CN1217291A - Transformation process without saturation tower - Google Patents
Transformation process without saturation tower Download PDFInfo
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- CN1217291A CN1217291A CN 97121017 CN97121017A CN1217291A CN 1217291 A CN1217291 A CN 1217291A CN 97121017 CN97121017 CN 97121017 CN 97121017 A CN97121017 A CN 97121017A CN 1217291 A CN1217291 A CN 1217291A
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- temperature
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- water
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000009466 transformation Effects 0.000 title description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007789 gas Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000002516 radical scavenger Substances 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 3
- 239000003245 coal Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000012459 cleaning agent Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000012629 purifying agent Substances 0.000 description 13
- 239000002699 waste material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 3
- 238000001784 detoxification Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910017060 Fe Cr Inorganic materials 0.000 description 2
- 229910002544 Fe-Cr Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008234 soft water Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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Abstract
The present invention discloses a carbon monoxide conversion process for preparing synthetic ammonia by using coal or residuum as raw material. Said process does not adopt saturation tower, but uses cleaning agent to implement the purification treatment of semi-water gas to remove the impurities of oxygen, etc. harmful to low-temp. conversion catalyst, and the Co-Mo series low-temp. conversion catalyst is filled in the convertor. By reducing conversion temp, the ton ammonia steam consumption of said conversion process having no saturation tower only is about 300 Kg.
Description
The present invention relates to a carbon monoxide conversion process for preparing synthetic ammonia by using coal or residual oil as raw material.
In the domestic ammonia synthesis industry, medium and small nitrogen fertilizer plants mostly use coal as raw materials to produce synthesis gas, and heat in conversion gas is recovered through a saturation tower, a hot water tower and a temperature-regulating water heater. With the development of the conversion process and the conversion catalyst, the heat in the conversion gas at the outlet of the conversion furnace is less and less, and if the conversion process is adopted, the temperature of the conversion gas at the outlet is more than 300 ℃, and H is higher2O/gas is more than 0.5; medium-series low process, outlet conversion gas temperature above 230 ℃, H20.2 to 0.3 of O/gas; thetotal low-temperature change process is carried out, the outlet change gas is 210-220 ℃, and H is2O/gas is 0.05-0.15. Thus, the effect of recovering heat by using the saturation tower is less and less obvious, and the possibility of recovering heat by other modes is provided.
Along with the expanded production and transformation of medium and small nitrogen fertilizers, the operating pressure is higher and higher, and the material of the saturation tower is required to be changed from carbon steel which is easy to corrode and perforate into stainless steel correspondingly, so that the equipment investment is increased. And a saturation tower is removed, so that a large amount of capital can be saved. Although some manufacturers of medium nitrogen fertilizers have adopted a conversion process without a saturation tower, semi-water gas is added with steam and then directly enters a conversion furnace, the conversion catalyst adopts a Fe-Cr system conversion catalyst, the temperature of the gas at the inlet of the conversion furnace is above 300 ℃, and the steam consumption is as high as more than one ton of steam consumed per ton of ammonia.
Carbon monoxide and H2The shift reaction of O is an exothermic reaction:
The invention aims to provide a conversion process which is free of a saturation tower and adopts a Co-Mo series low-temperature conversion catalyst so as to reduce the consumption of steam.
In order to achieve the purpose, the solution adopted by the invention is that after the semi-water gas from a compressor is subjected to heat exchange and temperature rise, the semi-water gas is firstly subjected to detoxification and deoxidization, namely enters a dry gas purifier for purification treatment, and then is added with steam and enters a shift converter filled with a Co-Mo series low-temperature-change catalyst; or firstly adding steam, then entering a purifying agent bed layer, performing detoxification and deoxidization, and then entering a Co-Mo low-variation catalyst bed layer.
Specifically, the invention is realized by the following method: cooling the semi-water gas from a compressor to remove oil, then carrying out heat exchange and heating, and feeding the semi-water gas into a dry gas purifier to remove impurities such as oxygen, carbonyl iron and the like; then adding steam, and feeding the steam into a shift converter filled with a Co-Mo series low-temperature shift catalyst; or firstly adding steam, then entering a purifying agent bed layer, carrying out detoxification and deoxidization, and then entering a Co-Mo low-variation catalyst bed layer; the shift converter can be oneor more than one, and can also be divided into two sections or more than two sections, the temperature of the two furnaces or the two sections is adjusted by water spraying or heat exchange, and the inlet temperature is controlled to be 170-250 ℃, preferably 180-220 ℃; the conversion gas out of the conversion furnace can directly enter a decarburization conversion boiler or enter a temperature-adjusting water heater to preheat hot water sprayed into the conversion furnace or sections; the temperature of the changed air out of the temperature-adjusting water heater is controlled to be higher than the dew point temperature, the changed air enters a hot water tower, after the excessive steam is condensed in the hot water tower, the soft water is heated again or the cold water directly enters a cold drain; hot water in the hot water tower or hot water from other sources can be partially or completely sprayed into the conversion furnace or the sections without passing through the temperature-regulating water heater.
