CN110562919A - (Sulfur-free) carbon monoxide medium-temperature shift catalyst and preparation method thereof - Google Patents
(Sulfur-free) carbon monoxide medium-temperature shift catalyst and preparation method thereof Download PDFInfo
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- CN110562919A CN110562919A CN201910976864.XA CN201910976864A CN110562919A CN 110562919 A CN110562919 A CN 110562919A CN 201910976864 A CN201910976864 A CN 201910976864A CN 110562919 A CN110562919 A CN 110562919A
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- carbon monoxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 229910017906 NH3H2O Inorganic materials 0.000 claims abstract description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 238000005457 optimization Methods 0.000 abstract description 2
- 239000003337 fertilizer Substances 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
Abstract
the invention relates to a (sulfur-free) carbon monoxide medium-temperature shift catalyst and a preparation method thereof, the components comprise Mn, Al, Si, Mg, Ce, Cu, Co, Mo, Zn, Ca, Li and other elements, the reaction solution comprises HNO3，NH3H2O，H20.5-8.0 wt% of Mn, 0.5-25.0 wt% of Al, 0.001-3.0 wt% of Si, 0.5-5.0 wt% of Mg, 0.1-5.0 wt% of Ce, 0.5-50.0 wt% of Cu, 0.1-3.0 wt% of Co, 0.1-10.0 wt% of Mo, 0.5-25.0 wt% of Zn, 0.5-3.0 wt% of Ca, 0.1-3.0 wt% of Li, and 0.1-3.0 wt% of HNO3The concentration of the solution is 0.01-10.0, NH3H20.01 to 10.0% of O complex solution and H2The balance being O. The invention selects harmless and more environment-friendly metal oxide components for production, and the operation temperature zone is 190-330 ℃ to realize real operation in the medium-temperature zone, thus not only avoiding the harm to human bodies in the production process, but also greatly reducing the industrial energy consumptionhigh catalyst change and water-carbon ratio reduction), subsequent supporting facilities have larger optimization margin, which has great benefits for energy-saving innovation of fertilizer enterprises and fills the blank of China in the field.
Description
Technical Field
The invention relates to the technical field of carbon monoxide medium-temperature shift catalysts, in particular to a (sulfur-free) carbon monoxide medium-temperature shift catalyst and a preparation method thereof.
Background
the technology has been developed by the company danish topsulo in the late nineties of the last century; the curtain people and others also research and develop the technology and perform industrial pilot test at the same time, and the effect reaches the design value; however, because of the serious shortage of industrial design basis and the shortage of natural gas resources in large-scale ammonia synthesis devices introduced only in 70 th of China, the ammonia synthesis devices which use natural gas or naphtha as raw materials are changed into coal as raw materials in succession at the beginning of the twentieth century, so that the technology is not matched and stranded with corresponding process device design, in the existing ammonia synthesis (hydrogen production) carbon monoxide conversion process which uses natural gas and pyrolysis gas as raw materials (low sulfur and is not applicable to sulfur-tolerant conversion process), a high-temperature conversion catalyst and a low-temperature conversion catalyst process are adopted to convert carbon monoxide into hydrogen and further reduce the content of carbon monoxide, the high-temperature conversion catalyst and the medium-temperature conversion catalyst in China are the same catalyst (namely the high-temperature conversion catalyst or the medium-temperature conversion catalyst in the literature and patents in the industry at present time are actually the same catalyst), the operating temperature region of the high-temperature conversion catalyst is 340-550 ℃, mainly changing the carbon monoxide content of about 13 percent of an inlet to about 3 percent; the operation temperature zone of the low-temperature-change catalyst is 190-240 ℃, and the carbon monoxide content of about 3% of an inlet is mainly changed to be below 0.4%; because the high temperature shift catalyst has high operation temperature and large energy consumption, and the production of the catalyst mainly composed of iron/chromium elements has great harm to human bodies and generates a large amount of ammonia-nitrogen wastewater which is difficult to treat, the existing high temperature shift catalyst has high operation temperature and large energy consumption, and the catalyst mainly composed of iron/chromium elements can generate F-T side reaction, so that the productivity is reduced and the device is damaged.
Disclosure of Invention
The invention aims to provide a (sulfur-free) carbon monoxide medium-temperature shift catalyst and a preparation method thereof, which aim to solve the problems that the existing high shift catalyst proposed in the background technology has high operation temperature and high energy consumption, and simultaneously solve the problems that the production of the catalyst mainly composed of iron/chromium elements is extremely harmful to human bodies and generates a large amount of ammonia-nitrogen wastewater which is difficult to treat.
