CN114477089A - Method for removing trace CO at low temperature - Google Patents
Method for removing trace CO at low temperature Download PDFInfo
- Publication number
- CN114477089A CN114477089A CN202011157519.2A CN202011157519A CN114477089A CN 114477089 A CN114477089 A CN 114477089A CN 202011157519 A CN202011157519 A CN 202011157519A CN 114477089 A CN114477089 A CN 114477089A
- Authority
- CN
- China
- Prior art keywords
- nickel
- hours
- reaction
- ruthenium
- supported 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 43
- 239000007789 gas Substances 0.000 claims abstract description 33
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 48
- 239000002243 precursor Substances 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- 239000011159 matrix material Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 13
- 238000011068 loading method Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 125000002883 imidazolyl group Chemical group 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- 239000007787 solid Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 5
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 5
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 5
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 5
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 5
- 108091006231 SLC7A2 Proteins 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- -1 nickel salt Chemical class 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009475 tablet pressing Methods 0.000 description 1
- 230000004580 weight loss Effects 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
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
- C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
- C01B3/586—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being a methanation reaction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0001—Separation or purification processing
- C01B2210/0003—Chemical processing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2210/00—Purification or separation of specific gases
- C01B2210/0043—Impurity removed
- C01B2210/005—Carbon monoxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of gas purification, and provides a method for removing trace CO at low temperature, which comprises the following steps: in a fixed bed reactor, the hydrogen-rich gas containing carbon oxides is contacted with a supported catalyst at the reaction temperature of 80-140 ℃, the pressure of 0.1-7.0 MPa and the gas space velocity of less than 6000h‑1Carrying out methanation reaction under the condition that the concentration of CO at the inlet is less than 3000 ppm; the supported catalyst comprises a substrate and ruthenium supported on the substrate, wherein the substrate comprises carbon and nickel which are supported by nitrogen doping, and at least part of the nickel forms coordination bonds with lone-pair electrons on the nitrogen. The method of the invention enables the methanation reaction to be carried out at a low temperature of less than 150 ℃ by adopting the supported catalyst, and can remove the CO content in the hydrogen-rich gas to be less than 3 ppm.
Description
Technical Field
The invention belongs to the field of gas purification, and particularly relates to a method for removing trace CO at low temperature.
Background
The most common noble metal catalysts in industry include supported Pd and Pt catalysts, and supported Ru noble metal catalysts are also used in industry, such as low temperature methanation reaction. Compared with other noble metal catalysts, the supported Ru catalyst has better industrial application prospect due to relatively low price.
At present, research on supported Ru catalysts mainly focuses on catalyst preparation and application, and catalysts required by reactions such as hydrogenation or dehydrogenation are obtained by using different carriers, different Ru precursors, different preparation methods and the like. For example, an alumina-supported Ru catalyst is prepared by an impregnation method with an alumina carrier; preparing a coconut shell carbon supported Ru catalyst by using a coconut shell carbon carrier through an impregnation method; the titanium dioxide supported Ru catalyst is obtained by a titanium dioxide carrier through methods of dipping, spraying and the like, and can be used for reactions such as hydrogenation and the like. However, the supported Ru catalyst has problems of low noble metal utilization efficiency, low reaction activity, poor actual reaction stability, and the like due to the preparation method, composition, structure, and the like.
The methanation catalyst is mainly used for deeply removing trace carbon oxides (mainly CO) in crude hydrogen in an ethylene device or an ammonia synthesis device, and generally the carbon oxides in the crude hydrogen need to be removed to less than 5ppm through a methanation reactor. The methanation catalyst mainly comprises a Ru catalyst and a Ni catalyst. Currently, the methanation catalyst commonly used is a Ni catalyst. The Ni catalyst is also classified into a high-temperature catalyst and a low-temperature catalyst. In an ethylene plant, the operating temperature of the high temperature catalyst is generally 280 to 350 ℃, and the operating temperature of the low temperature catalyst is generally 150 to 200 ℃. The low-temperature methanation catalyst has the advantages of energy conservation, environmental protection, safety and economy, thereby gradually replacing the high-temperature methanation process.
