CN1019663B - Process for refining raw gas of synthetic ammonia - Google Patents
Process for refining raw gas of synthetic ammoniaInfo
- Publication number
- CN1019663B CN1019663B CN90105545A CN90105545A CN1019663B CN 1019663 B CN1019663 B CN 1019663B CN 90105545 A CN90105545 A CN 90105545A CN 90105545 A CN90105545 A CN 90105545A CN 1019663 B CN1019663 B CN 1019663B
- Authority
- CN
- China
- Prior art keywords
- gas
- steam
- refining
- raw material
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 22
- 238000007670 refining Methods 0.000 title claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 66
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 7
- 239000003245 coal Substances 0.000 claims abstract description 6
- 230000023556 desulfurization Effects 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000005261 decarburization Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 230000011218 segmentation Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 230000035924 thermogenesis Effects 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 50
- 239000000618 nitrogen fertilizer Substances 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- -1 ammonia Chemical compound 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- Y02P20/121—
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a refining process of raw gas for synthesizing ammonia. It is especially suitable for refining the raw material gas of small and medium nitrogen fertilizer plants which use coal as raw material and adopt air and steam for gas making. After the raw material gas is transformed and decarbonizedUnder the condition of 5.0-15MPa, in the same refining tower with sectionally-filled desulfurization catalyst, methanol catalyst and methane catalyst the desulfurization reaction can be successively, respectively and continuously made, and reacted with H2The methanol and methane are generated and reacted to refine the raw material gas. And the heat energy of exothermic reaction generated in the refining process is utilized to preheat gas entering the tower, then the gas enters a heat recoverer to heat water to generate steam, and then the steam enters a circulating gas heater to form a circulating flow.
Description
The present invention relates to refining process for synthetic ammonia raw material gas, it is specially adapted to the coal is raw material, adopts middle-size and small-size nitrogen fertilizer plant unstripped gas refining of air, steam gas making.
Syngas for synthetic ammonia must be purified hydrogen and nitrogen, usually with air, the carbon monoxide and carbonic acid gas and a small amount of hydrogen sulfide that always contain 2-4% in the unstripped gas of the middle-size and small-size nitrogen fertilizer plant of steam gas making, the type nitrogen fertilizer plant all adopts copper to wash method (Jiang Shengjie at present, the synthetic ammonia engineering, second volume P318～368), not only to consume copper, acetic acid, raw materials such as ammonia, and consume a large amount of steam (500-600 kilogram/ton ammonia), need refrigerating capacity 5-10 ten thousand kilocalories again, and complex process, be raw material with oil or Sweet natural gas or be raw material at present with the coal, adopt the large-scale ammonia plant of steam oxygen gas making to adopt the methane method of purification (Zhang Chengfang, ammonia synthesis process and energy-conservation P273-96), but it is very high that it requires unstripped gas, i.e. H
2S≤0.1ppmCO+CO
2≤ 0.5%, therefore, single methanation process, not being suitable for the coal is raw material, with the middle-size and small-size nitrogen fertilizer plant refining process for synthetic ammonia raw material gas of air vapor gas making.
The object of the present invention is to provide a kind of both to the less demanding (CO+CO in the permission unstripped gas of unstripped gas
2Be 2～4%) do not consume industrial chemicals again, do not consume steam and refrigerating capacity, can also byproduct steam and methyl alcohol, and technology is simple, is applicable to the coal to be the process for refining of raw material with the middle-size and small-size nitrogen fertilizer plant syngas for synthetic ammonia of air vapor gas making.