In the invention, the gas purifier is filled with the purifying agent described in CN 97105846.6. The purifying agent can be prepared by an impregnation method or a blending method. When the impregnation method is adopted, the impregnation liquid can be a solution containing one or more elements of molybdenum, cobalt, iron, nickel, potassium, tungsten and platinum, and the impregnated carrier can be alumina, diaspore, titanium dioxide and waste catalyst, or a mixture thereof. When the waste catalyst is used as the carrier, it is preferable to use a waste iron-chromium-based shift catalyst, a waste cobalt-molybdenum-based shift catalyst or a waste hydrogenation catalyst. The purifying agent used in the invention can be prepared by drying and roasting after dipping. When the mixing method is adopted, the purifying agent used by the invention can be prepared by taking oxides, sulfides or salts of one or more elements of molybdenum, cobalt, iron, nickel, potassium, platinum, chromium, tungsten, aluminum and titanium, and carrying out the steps of kneading, drying, crushing, flaking and the like. In the cleaning agent, the content of active elements such as molybdenum, cobalt, iron, nickel, potassium, chromium, tungsten, platinum, etc. is generally not less than 10.0% (calculated by oxide or sulfide), preferably not less than 17.0%. The purifying agent is used for enabling most of oxygen to be catalytically converted, so that the hot spot temperature of the shift converter is reduced; meanwhile, all carbonyl iron is subjected to catalytic thermal decomposition on a purifying agent, so that the carbonyl iron cannot enter a conversion section to block a conversion catalyst.
Because the purifying agent is used for purifying the semi-water gas and reducing the oxygen content in the semi-water gas, in the conversion process without a saturation tower,Co-Mo low-shift catalyst can be used to lower shift temp. so as to raise CO and H2The equilibrium conversion of O is such that only about 300Kg of steam is consumed per ton of ammonia.
The present invention is further illustrated by the following examples.
In the figure, 1 is a heat exchanger, 2 is a dry gas purifying furnace, 3 is a first humidifier, 4 is a first shift converter, 5 is a second humidifier, 6 is a third humidifier, 7 is a second shift converter, 8 is a temperature-adjusting water heater, 9 is a hot water tower, and 10 is a hot water pump. Example 1
According to the flow shown in figure 1, deoiled 0.8MPa semi-water gas is heated to 200-220 ℃ through a heat exchanger 1, enters a dry gas purifier 2, the purifying agent is the purifying agent described in patent application CN97105846.6, steam is added in front of a first humidifier 3, the temperature is adjusted to 170-300 ℃, the semi-water gas enters a first section of a shift converter 4, the shift converter is filled with a QCS-02 sulfur-tolerant shift catalyst, the temperature is increased to about 300 ℃, the semi-water gas enters a humidifier 5, the temperature is adjusted to 170-250 ℃, the semi-water gas enters a second section of the shift converter 4, the temperature is increased to about 300 ℃, the temperature is adjusted to 170-250 ℃ through a humidifier 6, the semi-water gas enters a second shift converter 7, the outlet shift gas is controlled to be CO less than 1.5 percent and the temperature is 210-250 ℃, the semi-water gas enters the heat exchanger 1, then enters a temperature adjusting water heater 8, the temperature is controlled to be above the dew point temperature, the hot water tower, one part is sprayed into the humidifier, and the other part is used for heating the copper liquid. Example 2
According to the flow shown in figure 2, deoiled 1.35MPa semi-water gas is heated by a heat exchanger 1 and added with steam, the temperature of the inlet is controlled to be about 200 ℃, the gas enters a first section of a shift converter 4, the purifying agent described in the patent application CN97105846.6 is filled in the upper part of the first section of the converter, QCS-02 catalysts are filled in the lower part, a second section and a third section of the converter, the gas from the first section is cooled to 200-220 ℃ by a humidifier 3 and enters the second section, the reaction gas from the second section is sprayed with water in the converter and is cooled to 200 ℃, the reaction gas enters the third section, the CO of the gas from the third section is controlled to be less than 0.5 percent and enters the heat exchanger 1, then enters a temperature regulating water heater 8, the temperature. Hot water in the hot water tower enters the temperature-adjusting water heater 8 after being pressurized by the hot water pump 10, and enters the humidifier 3 and is sprayed into the shift converter 4 after being heated. Example 3
According to the flow shown in figure 3, deoiled 2.3MPa semi-water gas is heated by a heat exchanger 1, steam is added, the temperature is controlled to be about 230 ℃, the gas enters a first section of a shift converter 4, the purifying agent described in the patent application CN97105846.6 is filled in the upper part of the first section, and QCS-02 catalysts are filled in the lower part and the three sections. The first-stage reaction gas is controlled to be about 300 ℃ after being sprayed with water and cooled, enters the second stage of the shift converter 4, the second stage is filled with a B117 catalyst, the second-stage reaction gas is controlled to be about 230 ℃ after being sprayed with water and cooled, enters the third stage of the shift converter 4, CO is controlled to be 7-10% at an outlet of the third stage, and enters the decarburization shift boiler after passing through the heat exchanger 1 and the water heater 8. The soft water is heated by the temperature-adjusting water heater 8 and then directly sprayed into the shift converter 4.
Claims (4)
1. A CO conversion process without saturation tower and using Co-Mo series low-temp catalyst features that the semi-water gas used in the conversion process is purified to remove oxygen and carbonyl iron impurities.
2. The process of claim 1, wherein the shift converter can be one or more than one, each shift converter can be one or more than one section, the temperature of the converter or the sections is adjusted by water spraying or heat exchange, and the inlet temperature is controlled to be 170-250 ℃.
3. The process according to claim 2, wherein the inlet temperature is controlled to be 180 to 220 ℃.
4. The process as claimed in claim 1, wherein the scavenger used for purifying the semiwater gas contains one or more compounds of molybdenum, cobalt, iron, nickel, potassium, tungsten and platinum as active components, and the content of the compound is not less than 10.0% in terms of oxide or sulfide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97121017 CN1064928C (en) | 1997-11-19 | 1997-11-19 | Transformation process without saturation tower |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97121017 CN1064928C (en) | 1997-11-19 | 1997-11-19 | Transformation process without saturation tower |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1217291A true CN1217291A (en) | 1999-05-26 |
| CN1064928C CN1064928C (en) | 2001-04-25 |
Family
ID=5176141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97121017 Expired - Fee Related CN1064928C (en) | 1997-11-19 | 1997-11-19 | Transformation process without saturation tower |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1064928C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105770C (en) * | 2000-06-12 | 2003-04-16 | 中国石化集团齐鲁石油化工公司 | Process for cleaning raw gas in conversion reaction |
| WO2004013040A1 (en) * | 2002-08-01 | 2004-02-12 | Johnson Matthey Public Limited Company | Process for producing hydrogen including a water gas shift reaction |
| CN100361889C (en) * | 2006-03-16 | 2008-01-16 | 五环科技股份有限公司 | Secondary transformation technological method of high concentration carbon monooxide |
| CN101862626A (en) * | 2010-05-10 | 2010-10-20 | 湖北双雄催化剂有限公司 | Full-low temperature shifting flow for heating humidified water of shifting furnace by using heat at shifting outlet |
| CN102530862A (en) * | 2012-03-12 | 2012-07-04 | 浠水县福瑞德化工有限责任公司 | Carbon monoxide conversion method for ammonia synthesis |
| CN103241712A (en) * | 2013-04-09 | 2013-08-14 | 内蒙古乌拉山化肥有限责任公司 | Semi-water gas treatment method |
-
1997
- 1997-11-19 CN CN 97121017 patent/CN1064928C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105770C (en) * | 2000-06-12 | 2003-04-16 | 中国石化集团齐鲁石油化工公司 | Process for cleaning raw gas in conversion reaction |
| WO2004013040A1 (en) * | 2002-08-01 | 2004-02-12 | Johnson Matthey Public Limited Company | Process for producing hydrogen including a water gas shift reaction |
| CN100361889C (en) * | 2006-03-16 | 2008-01-16 | 五环科技股份有限公司 | Secondary transformation technological method of high concentration carbon monooxide |
| CN101862626A (en) * | 2010-05-10 | 2010-10-20 | 湖北双雄催化剂有限公司 | Full-low temperature shifting flow for heating humidified water of shifting furnace by using heat at shifting outlet |
| CN101862626B (en) * | 2010-05-10 | 2012-08-22 | 湖北双雄催化剂有限公司 | Full-low temperature shifting flow for heating humidified water of shifting furnace by using heat at shifting outlet |
| CN102530862A (en) * | 2012-03-12 | 2012-07-04 | 浠水县福瑞德化工有限责任公司 | Carbon monoxide conversion method for ammonia synthesis |
| CN103241712A (en) * | 2013-04-09 | 2013-08-14 | 内蒙古乌拉山化肥有限责任公司 | Semi-water gas treatment method |
| CN103241712B (en) * | 2013-04-09 | 2016-03-16 | 内蒙古乌拉山化肥有限责任公司 | A kind of semi-water gas treatment process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1064928C (en) | 2001-04-25 |
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