In order to achieve the purpose, the invention provides the following technical scheme: a catalyst for the medium-temp conversion of CO (sulfur-free one) is prepared from Mn, Al, Si, Mg, Ce, Cu, Co, Mo, Zn, Ca and Li, and the reaction solution containing HNO3，NH3H2O，H20.5-8.0 wt% of Mn, 0.5-25.0 wt% of Al, 0.001-3.0 wt% of Si, 0.5-5.0 wt% of Mg, 0.1-5.0 wt% of Ce, 0.5-50.0 wt% of Cu, 0.1-3.0 wt% of Co, 0.1-10.0 wt% of Mo, 0.5-25.0 wt% of Zn, 0.5-3.0 wt% of Ca, 0.1-3.0 wt% of Li, and 0.1-3.0 wt% of HNO3The concentration of the solution is 0.01-10.0 wt%, and NH3H20.01-10.0 wt% of O complex solution and H2The balance being O.
Preferably, 2-5 of Mn, Al, Si, Mg, Ce, Cu, Co, Mo, Zn, Ca and Li are selected to form active component metals or oxides.
Preferably, the grain size of the Mn, Al, Si, Mg, Ce, Cu, Co, Mo, Zn, Ca and Li is 1-5 nm.
Preferably, the specific steps are as follows;
1) Putting the metal or oxide of the required active component in the corresponding acid liquid (HNO)3) Or lye (NH)3H2o) to HNO3The concentration of the solution is 0.01-10.0 wt%, and NH3H20.01-10.0 wt% of O complex solution;
2) Adding a proper amount of pure water to prepare a solution with the concentration of 0.001-5.0 wt%, and uniformly stirring; neutralizing the alkali solution at 50-200 ℃ until the specific gravity is 0.001-2.0 wt%, and aging to obtain a precipitation product, wherein the pH value of the precipitation condition is controlled to be 5.0-11.0, and the precipitation temperature is 50-120 ℃;
3) Adding 2-4 coordination complex auxiliary agents of Mn, Al, Si, Mg, Ce, Cu, Co, Mo, Zn, Li and Ca elements, uniformly mixing, washing, settling, removing impurities, drying at 50-200 ℃ after filter pressing, calcining at 200-750 ℃ with the water content controlled at 1-20%, grinding, granulating, drying, tabletting, forming and packaging.
Compared with the prior art, the invention selects harmless and more environment-friendly metal oxide components for production, and the operation temperature zone is 190-330 ℃, so that the operation is really realized in the medium-temperature area, thereby not only avoiding the harm to human bodies in the production process, but also avoiding the occurrence of F-T side reaction, and greatly reducing the industrial energy consumption.
Drawings
FIG. 1 is a schematic process flow diagram of a (sulfur-free) medium-temperature carbon monoxide shift catalyst and a preparation method thereof.
Detailed Description
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: a catalyst for medium-temp conversion of CO (sulfur-free one) is prepared from Mn, Al, Si, Mg, Ce, Cu, Co, Mo, Zn, Ca andLi element, the reaction solution includes HNO3，NH3H2O，H20.5 to 8.0 wt% of O, Mn, 0.5 to 25.0 wt% of Al, 0.001 to 3.0 wt% of Si, 0.5 to 5.0 wt% of Mg, 0.1 to 5.0 wt% of Ce, 0.5 to 50.0 wt% of Cu, 0.1 to 3.0 wt% of Co, 0.1 to 10.0 wt% of Mo, 0.5 to 25.0 wt% of Zn, 0.5 to 3.0 wt% of Ca, 0.1 to 3.0 wt% of Li, and HNO3The concentration of the solution is 0.01-10.0, NH3H20.01 to 10.0% of O complex solution and H2The balance being O.
2-5 of Mn, Al, Si, Mg, Ce, Cu, Co, Mo, Zn, Ca and Li are selected to form active component metals or oxides.
The particles of Mn, Al, Si, Mg, Ce, Cu, Co, Mo, Zn, Ca and Li are 1-5 nanometers.
The method comprises the following specific steps;
1) putting the metal or oxide of the required active component in the corresponding acid liquid (HNO)3) Or lye (NH)3H2O) to HNO3The concentration of the solution is 0.01-10.0 wt%, and NH3H20.01-10.0 wt% of O complex solution;
2) Adding a proper amount of pure water to prepare a solution with the concentration of 0.001-5.0 wt%, and uniformly stirring; neutralizing the alkali solution at 50-200 ℃ until the specific gravity is 0.001-2.0 wt%, aging to obtain a precipitation product, controlling the pH value of the precipitation condition to be 5.0-11.0 wt%, and controlling the precipitation temperature to be 50-120 ℃;
3) Adding 2-4 coordination complex assistants of Mn, Al, Si, Mg, Ce, Cu, Co, Mo, Zn, Li, Ca and other elements, mixing homogeneously, washing, settling to remove impurities, press filtering, stoving at 50-200 deg.c, heat treatment at 200-750 deg.c to water content of 1-20%, grinding, pelletizing, stoving, tabletting and packing, the present invention selects harmless and environment friendly metal oxide component to produce while avoiding F-T side reaction and has operation temperature of 190-330 deg.c to realize operation in medium temperature area, the invention can change the carbon monoxide content of about 15 percent of the inlet to less than 1 percent (can completely replace the traditional high-temperature catalyst and reduce the water-carbon ratio), and subsequent supporting facilities have larger optimization margin.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents of some features of the invention can be substituted without departing from the spirit and scope of the invention.
Claims (4)
1. A (sulfur-free) medium-temp. CO conversion catalyst is prepared from 2-5 elements including Mn, Al, Si, Mg, Ce, Cu, Co, Mo, Zn, Ca and Li, and the reaction solution containing HNO3，NH3H2O and H20.5-8.0 wt% of Mn, 0.5-25.0 wt% of Al, 0.001-3.0 wt% of Si, 0.5-5.0 wt% of Mg, 0.1-5.0 wt% of Ce, 0.5-50.0 wt% of Cu, 0.1-3.0 wt% of Co, 0.1-10.0 wt% of Mo, 0.5-25.0 wt% of Zn, 0.5-3.0 wt% of Ca, 0.1-3.0 wt% of Li, and 0.1-3.0 wt% of HNO3The concentration of the solution is 0.01-10.0 wt%, and NH3H20.01-10.0 wt% of O complex solution and H2The balance being O.
2. The (sulfur-free) medium-temperature carbon monoxide shift catalyst and the preparation method thereof according to claim 1, wherein the catalyst comprises: 2-5 of Mn, Al, Si, Mg, Ce, Cu, Co, Mo, Zn, Ca and Li are selected to form active component metals or oxides.
3. The (sulfur-free) medium-temperature carbon monoxide shift catalyst and the preparation method thereof according to claim 1, wherein the catalyst comprises: the grain size of the Mn, Al, Si, Mg, Ce, Cu, Co, Mo, Zn, Ca and Li is 1-5 nanometers.
4. A (sulfur-free) medium-temperature carbon monoxide shift catalyst and a preparation method thereof according to claims 1-3, wherein: the specific steps are as follows;
1) Putting the metal or oxide of the required active component in the corresponding acid liquid (HNO)3) Or lye (NH)3H2O) to HNO3The concentration of the solution is 0.01-10.0 wt%, and NH3H20.01-10.0 wt% of O complex solution;
2) Adding a proper amount of pure water to prepare a solution with the concentration of 0.001-5.0 wt%, and uniformly stirring; neutralizing the alkali solution at 50-200 ℃ until the specific gravity is 0.001-2.0 wt%, and aging to obtain a precipitation product, wherein the pH value of the precipitation condition is controlled to be 5.0-11.0, and the precipitation temperature is 50-120 ℃;
3) adding 2-4 coordination complex auxiliary agents of Mn, Al, Si, Mg, Ce, Cu, Co, Mo, Zn, Li and Ca elements, uniformly mixing, washing and settling, drying at 50-200 ℃ after filter pressing, calcining at 200-750 ℃ with the water content controlled at 1-20%, grinding, granulating and drying, tabletting, forming and packaging.
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| CN201910976864.XA CN110562919A (en) | 2019-10-15 | 2019-10-15 | (Sulfur-free) carbon monoxide medium-temperature shift catalyst and preparation method thereof |
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| CN201910976864.XA CN110562919A (en) | 2019-10-15 | 2019-10-15 | (Sulfur-free) carbon monoxide medium-temperature shift catalyst and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322672A (en) * | 2001-02-26 | 2001-11-21 | 福州大学化肥催化剂国家工程研究中心 | Dip loading chromium-free middle temperature CO converting catalyst |
| CN1986057A (en) * | 2006-12-13 | 2007-06-27 | 湖北双雄催化剂有限公司 | Preparing method of counterpoison for protecting Co-Mo Co of anti-sulfur change catalyst |
| CN105536803A (en) * | 2016-01-22 | 2016-05-04 | 盘锦迪宝催化剂技术有限公司 | Copper-filled carbon monoxide medium temperature shift catalyst and preparation method thereof |
| CN106925355A (en) * | 2017-03-31 | 2017-07-07 | 福州大学化肥催化剂国家工程研究中心 | A kind of maceration extract and the method that sulfur-resistant transformation catalyst is prepared using the maceration extract |
-
2019
- 2019-10-15 CN CN201910976864.XA patent/CN110562919A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1322672A (en) * | 2001-02-26 | 2001-11-21 | 福州大学化肥催化剂国家工程研究中心 | Dip loading chromium-free middle temperature CO converting catalyst |
| CN1986057A (en) * | 2006-12-13 | 2007-06-27 | 湖北双雄催化剂有限公司 | Preparing method of counterpoison for protecting Co-Mo Co of anti-sulfur change catalyst |
| CN105536803A (en) * | 2016-01-22 | 2016-05-04 | 盘锦迪宝催化剂技术有限公司 | Copper-filled carbon monoxide medium temperature shift catalyst and preparation method thereof |
| CN106925355A (en) * | 2017-03-31 | 2017-07-07 | 福州大学化肥催化剂国家工程研究中心 | A kind of maceration extract and the method that sulfur-resistant transformation catalyst is prepared using the maceration extract |
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Application publication date: 20191213 |