Purpose of the present invention can reach by following measure: unstripped gas is after conversion, decarburization, under the 5.0-15MPa condition, be equipped with in the treating tower of desulfurization catalyst, catalyst for methanol, methanation catalyst a segmentation, carry out desulphurization reaction successively, respectively, continuously, with H
2Generate the methyl alcohol reaction and generate methane reaction, make most of carbon monoxide in the unstripped gas, carbonic acid gas generate methyl alcohol, the remaining methane that then generates, wherein methyl alcohol becomes the byproduct recovery, and methane then reclaims the usefulness that acts as a fuel after the emptying in synthetic ammonia process.Because above reaction is thermopositive reaction, can utilize its heat energy preheating to advance tower gas, and outside treating tower, be equipped with interchanger and heat reclamation device, make whole technology form the working cycle of a preheating → refining (heat release) → heat regenerator (generation steam) → recirculation heater → water cooler (methyl alcohol separation) → ammonia synthesis.
Below in conjunction with accompanying drawing to the present invention in advance to describe in detail:
Accompanying drawing is a process flow sheet of the present invention.
After unstripped gas and circulating air mix, enter carbon oil filter (1), separate profit and carbide at this, enter circulating gas heater (3), gas is heated to 70-100 ℃, enters treating column (4), in tower, at first pass through preheating section, gas is reacted the after heat gas-heated to 200-230 ℃ at this, then enters successively first paragraph in the tower, H in the gas2S removes by the following formula reaction:
After the desulfurization in the unstripped gas sulphur content can reach below the 1ppm.
Unstripped gas after the desulfurization enters second section again, CO, CO in the gas
2Generate methyl alcohol by following reaction formula,
At this moment, CO, CO in the unstripped gas
2Summation enters the 3rd section again less than 0.5%, makes remaining CO and CO by following reaction formula
2Further purify:
At this moment, CO and CO in the unstripped gas
2Summation is less than 10ppm.
Because above reaction is thermopositive reaction, therefore can reach 370-380 ℃ from the 3rd section gas temperature that comes out, enter preheating section and advance tower gas with preheating, preheating is advanced hot air temperature behind the tower gas and is dropped to 270-280 ℃ and go out tower.Enter heat regenerator (2) then, here with the steam of water heating and generation 0.7-0.9MPa, temperature drops to 140-160 ℃, enters recirculation heater (3), the circulation gas temperature is heated to 100 ℃ by normal temperature, former hot gas is then reduced to 60-80 ℃, enters water cooler (5), with cold water hot gas is cooled to be lower than 40 ℃ indirectly, this moment, methanol condensed was a liquid, enter methanol separator (6), methyl alcohol is separated, but one ton of ammonia by-product of every product methyl alcohol 70-100 kilogram.Gas is divided into two strands then, and a part is sent to ammonia synthesis converter, and another part mixes with unstripped gas after circulator (7) pressurization, continues the circulation said process.
Embodiment:
Tolerance is 16050 mark rice
3In/time, pressure is that 12-13MPa contains CO2.2%, CO
20.2%, H
272.6%, N
222%, CH
42%, H
2S0.005g/m
3Unstripped gas and circulation gas enter carbon oil strainer → recirculation heater, gas is heated to 80-100 ℃, enters the scavenging tower of a high 13000mm then, earlier through preheating section, gas is heated to 200-230 ℃, enters dress zinc-manganese sweetening agent 0.5m then successively
3Desulfurization section, dress copper catalyst 25m
3The methyl alcohol section, dress nickel catalyzator 1m
2The methane section, go out treating tower tolerance and be 15040 mark rice
3In/time, contain H in giving vent to anger
271.56%, H
229.11%, CH
42.6%, CH
3OH2.02%, CO+CO
2≤ 10ppm, H
2S≤1ppm, gas temperature are 370-380 ℃, enter preheating section → heat regenerator → recirculation heater → water cooler → methanol separator then successively, pay and produce methyl alcohol 305m
3/ h enters ammonia synthesis converter then, produce 5 tons of ammonia/time.
The process for refining of syngas for synthetic ammonia of the present invention and copper wash method and the simple methane method of purification relatively has following advantage:
Wash method relatively with copper, the one, simplified technique, and do not consume copper, the raw materials of industry such as acetic acid, ammonia, do not consume steam and refrigerating capacity, also can pay and produce methyl alcohol and steam, reduced cost, and since gas-solid reaction than gas liquid reaction good stability, operating reliability is strong.