The reaction temperature of the existing low-temperature methanation catalyst is not less than 150 ℃. While the reaction below 150 ℃ has extremely high requirements on the activity of the catalyst, the traditional methanation catalyst needs high-temperature roasting in the preparation process, and the high-temperature roasting causes considerable sintering of metal particles, so that the utilization rate of active metal is reduced, and finally the reaction activity of the catalyst is low, so that the methanation reaction below 150 ℃ cannot be met.
Therefore, for low-temperature methanation reaction, the development of a catalyst which has high activity at lower temperature (less than 150 ℃) is of great significance for the methanation process.
Disclosure of Invention
The invention aims to provide a method for removing trace CO at low temperature. The method of the invention enables the methanation reaction to be carried out at a low temperature of less than 150 ℃ by adopting the supported catalyst, and can remove the CO content in the hydrogen-rich gas to be less than 3 ppm.
In order to achieve the above object, the present invention provides a method for removing trace CO at low temperature, comprising: in a fixed bed reactor, the hydrogen-rich gas containing carbon oxides is contacted with a supported catalyst at the reaction temperature of 80-140 ℃, the pressure of 0.1-7.0 MPa and the gas space velocity of not more than 6000h-1Carrying out methanation reaction under the condition that the concentration of CO at the inlet is not more than 3000 ppm; wherein the supported catalyst comprises a substrate and ruthenium supported thereon, the substrate comprises nitrogen-doped support carbon and nickel, and at least part of the nickel forms coordination bonds with lone-pair electrons on the nitrogen.
The invention provides a low-temperature methanation removal method of trace CO in a hydrogen-rich gas, in a adopted supported catalyst, a substrate is nitrogen-doped carrier carbon obtained by high-molecular carbonization and is combined with nickel, a coordination bond exists between nitrogen in the substrate and metal nickel, so that the nickel is dispersed more uniformly, a valence electron structure is changed due to the coordination bond, the supported ruthenium metal is combined, the utilization rate of an active component is high, the trace CO in the hydrogen-rich gas can be removed to 3ppm or even below 1ppm at lower temperature, and the stability of the catalyst is higher.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a method for removing trace CO at low temperature, which comprises the following steps: in a fixed bed reactor, a hydrogen-rich gas containing carbon oxides is contacted with a supported catalyst, and low-temperature methanation reaction is carried out.
The source of the crude hydrogen gas containing carbon oxides (gas to be purified) is not particularly limited in the present invention, and may be, for example, crude hydrogen gas produced by a process such as ethylene cracking.
According to the invention, the low-temperature methanation reaction has the reaction temperature of 80-140 ℃, the pressure of 0.1-7.0 MPa and the gas space velocity of not less than 6000h-1And the inlet CO concentration is not less than 3000 ppm.
According to the invention, in the low-temperature methanation reaction, the reaction temperature is, for example, 80 ℃, 100 ℃, 110 ℃, 130 ℃ or 140 ℃; a pressure of, for example, 2MPa, 3MPa, 4MPa or 5 MPa; the gas space velocity is, for example, 500h-1、800h-1、1000h-1、1500h-1、2000h-1、3000h-1、4000h-1、5000h-1Or 6000h-1(ii) a The inlet CO concentration is, for example, 200ppm, 500ppm, 1000ppm, 2000ppm or 3000 ppm.
Preferably, the reaction temperature is 80-130 ℃, the pressure is 2.0-4.0 MPa, and the gas space velocity is not more than 2000h-1And an inlet CO concentration of not more than 2000 ppm. More preferably, the space velocity of the gas is 200-2000 h-1。
According to the invention, the supported catalyst comprises a substrate and ruthenium supported thereon, the substrate comprises nitrogen-doped support carbon and nickel, and at least part of the nickel forms coordination bonds with lone-pair electrons on the nitrogen.
According to the invention, the matrix can be formed by carbonizing a polymeric carrier. Wherein the macromolecular carrier is a complex of a polymer containing imidazole side groups and a nickel precursor (nickel salt). In the high molecular carrier, coordination bonds are formed between nickel and lone-pair electrons on nitrogen atoms in imidazole side groups, after high-temperature carbonization, the polymer is dehydrogenated and weightlessly to form carbon, nitrogen elements on imidazole groups of the polymer partially remain due to the coordination with nickel, and then a nitrogen-doped carbon material is formed, and nickel salt is decomposed by utilizing the high temperature of carbonization, so that nickel-containing element products such as nickel oxide, nickel simple substances and the like can be generated. In the matrix, nitrogen in the carrier carbon can be combined with nickel through coordination bonds, so that the nickel is dispersed more uniformly.
According to the invention, in the polymer containing the imidazole side group, the molecular chain of the polymer contains a repeating structural unit, and the repeating structural unit contains the imidazole group so as to form the side chain of the whole molecule. The imidazole side group-containing polymer of the present invention is not particularly limited as long as a carbon support can be formed by carbonization. Preferably, the polymer containing pendant imidazole groups is selected from polyvinylimidazole or a copolymer of vinylimidazole and divinylbenzene. According to one embodiment, the polymer containing pendant imidazole groups is polyvinylimidazole. The polyvinylimidazoles may be prepared by methods well known in the art or may be obtained commercially. Generally, the polymerization degree (Xn) of the polyvinylimidazole can be 1000 to 10000, for example, the polyvinylimidazole with polymerization degree (Xn) of 2000 is obtained by taking AIBN as an initiator and toluene as a solvent and reacting in a hydrothermal kettle at 60 ℃.
In the invention, in the supported catalyst, the weight ratio of the matrix to the ruthenium content is 100 to (0.01-1.0), preferably 100 to (0.1-0.5); the nickel content in the matrix is 10-60 wt%, preferably 50-60 wt%. The ruthenium content was calculated from the charge and the nickel content was determined by X-ray fluorescence spectroscopy (XRF) analysis.
According to the present invention, the supported catalyst can be prepared by a method comprising the steps of:
1) dropwise adding the alcohol solution of the nickel precursor into the alcohol solution of the polymer containing the imidazole side group to perform a coordination reaction to obtain a reaction product of the polymer containing the imidazole side group and a complex of the nickel precursor;
2) separating the reaction product to obtain the complex serving as a high-molecular carrier;
3) carbonizing the polymer carrier to produce nitrogen-doped carrier carbon combined with nickel oxide;
4) carrying out hydrotreating on the carrier carbon in the step 3) to obtain a reduced matrix;
5) and (3) contacting the aqueous solution of the ruthenium precursor with the reduced substrate, and loading ruthenium on the substrate through adsorption and displacement reaction to obtain the supported catalyst.
According to the invention, the purpose of step 1) is to coordinate and combine the nickel precursor with the imidazole group in the polymer to form a complex of the polymer containing the imidazole side group and the nickel precursor. The coordination reaction is carried out under stirring conditions, and the stirring conditions comprise: the stirring speed is 50-600 rpm, preferably 200-400 rpm; the stirring time is 0.5 to 12 hours, preferably 3 to 8 hours.
The alcohol solvent is not particularly limited in the present invention, as long as it can form a homogeneous solution with the nickel precursor and can dissolve the polymer containing the imidazole side group. In general, the alcohol solvent may be selected from lower alcohols of C1 to C4, and examples thereof include methanol and ethanol.
In the alcohol solution of the polymer containing the imidazole side group, the concentration of the polymer containing the imidazole side group can be 0.01-0.1 g/mL.
The nickel precursor is not particularly limited in the present invention and can be selected with reference to the prior art. Typically, the nickel precursor may be selected from nickel nitrate or nickel chloride, preferably nickel nitrate. In the alcohol solution of the nickel precursor, the concentration of the nickel precursor can be 0.01-0.1 g/mL.
According to the present invention, the solid-liquid separation method of step 2) is well known in the art, and generally comprises processes of filtration, washing (for example, washing with toluene), drying, and the like. The drying is usually carried out under a vacuum condition, the drying temperature can be 60-80 ℃, and the drying time can be 4-8 hours.
According to the invention, in step 3), the carbonization can be carried out in an inert atmosphere, for example, in nitrogen, and the carbonization temperature can be 300-800 ℃; the carbonization time may be 1 to 12 hours. Preferably, the carbonization temperature is 400-600 ℃, and the carbonization time is 3-6 hours, so that the catalytic activity and the stability of the catalyst can be further improved.
According to the present invention, in step 4), the nickel oxide bonded to the carrier carbon can be reduced to elemental nickel by the hydrotreating, thereby obtaining a reduced matrix. The temperature of the hydrotreatment can be 400-500 ℃; the hydrotreating time may be 2 to 24 hours, preferably 4 to 12 hours.
According to the invention, in step 5), the reduced substrate can be dippedSoaking in the aqueous solution of the ruthenium precursor for 1-48 hours, preferably soaking the reduced substrate in the aqueous solution of the ruthenium precursor for 12-36 hours. By the soaking, the ruthenium precursor is dispersed and adsorbed on the substrate, and the ruthenium provided by the ruthenium precursor is provided by the nickel simple substance3+Reducing the nickel elementary substance into Ru, and oxidizing the nickel elementary substance into nickel metal ions, so that the ruthenium (Ru) is loaded on the substrate.
The ruthenium precursor is also not particularly limited by the present invention and may be selected with reference to the prior art. For example, the ruthenium precursor may be ruthenium nitrate or ruthenium chloride. The concentration of ruthenium in the aqueous solution of the ruthenium precursor may be (5X 10)-6)～(1×10-3)g/mL。
According to one embodiment, the concentration of the alcohol solution of the polymer containing the imidazole side group is 0.01-0.1 g/mL, the concentration of the alcohol solution of the nickel precursor is 0.01-0.1 g/mL, and the volume ratio of the dosage of the alcohol solution of the polymer containing the imidazole side group to the dosage of the alcohol solution of the nickel precursor is (0.2-20): 1; the amount of the ruthenium precursor is such that the weight ratio of the matrix to the ruthenium content in the supported catalyst is 100 to (0.01-1.0).
According to a specific embodiment, the supported catalyst is prepared by: under stirring, dripping a methanol solution of nickel nitrate into a methanol solution of polyvinyl imidazole, and keeping stirring for 0.5-12 hours to generate a complex serving as a polymer carrier; filtering the obtained reaction product, washing the reaction product with methanol for multiple times, drying the reaction product in vacuum at 60-80 ℃ for 4-8 hours, roasting the obtained solid powder in a nitrogen atmosphere at 300-800 ℃ for 1-12 hours (weight loss), treating the solid powder in hydrogen at 400-500 ℃ for 2-24 hours, soaking the solid subjected to hydrogenation treatment in an aqueous solution of a ruthenium precursor for 1-48 hours in the absence of air, performing adsorption and displacement (redox) reactions in the soaking process, filtering, washing the solid powder with deionized water to be nearly neutral to obtain a supported catalyst, and placing the supported catalyst in deionized water for storage.
The method for removing the trace carbon oxides has the advantages that the utilization rate of the active components of the adopted supported catalyst is high, the catalytic activity is high, the strength is high, and the trace CO in the hydrogen-rich gas can be removed to be below 3ppm at the temperature lower than 150 ℃. The method is suitable for further removing a very small amount of CO in devices such as dehydrogenation devices, pressure swing adsorption devices and the like.
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples.
Example 1
20mL of a methanol solution of polyvinyl imidazole (Xn: 2000) with a concentration of 0.05g/mL, and 10mL of a methanol solution of nickel nitrate with a concentration of 0.05 g/mL; dripping a methanol solution of nickel nitrate into a methanol solution of polyvinyl imidazole under the stirring state of the rotating speed of 300rpm, and then keeping stirring for 4 hours to generate a precipitate; filtering the stirred product, washing the obtained solid with methanol for 3 times, and then carrying out vacuum drying at 80 ℃ for 4 hours to obtain solid powder; and then the solid powder is roasted for 4h at 400 ℃ in a nitrogen atmosphere to obtain the N-Ni/C-1 matrix with the nickel loading of 54 wt%.
Taking 50g of N-Ni/C-1 matrix, reducing the N-Ni/C-1 matrix for 8 hours at 450 ℃, and placing the reduced matrix in 500mL of Ru under the condition of air isolation3+Aqueous solution (Ru)3+Is 1 × 10-4g/mL ruthenium nitrate aqueous solution) for 24 hours, loading Ru on a substrate through adsorption and displacement reaction, filtering, washing with deionized water to be nearly neutral to obtain a supported catalyst containing 0.1 wt% of Ru, placing the supported catalyst in the deionized water for storage, and marking the catalyst as CAT-1.
Measuring 10mL of CAT-1 catalyst, loading the CAT-1 catalyst into a stainless steel fixed bed reactor, introducing high-purity nitrogen with the flow rate of 300mL/min, heating to 120 ℃, and keeping for 2 hours; then, the reaction was switched to the feed gas reaction (containing 2000ppm CO) and other specific reaction conditions were as shown in Table 1. The gas composition after the reaction is analyzed by gas chromatography, the chromatographic detector is FID, and the CO content can be accurate to 1 ppm. Table 1 gives the detailed evaluation results. The smaller the outlet CO content (ppm), the higher the activity of the catalyst.
TABLE 1
Example 2
20mL of a methanol solution of polyvinyl imidazole (Xn: 2000) with a concentration of 0.05g/mL, and 10mL of a methanol solution of nickel nitrate with a concentration of 0.05 g/mL; under the state of stirring at the rotating speed of 300rpm, dripping a methanol solution of nickel nitrate into a methanol solution of polyvinyl imidazole, and keeping stirring for 3 hours to generate a precipitate; filtering the stirred product, washing the obtained solid with methanol for 3 times, and vacuum-drying at 80 ℃ for 4 hours to obtain solid powder; and then the solid powder is roasted for 3 hours at 600 ℃ in the nitrogen atmosphere to obtain the N-Ni/C-2 matrix with the nickel loading of 58 wt%.
Taking 50g of N-Ni/C-2 matrix, reducing the N-Ni/C-2 matrix for 4 hours at 500 ℃, and placing the N-Ni/C-2 matrix in 500mL of Ru under the condition of air isolation3+Aqueous solution (Ru)3+Is 3 x 10-4g/mL ruthenium nitrate aqueous solution) for 30 hours, loading Ru on a substrate through adsorption and displacement reaction, filtering, washing with deionized water to be nearly neutral to obtain a supported catalyst containing 0.3 wt% of Ru, and placing the supported catalyst in the deionized water for storage, wherein the catalyst is marked as CAT-2.
Measuring 10mL of CAT-2 catalyst, loading the CAT-2 catalyst into a stainless steel fixed bed reactor, introducing high-purity nitrogen with the flow rate of 300mL/min, heating to 110 ℃, and keeping for 2 hours; then, the reaction was switched to the reaction of raw material gas (containing 2000ppm CO), and other specific reaction conditions were as shown in Table 2. The gas composition after the reaction is analyzed by gas chromatography, the chromatographic detector is FID, and the CO content can be accurate to 1 ppm. Table 2 gives the detailed evaluation results.
TABLE 2
Example 3
Measuring 10mL of catalyst CAT-1, loading the catalyst CAT-1 into a stainless steel fixed bed reactor, introducing high-purity nitrogen with the flow rate of 300mL/min, heating to 140 ℃, and keeping for 2 hours; then, the reaction was switched to the feed gas reaction (containing 3000ppm CO) and other specific reaction conditions were as shown in Table 3. The gas composition after the reaction is analyzed by gas chromatography, the chromatographic detector is FID, and the CO content can be accurate to 1 ppm. Table 3 gives the detailed evaluation results.
TABLE 3
Example 4
Measuring 10mL of CAT-2 catalyst, loading the CAT-2 catalyst into a stainless steel fixed bed reactor, introducing high-purity nitrogen with the flow rate of 300mL/min, heating to 80 ℃, and keeping for 3 hours; then, the reaction was switched to the feed gas reaction (containing 200ppm CO), and other specific reaction conditions were as shown in Table 4. The gas composition after the reaction is analyzed by gas chromatography, the chromatographic detector is FID, and the CO content can be accurate to 1 ppm. Table 4 gives the detailed evaluation results.
TABLE 4
Comparative example 1
The traditional load type Ru/Al is prepared by adopting an equivalent impregnation method2O3. Specifically, 10mL of Ru was taken3+Adding ruthenium nitrate water solution with concentration of 0.003g/mL into 10g of macroporous alumina carrier (carrier water absorption rate is 105%), equivalently impregnating, filtering, drying the obtained solid at 110 ℃ for 12 hours, and roasting at 450 ℃ in air for 4 hours to obtain Ru/Al containing 0.3 wt% of Ru2O3Catalyst, noted CAT-D1.
Weighing 10mL of catalyst CAT-D1, loading into a stainless steel fixed bed reactor, and reducing for 2 hours at 350 ℃ by using hydrogen; then, the reaction was switched to the reaction of raw material gas (containing CO 2000ppm), and other specific reaction conditions were as shown in Table 5. The gas composition after the reaction is analyzed by gas chromatography, the chromatographic detector is FID, and the CO content can be accurate to 1 ppm. Table 5 gives the detailed evaluation results.
TABLE 5
Comparative example 2
The nickel metal catalyst supported on alumina was prepared by a tablet pressing method. 1kg of basic nickel carbonate NiCO3·2Ni(OH)2·4H2Mixing O with a certain amount of pseudo-boehmite, kneading, sieving to obtain small particles, drying at 160 ℃ for 24 hours, roasting at 400 ℃ for 4 hours, tabletting to obtain cylindrical catalyst particles with the diameter of phi 3mm multiplied by 3mm, reducing with hydrogen at 450 ℃ for 24 hours, and marking as CAT-D2, wherein the catalyst particles contain 56 wt% of nickel metal.
Weighing 10mL of catalyst CAT-D2, loading the catalyst CAT-D2 into a stainless steel fixed bed reactor, and reducing the catalyst at 240 ℃ by using hydrogen to remove oxides on the surface for 2 hours; then the reaction was switched to the reaction of raw material gas containing CO 2000ppm, and other specific reaction conditions were as shown in Table 6. The gas composition after the reaction is analyzed by gas chromatography, the chromatographic detector is FID, and the CO content can be accurate to 1 ppm. Table 6 gives the detailed evaluation results.
TABLE 6
The results of the comparative examples 1-4 and 1-2 show that the catalyst adopted by the method can remove trace CO to below 3ppm at the temperature of 80-140 ℃, and the catalyst can keep higher activity along with the reaction operation; the activity of the catalyst in the comparative example 1-2 at 80-140 ℃ is obviously lower than that of the catalyst in the example 1-4, the purification and removal of CO cannot be realized, and the CO removal effect is gradually poor along with the reaction operation. In conclusion, the method can effectively and effectively remove trace CO in the hydrogen-rich gas at lower temperature, and the catalyst has higher stability.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (10)
1. A method for removing trace CO at low temperature is characterized by comprising the following steps: in a fixed bed reactor, the hydrogen-rich gas containing carbon oxides is contacted with a supported catalyst at the reaction temperature of 80-140 ℃, the pressure of 0.1-7.0 MPa and the gas space velocity of not more than 6000h-1Carrying out methanation reaction under the condition that the concentration of CO at the inlet is not more than 3000 ppm; wherein the supported catalyst comprises a substrate and ruthenium supported thereon, the substrate comprises nitrogen-doped support carbon and nickel, and at least part of the nickel forms coordination bonds with lone-pair electrons on the nitrogen.
2. The method of claim 1, wherein the supported catalyst comprises the base and the ruthenium in a weight ratio of 100: (0.01-1.0); the nickel content in the matrix is 10-60 wt%.
3. The method of claim 1 or 2, wherein the matrix is formed by carbonizing a polymeric support, which is a complex of a polymer containing pendant imidazole groups and a nickel precursor.
4. The method of claim 3, wherein the polymer containing pendant imidazole groups is selected from polyvinylimidazole or a vinylimidazole-divinylbenzene copolymer.
5. The process of claim 3 or 4, wherein the supported catalyst is prepared by a process comprising:
1) dropwise adding the alcohol solution of the nickel precursor into the alcohol solution of the polymer containing the imidazole side group to perform a coordination reaction to obtain a reaction product of the polymer containing the imidazole side group and a complex of the nickel precursor;
2) separating the reaction product to obtain the complex serving as a high-molecular carrier;
3) carbonizing the polymer carrier to produce nitrogen-doped carrier carbon combined with nickel oxide;
4) carrying out hydrotreating on the carrier carbon in the step 3) to obtain a reduced matrix;
5) enabling the aqueous solution of the ruthenium precursor to contact the reduced substrate, and loading ruthenium on the substrate through adsorption and displacement reaction to obtain a supported catalyst;
preferably, the concentration of the alcohol solution of the polymer containing the imidazole side group is 0.01-0.1 g/mL, the concentration of the alcohol solution of the nickel precursor is 0.01-0.1 g/mL, and the volume ratio of the usage amount of the alcohol solution of the polymer containing the imidazole side group to the usage amount of the alcohol solution of the nickel precursor is (0.2-20): 1; the dosage of the ruthenium precursor is such that the weight ratio of the matrix to the ruthenium content in the obtained supported catalyst is 100: 0.01-1.0.
6. The method according to claim 5, wherein in step 1), the coordination reaction is carried out under stirring conditions comprising: the stirring speed is 50-600 rpm, preferably 200-400 rpm; the stirring time is 0.5 to 12 hours, preferably 3 to 8 hours.
7. The method according to claim 5 or 6, wherein in step 3), the carbonization conditions comprise: the temperature is 300-800 ℃, preferably 400-600 ℃; the time is 1 to 12 hours, preferably 3 to 6 hours.
8. The process of any one of claims 5-7, wherein the hydrotreating conditions in step 4) include: the temperature is 400-500 ℃, and the time is 2-24 hours, preferably 4-12 hours.
9. The method according to any one of claims 5-8, wherein step 5) comprises: and soaking the reduced substrate for 1-48 hours by using an aqueous solution of a ruthenium precursor, preferably for 12-36 hours.
10. The method of claim 1, wherein the reaction temperature is 80-130 ℃, the pressure is 2.0-4.0 MPa, and the gas space velocity is not more than 2000h-1And an inlet CO concentration of not more than 2000 ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011157519.2A CN114477089B (en) | 2020-10-26 | 2020-10-26 | Method for removing trace CO at low temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011157519.2A CN114477089B (en) | 2020-10-26 | 2020-10-26 | Method for removing trace CO at low temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114477089A true CN114477089A (en) | 2022-05-13 |
| CN114477089B CN114477089B (en) | 2023-10-27 |
Family
ID=81471394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011157519.2A Active CN114477089B (en) | 2020-10-26 | 2020-10-26 | Method for removing trace CO at low temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114477089B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114832859A (en) * | 2022-06-07 | 2022-08-02 | 浙江天蓝环保技术股份有限公司 | Catalyst for purifying CVOCs and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4695446A (en) * | 1982-12-22 | 1987-09-22 | Studiengesellschaft Kohle Mbh | Method of separating and purifying hydrogen |
| US20030012996A1 (en) * | 2001-06-26 | 2003-01-16 | Stefan Bitterlich | Fuel cell |
| CN102481553A (en) * | 2009-07-03 | 2012-05-30 | 宫田清蔵 | Oxidation catalyst, reduction catalyst, and catalyst for purging exhaust gas |
| CN104512864A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Method for removing micro-scale carbon monoxide at low temperature |
| CN105195138A (en) * | 2015-09-17 | 2015-12-30 | 福州大学 | Visible-light response supported-type Ru catalyst |
| CN107043089A (en) * | 2017-05-19 | 2017-08-15 | 福州大学化肥催化剂国家工程研究中心 | A kind of isobaric technique of the ammonia synthesis co-production containing carbon chemicals |
| CN110404573A (en) * | 2019-06-28 | 2019-11-05 | 中国科学技术大学 | A kind of preparation method and application of extra small palladium-base alloy material |
| CN110586155A (en) * | 2019-08-27 | 2019-12-20 | 浙江工业大学 | Application of carbon nano tube embedded metal particle catalyst in CO selective oxidation purification reaction in hydrogen-rich gas |
-
2020
- 2020-10-26 CN CN202011157519.2A patent/CN114477089B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4695446A (en) * | 1982-12-22 | 1987-09-22 | Studiengesellschaft Kohle Mbh | Method of separating and purifying hydrogen |
| US20030012996A1 (en) * | 2001-06-26 | 2003-01-16 | Stefan Bitterlich | Fuel cell |
| CN102481553A (en) * | 2009-07-03 | 2012-05-30 | 宫田清蔵 | Oxidation catalyst, reduction catalyst, and catalyst for purging exhaust gas |
| CN104512864A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Method for removing micro-scale carbon monoxide at low temperature |
| CN105195138A (en) * | 2015-09-17 | 2015-12-30 | 福州大学 | Visible-light response supported-type Ru catalyst |
| CN107043089A (en) * | 2017-05-19 | 2017-08-15 | 福州大学化肥催化剂国家工程研究中心 | A kind of isobaric technique of the ammonia synthesis co-production containing carbon chemicals |
| CN110404573A (en) * | 2019-06-28 | 2019-11-05 | 中国科学技术大学 | A kind of preparation method and application of extra small palladium-base alloy material |
| CN110586155A (en) * | 2019-08-27 | 2019-12-20 | 浙江工业大学 | Application of carbon nano tube embedded metal particle catalyst in CO selective oxidation purification reaction in hydrogen-rich gas |
Non-Patent Citations (2)
| Title |
|---|
| WILLIAMSON, DL ET AL.: "Highly Selective, Iron-Driven CO2 Methanation", 《ENERGY TECHNOLOGY》, vol. 7, no. 2, pages 294 - 306 * |
| 德国巴斯夫欧洲公司等: "用于一氧化碳选择性甲烷化的钌、铼基催化剂", 《齐鲁石油化工》, vol. 46, no. 02, pages 147 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114832859A (en) * | 2022-06-07 | 2022-08-02 | 浙江天蓝环保技术股份有限公司 | Catalyst for purifying CVOCs and preparation method thereof |
| CN114832859B (en) * | 2022-06-07 | 2024-02-20 | 浙江天蓝环保技术股份有限公司 | CVOCs purifying catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114477089B (en) | 2023-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103736487A (en) | Method for preparing supported metal catalyst through solvent-free mechanical mixing | |
| CN107159287B (en) | Pt/α-MoC1-xApplication of supported catalyst in catalytic hydrogenation reaction | |
| CN113578316A (en) | Preparation of supported porous nano platinum-ruthenium alloy catalyst and application of supported porous nano platinum-ruthenium alloy catalyst in preparation of chloroaniline by hydrogenation of chloronitrobenzene | |
| CN114477089B (en) | Method for removing trace CO at low temperature | |
| CN114497630B (en) | Organic liquid material for hydrogen storage, catalytic hydrogen storage system and hydrogen storage method | |
| CN114477088B (en) | Method for removing CO | |
| CN110732327A (en) | carbon material-coated nickel catalyst and method for preparing primary amine compound by using same | |
| CN114950471B (en) | Nickel-based catalyst, preparation method thereof and application thereof in selective hydrogenation of acetylene in ethylene | |
| CN114345336B (en) | Transition metal molybdenum modified palladium silver-alumina catalyst, and preparation method and application thereof | |
| CN106928004B (en) | A kind of selective hydrogenation method of C 3 fractions | |
| CN112844398B (en) | Catalyst for hydrogenation of carbon four-superimposed product and preparation method thereof | |
| CN111974405A (en) | CO selective methanation method | |
| CN113385187A (en) | Pyrolysis gas deoxidation catalyst and preparation method and application thereof | |
| CN114471608B (en) | Method for refining and purifying diethylene glycol through hydrofining | |
| CN113952957A (en) | Nickel series hydrogenation catalyst and preparation method and application thereof | |
| CN114477090B (en) | Method for removing carbon oxides in crude hydrogen gas | |
| CN115779895B (en) | Perovskite catalyst and preparation method and application thereof | |
| CN114452964B (en) | Dual-function catalyst and preparation method and application thereof | |
| CN114011432B (en) | 3-hydroxy propanal hydrogenation catalyst and its preparation method and use | |
| CN113042025B (en) | Non-metal porous carbon material catalyst prepared by taking saccharides as raw materials and preparation method and application thereof | |
| CN109529920B (en) | Supported titanium boride catalyst for light alkane isomerization and preparation method and using method thereof | |
| CN118122356A (en) | Carbon two-selective hydrogenation catalyst under high-carbon four-working condition and preparation method thereof | |
| CN114713187A (en) | Liquid light hydrocarbon component adsorption dearsenic agent and preparation method thereof | |
| CN1429889A (en) | Selective hydrogenation catalyst | |
| CN106928012A (en) | A kind of back end hydrogenation technique of carbon two removes alkynes method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |