in that the H that contains that makes
2, CO, CO
2, N
2, CH
4Remove the unstripped gas that methyl alcohol is synthesized nuisance Deng what form 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 CO, CO through methods such as methanations
2Synthetic Deng deammoniation behind the ammonia synthesis obnoxious flavour.
2. according to the synthetic method of producing methyl alcohol and ammonia of the classification of claim 1, the pressure that it is characterized in that low pressure methanol synthesis is 4～9MPa.
3. according to the synthetic method of producing methyl alcohol and ammonia of the classification of claim 1, the pressure that it is characterized in that the high pressure synthesizing methanol is 10～32MPa.
4. according to the synthetic method of producing methyl alcohol and ammonia of the classification of claim 1, it is characterized in that methyl alcohol that low pressure methanol synthesis produces and high pressure methanol output ratio are greater than 2.
5. according to the synthetic method of producing methyl alcohol and ammonia of the classification of claim 1, 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 true CN1847208A (en) | 2006-10-18 |
| CN100596293C CN100596293C (en) | 2010-03-31 |
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| 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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| Country | Link |
|---|---|
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Cited By (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 |
-
2005
- 2005-04-14 CN CN200510056689A patent/CN100596293C/en not_active Expired - Fee Related
Cited By (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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100596293C (en) | 2010-03-31 |
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