Compare with the simple methane method of purification, CO is no more than at most 0.5% in the unstripped gas because the simple methane method of purification requires, in order to reduce CO in the unstripped gas, must consume a large amount of steam in transformation system makes it be transformed to hydrogen, and the present invention is owing to enter the methane section through the methyl alcohol section first again, so can allow in the unstripped gas there to be than great fluctuation process (2-4%) CO content, thereby conversion consumption steam can reduce significantly, and can also by-product methyl alcohol.
Claims (1)
1, a kind of is raw material with the coal, adopt the process for refining of the syngas for synthetic ammonia of air, steam gas making, it is characterized in that the later unstripped gas of process conversion decarburization is under the 5.0-15MPa condition, in the treating tower of desulfurization catalyst, catalyst for methanol, methanation catalyst (ratio of three kinds of catalyzer is 1: 5: 2) is equipped with in same segmentation, carry out desulphurization reaction successively, respectively, continuously, with H
2Generate the methyl alcohol reaction and generate methane reaction, and the heat energy that utilizes these thermopositive reaction to produce, to advance tower gas and be preheating to 200-230 ℃, enter heat regenerator again water is added thermogenesis 0.7-0.9MPa steam, enter circulating gas heater again, circulation gas is heated to 100 ℃ from normal temperature, constitutes the circulation process of a preheating → refining (heat release) → recovery of heat (generation steam) → recirculation heater → water cooler (methyl alcohol separation) → ammonia synthesis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90105545A CN1019663B (en) | 1990-09-04 | 1990-09-04 | Process for refining raw gas of synthetic ammonia |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90105545A CN1019663B (en) | 1990-09-04 | 1990-09-04 | Process for refining raw gas of synthetic ammonia |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1053219A CN1053219A (en) | 1991-07-24 |
| CN1019663B true CN1019663B (en) | 1992-12-30 |
Family
ID=4879359
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90105545A Expired CN1019663B (en) | 1990-09-04 | 1990-09-04 | Process for refining raw gas of synthetic ammonia |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1019663B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043469C (en) * | 1994-03-30 | 1999-05-26 | 湖南安淳节能技术有限公司 | Ammonia-alcohol ratio adjustable technology for refining raw-material gas for synthesis of ammonia |
| JPH1157397A (en) * | 1997-06-11 | 1999-03-02 | Mitsubishi Heavy Ind Ltd | Gas purifying method |
| JPH1135957A (en) * | 1997-07-22 | 1999-02-09 | Mitsubishi Heavy Ind Ltd | Gas refining and gas refining facility |
| JP4227676B2 (en) * | 1997-08-29 | 2009-02-18 | 三菱重工業株式会社 | Gas purification equipment |
| JP3764568B2 (en) * | 1997-10-03 | 2006-04-12 | 三菱重工業株式会社 | Gas purification method and gas purification apparatus |
| CN100339298C (en) * | 2004-05-08 | 2007-09-26 | 吕仲明 | Non-isostatic alcoholization alkylation process for purifying raw gas for ammonia synthesis |
| CN1299971C (en) * | 2004-12-10 | 2007-02-14 | 南化集团研究院 | Technique for deep purifying material gas for synthesizing ammonia |
| CN110482568A (en) * | 2019-08-12 | 2019-11-22 | 上海国际化建工程咨询有限公司 | A kind of by-product alkanol for medium and small nitrogen fertilizer factory to be transformed and the method and system of cold and hot joint purification |
| CN113479905B (en) * | 2021-06-29 | 2022-08-05 | 福州大学化肥催化剂国家工程研究中心 | Self-deoxidization ammonia synthesis tower and renewable energy source ammonia synthesis system |
-
1990
- 1990-09-04 CN CN90105545A patent/CN1019663B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1053219A (en) | 1991-07-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |