CN114477089B - Method for removing trace CO at low temperature - Google Patents
Method for removing trace CO at low temperature Download PDFInfo
- Publication number
- CN114477089B CN114477089B CN202011157519.2A CN202011157519A CN114477089B CN 114477089 B CN114477089 B CN 114477089B CN 202011157519 A CN202011157519 A CN 202011157519A CN 114477089 B CN114477089 B CN 114477089B
- Authority
- CN
- China
- Prior art keywords
- nickel
- hours
- reaction
- matrix
- ruthenium
- 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.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000003054 catalyst Substances 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 45
- 239000007789 gas Substances 0.000 claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 30
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 229910052757 nitrogen 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
- 229910002090 carbon oxide Inorganic materials 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 51
- 239000002243 precursor Substances 0.000 claims description 32
- 239000011159 matrix material Substances 0.000 claims description 29
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000003763 carbonization Methods 0.000 claims description 12
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 238000006073 displacement reaction Methods 0.000 claims description 5
- 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
- 238000002791 soaking Methods 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims 1
- 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
- 238000005406 washing Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000001914 filtration 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 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
- 230000000694 effects Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 4
- 125000002883 imidazolyl group Chemical group 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000011068 loading method Methods 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 group [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 4
- 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 3
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 3
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 3
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 3
- 108091006231 SLC7A2 Proteins 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000126 substance Substances 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
- 229910018072 Al 2 O 3 Inorganic materials 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
- 125000004432 carbon atom Chemical group C* 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
- 238000002955 isolation Methods 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
- 150000002739 metals Chemical class 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
- 229910000008 nickel(II) carbonate Inorganic materials 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 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
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying 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
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 oxide is contacted with a supported catalyst, and the reaction temperature is 80-140 ℃, the pressure is 0.1-7.0 MPa, and the gas space velocity is less than 6000h ‑1 Methanation reaction is carried out 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 thereon, the substrate comprises nitrogen-doped carrier carbon and nickel, and a coordination bond is formed between at least part of the nickel and lone pair electrons on the nitrogen. The method of the invention enables methanation reaction to be carried out at a low temperature of less than 150 ℃ by adopting the supported catalyst, and can remove CO content in hydrogen-rich gas to below 3 ppm.
Description
Technical Field
The invention belongs to the field of gas purification, and in particular relates to a method for removing trace CO at a 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 reactions. Compared with other noble metal catalysts, the supported Ru catalyst has a relatively low price and a relatively good industrial application prospect.
At present, research on supported Ru catalysts mainly focuses on catalyst preparation and application, and catalysts required by hydrogenation or dehydrogenation reactions are obtained by using different carriers, different Ru precursors, different preparation methods and the like. For example, alumina-supported Ru catalysts are prepared by impregnation with an alumina carrier; the Ru catalyst supported by the coconut shell carbon is prepared by using a coconut shell carbon carrier through an impregnation method; titanium dioxide is used as a titanium dioxide carrier, and the titanium dioxide loaded Ru catalyst is obtained through methods of dipping, spraying and the like, and can be used for hydrogenation and the like. However, the supported Ru catalyst has problems such as low noble metal utilization efficiency, low reactivity, and poor practical reaction stability due to its preparation method, composition, structure, and the like.
Methanation catalysts are mainly used for deep removal of trace amounts of carbon oxides (mainly CO) in crude hydrogen in ethylene units or ammonia synthesis units, and generally require that the carbon oxides in the crude hydrogen be removed to less than 5ppm by a methanation reactor. The methanation catalyst mainly comprises a Ru catalyst and a Ni catalyst. Currently, the commonly used methanation catalyst is a Ni catalyst. Ni catalysts are also classified into high temperature catalysts and low temperature catalysts. In ethylene units, the high temperature catalyst typically operates at a temperature of 280 to 350 ℃ and the low temperature catalyst typically operates at a temperature of 150 to 200 ℃. The low-temperature methanation catalyst has the advantages of energy conservation, environmental protection, safety and economy, so that the high-temperature methanation process is gradually replaced.
The reaction temperature of the existing low-temperature methanation catalyst is not less than 150 ℃. The reaction at the temperature lower than 150 ℃ has extremely high requirements on the activity of the catalyst, and the traditional methanation catalyst needs high-temperature roasting in the preparation process, so that a great amount of metal particles are sintered due to the high-temperature roasting, the utilization rate of active metals is reduced, and finally the reaction activity of the catalyst is low, so that the methanation reaction at the temperature lower than 150 ℃ cannot be satisfied.
Therefore, for low temperature methanation reactions, the development of a catalyst that is highly active at lower temperatures (less than 150 ℃) is of great importance for methanation processes.
Disclosure of Invention
The invention aims to provide a method for removing trace CO at a low temperature. The method of the invention enables methanation reaction to be carried out at a low temperature of less than 150 ℃ by adopting the supported catalyst, and can remove CO content in hydrogen-rich gas to below 3 ppm.
In order to achieve the above object, the present invention provides a method for removing trace CO at low temperature, the method comprising: in a fixed bed reactor, contacting a hydrogen-rich gas containing carbon oxide with a supported catalyst at a reaction temperature of 80-140 ℃ and a pressure of 0.1-7.0 MPa, and a gas space velocity of not more than 6000h -1 Methanation reaction is carried out under the condition that the concentration of CO at the inlet is not more than 3000 ppm; wherein the supported catalyst comprises a matrix and ruthenium supported thereon, the matrix comprises nitrogen-doped carrier carbon and nickel, and a coordination bond is formed between at least part of nickel and lone pair electrons on nitrogen.
The invention provides a low-temperature methanation removal method of trace CO in hydrogen-rich gas, wherein in the adopted supported catalyst, a matrix is nitrogen-doped carrier carbon obtained by high-molecular carbonization and is combined with nickel, coordination bonds exist between nitrogen and metallic nickel in the matrix, so that nickel is more uniformly dispersed, a valence electronic structure is changed due to the coordination bonds, the utilization rate of an active component is high by combining with supported ruthenium metal, the trace CO in the hydrogen-rich gas can be removed to 3ppm or even below 1ppm at a 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 specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
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 subjected to a low temperature methanation reaction.
The source of the crude hydrogen gas (gas to be purified) containing carbon oxides is not particularly limited in the present invention, and for example, the crude hydrogen gas produced by a process such as ethylene cracking may be used.
According to the invention, the reaction temperature of the low-temperature methanation reaction is 80-140 ℃, the pressure is 0.1-7.0 MPa, and the gas space velocity is not less than 6000h -1 The inlet CO concentration is not less than 3000ppm.
According to the invention, in the low temperature methanation reaction, the reaction temperature is, for example, 80 ℃, 100 ℃, 110 ℃, 130 ℃, or 140 ℃; the pressure is, for example, 2MPa, 3MPa, 4MPa or 5MPa; the gas space velocity is, for example, 500h -1 、800h -1 、1000h -1 、1500h -1 、2000h -1 、3000h -1 、4000h -1 、5000h -1 Or 6000h -1 The method comprises the steps of carrying out a first treatment on the surface of the The inlet CO concentration is, for example, 200ppm, 500ppm, 1000ppm, 2000ppm or 3000ppm.
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 -1 The inlet CO concentration is no greater than 2000ppm. More preferably, the gas space velocity is 200 to 2000h -1 。
According to the invention, the supported catalyst comprises a matrix and ruthenium supported thereon, the matrix comprising nitrogen-doped support carbon and nickel, and coordination bonds being formed between at least part of the nickel and lone pair electrons on the nitrogen.
According to the invention, the matrix can be formed by carbonization of a polymeric support. Wherein the high molecular carrier is a complex of a polymer containing imidazole side groups and a nickel precursor (nickel salt). In the polymer carrier, coordination bonds are formed between nickel and lone pair electrons on nitrogen atoms in imidazole side groups, after high-temperature carbonization, polymers are dehydrogenated and weightlessly formed into carbon, nitrogen elements on imidazole groups of the polymers are partially reserved due to coordination with nickel, then nitrogen-doped carbon materials are formed, nickel salts are decomposed by utilizing carbonized high temperature, and 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 imidazole side groups, the molecular chain of the polymer comprises a repeated structural unit, and the repeated structural unit comprises imidazole groups so as to form side chains of the whole molecule. The polymer containing imidazole side groups is not particularly limited in the present invention, as long as the carbon support can be formed by carbonization. Preferably, the polymer containing imidazole side 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, and are also commercially available. In general, the polymerization degree (Xn) of the polyvinylimidazole may be 1000 to 10000, for example, using AIBN as an initiator and toluene as a solvent, and reacting at 60 ℃ in a hydrothermal kettle to obtain polyvinylimidazole having a polymerization degree (Xn) of 2000.
In the present invention, the weight ratio of the base to the ruthenium content in the supported catalyst is 100: (0.01-1.0), preferably 100: (0.1-0.5); the nickel content of the matrix is 10 to 60 wt.%, preferably 50 to 60 wt.%. The ruthenium content was calculated from the feed amount and the nickel content was measured by X-ray fluorescence spectroscopy (XRF) analysis.
According to the invention, the supported catalyst can be prepared by a process comprising the steps of:
1) Adding an alcohol solution of a nickel precursor into an alcohol solution of a polymer containing imidazole side groups in a dropwise manner to carry out a coordination reaction, so as to obtain a reaction product of a complex of the polymer containing imidazole side groups and the nickel precursor;
2) Separating the reaction product to obtain the complex serving as a high molecular carrier;
3) Carbonizing the polymer carrier to generate nitrogen-doped carrier carbon combined with nickel oxide;
4) Hydrotreating the carrier carbon of the step 3) to obtain a reduced matrix;
5) And (3) enabling the aqueous solution of the ruthenium precursor to contact with the reduced matrix, and carrying out adsorption and displacement reaction to enable ruthenium to be loaded on the matrix, so as 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 groups in the polymer to form a complex of the polymer containing imidazole side groups and the nickel precursor. The coordination reaction is carried out under stirring conditions including: 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 dissolve the polymer containing imidazole side groups. In general, the alcohol solvent may be selected from lower alcohols having 1 to 4 carbon atoms, and may be methanol, ethanol, or the like.
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 and may 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 includes filtration, washing (e.g., washing with toluene), drying, and the like. The drying is usually carried out under vacuum conditions, the drying temperature may be 60 to 80 ℃, and the drying time may be 4 to 8 hours.
According to the invention, in step 3), the carbonization may be carried out in an inert atmosphere, for example in nitrogen, and the carbonization temperature may 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 stability of the catalyst can be further improved.
According to the invention, in step 4), the nickel oxide bound to the support carbon can be reduced to elemental nickel by means of the hydrotreatment, thus 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 may be immersed in the aqueous solution of the ruthenium precursor for 1 to 48 hours, preferably the reduced substrate is immersed in the ruthenium precursorAnd the precursor is in aqueous solution for 12 to 36 hours. Through the soaking, the ruthenium precursor is dispersed and adsorbed on the matrix, and the Ru provided by the ruthenium precursor is obtained by utilizing the simple substance of nickel 3+ Reduced to Ru while the elemental nickel is oxidized to nickel metal ions, so that ruthenium (Ru) is supported on the substrate.
The ruthenium precursor is also not particularly limited in the present invention, and can be selected with reference to the prior art. For example, the ruthenium precursor can be ruthenium nitrate or ruthenium chloride. The concentration of ruthenium in the aqueous solution of the ruthenium precursor may be (5×10) -6 )～(1×10 -3 )g/mL。
According to one embodiment, the concentration of the alcoholic solution of the polymer with imidazole side groups is 0.01-0.1 g/mL, the concentration of the alcoholic solution of the nickel precursor is 0.01-0.1 g/mL, and the volume ratio of the alcoholic solution of the polymer with imidazole side groups to the alcoholic solution of the nickel precursor is (0.2-20) to 1; the ruthenium precursor is used in such an amount that the weight ratio of the base to the ruthenium content in the resulting supported catalyst is 100:0.01-1.0.
According to a specific embodiment, the supported catalyst is prepared by the following method: dropwise adding a methanol solution of nickel nitrate into a methanol solution of polyvinyl imidazole under stirring, and keeping stirring for 0.5-12 hours to generate a complex serving as a high 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 at 300-800 ℃ for 1-12 hours (weight loss) in nitrogen atmosphere, then treating the solid powder at 400-500 ℃ for 2-24 hours in hydrogen, then soaking the hydrotreated solid in an aqueous solution of ruthenium precursor for 1-48 hours under the condition of isolating air, carrying out adsorption and displacement (redox) reaction in the soaking process, filtering the reaction product, washing the reaction product to be nearly neutral by using deionized water, and storing the reaction product in deionized water.
The method for removing trace carbon oxides provided by the invention 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 trace CO in hydrogen-rich gas can be removed to below 3ppm at the temperature lower than 150 ℃. The method is suitable for further removing the minimum CO in the devices such as dehydrogenation, pressure swing adsorption and the like.
The present invention will be further described with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
Taking 20mL of methanol solution with the concentration of 0.05g/mL of polyvinyl imidazole (Xn=2000), and taking 10mL of methanol solution with the concentration of 0.05g/mL of nickel nitrate; dripping a methanol solution of nickel nitrate into a methanol solution of polyvinyl imidazole under the stirring condition of 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 drying the solid in vacuum at 80 ℃ for 4 hours to obtain solid powder; and roasting the solid powder in a nitrogen atmosphere at 400 ℃ for 4 hours to obtain the N-Ni/C-1 matrix with the nickel loading of 54 weight percent.
Taking 50g of N-Ni/C-1 matrix, reducing with hydrogen at 450 ℃ for 8 hours, placing the reduced matrix in 500mL Ru under the condition of isolating air 3+ Aqueous solution (Ru) 3+ Is 1X 10 -4 g/mL ruthenium nitrate aqueous solution), loading Ru on a substrate by adsorption and displacement reaction, filtering, washing with deionized water to be nearly neutral to obtain a supported catalyst containing 0.1wt% Ru, placing in deionized water for preservation, and recording the catalyst as CAT-1.
10mL of catalyst CAT-1 is measured and is filled into a stainless steel fixed bed reactor, high-purity nitrogen is introduced, the nitrogen flow is 300mL/min, and the temperature is raised to 120 ℃ and maintained for 2 hours; then, the reaction was switched to the feed gas reaction (containing 2000ppm CO), and other specific reaction conditions are shown in Table 1. The gas composition after the reaction was analyzed by gas chromatography, the chromatographic detector was FID, and the CO content could be accurate to 1ppm. The detailed evaluation results are given in table 1. The smaller the outlet CO content (ppm) the higher the activity of the catalyst.
TABLE 1
Example 2
Taking 20mL of methanol solution with the concentration of 0.05g/mL of polyvinyl imidazole (Xn=2000), and taking 10mL of methanol solution with the concentration of 0.05g/mL of nickel nitrate; dripping the methanol solution of nickel nitrate into the methanol solution of polyvinyl imidazole under the stirring state of rotating speed 300rpm, and keeping stirring for 3 hours to generate 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 roasting the solid powder in a nitrogen atmosphere at 600 ℃ for 3 hours to obtain the N-Ni/C-2 matrix with 58 weight percent of nickel loading.
50g of N-Ni/C-2 matrix is taken and reduced with hydrogen at 500 ℃ for 4 hours, and is placed in 500mL Ru under the condition of air isolation 3+ Aqueous solution (Ru) 3+ Is 3X 10 -4 g/mL ruthenium nitrate aqueous solution) for 30 hours, loading Ru on a matrix through adsorption and displacement reaction, filtering, washing to be nearly neutral by using deionized water to obtain a supported catalyst containing 0.3wt% Ru, and placing the supported catalyst in the deionized water for preservation, wherein the catalyst is named CAT-2.
10mL of CAT-2 catalyst is measured and filled into a stainless steel fixed bed reactor, high-purity nitrogen is introduced, the nitrogen flow is 300mL/min, and the temperature is raised to 110 ℃ and maintained for 2 hours; then, the reaction was switched to feed gas (2000 ppm CO) and other specific reaction conditions are shown in Table 2. The gas composition after the reaction was analyzed by gas chromatography, the chromatographic detector was FID, and the CO content could be accurate to 1ppm. The detailed evaluation results are given in table 2.
TABLE 2
Example 3
10mL of catalyst CAT-1 is measured and is filled into a stainless steel fixed bed reactor, high-purity nitrogen is introduced, the nitrogen flow is 300mL/min, and the temperature is raised to 140 ℃ and maintained for 2 hours; then, the reaction was switched to feed gas reaction (containing 3000ppm CO), and other specific reaction conditions are shown in Table 3. The gas composition after the reaction was analyzed by gas chromatography, the chromatographic detector was FID, and the CO content could be accurate to 1ppm. The detailed evaluation results are given in table 3.
TABLE 3 Table 3
Example 4
10mL of catalyst CAT-2 is measured and is filled into a stainless steel fixed bed reactor, high-purity nitrogen is introduced, the nitrogen flow is 300mL/min, and the temperature is raised to 80 ℃ and maintained for 3 hours; then, the reaction was switched to the feed gas reaction (containing 200ppm CO), and other specific reaction conditions are shown in Table 4. The gas composition after the reaction was analyzed by gas chromatography, the chromatographic detector was FID, and the CO content could be accurate to 1ppm. The detailed evaluation results are given in table 4.
TABLE 4 Table 4
Comparative example 1
The equivalent impregnation method is adopted to prepare the traditional load Ru/Al 2 O 3 . Specifically, 10mL Ru was taken 3+ Ruthenium nitrate aqueous solution with concentration of 0.003g/mL is added with 10g macroporous alumina carrier (carrier water absorption rate is 105%), after equal impregnation, the obtained solid is filtered, dried for 12 hours at 110 ℃, and baked for 4 hours at 450 ℃ in air, thus obtaining Ru/Al containing 0.3wt% Ru 2 O 3 The catalyst was designated CAT-D1.
10mL of catalyst CAT-D1 is measured and is filled into a stainless steel fixed bed reactor, and is reduced by hydrogen for 2 hours at 350 ℃; then, the reaction was switched to feed gas (CO 2000 ppm) and other specific reaction conditions are shown in Table 5. The gas composition after the reaction was analyzed by gas chromatography, the chromatographic detector was FID, and the CO content could be accurate to 1ppm. The detailed evaluation results are given in table 5.
TABLE 5
Comparative example 2
The alumina-supported nickel metal catalyst is prepared by a tabletting method. Firstly, 1kg of basic nickel carbonate NiCO 3 ·2Ni(OH) 2 ·4H 2 After mixing and kneading O and a certain amount of pseudo-boehmite, sieving to form small particles, drying at 160 ℃ for 24 hours, roasting at 400 ℃ for 4 hours, tabletting and forming to form cylindrical catalyst particles with phi 3mm multiplied by 3mm, reducing with hydrogen at 450 ℃ for 24 hours, and recording as CAT-D2, wherein the nickel metal contains 56 weight percent.
10mL of catalyst CAT-D2 is measured and is filled into a stainless steel fixed bed reactor, firstly, the catalyst is reduced by hydrogen at 240 ℃ to remove oxide on the surface, and the reduction time is 2 hours; then, the reaction was switched to a feed gas containing 2000ppm CO, and other specific reaction conditions are shown in Table 6. The gas composition after the reaction was analyzed by gas chromatography, the chromatographic detector was FID, and the CO content could be accurate to 1ppm. The detailed evaluation results are given in table 6.
TABLE 6
As can be seen from the results of comparative examples 1-4 and comparative examples 1-2, the catalyst used in the method of the invention can realize the removal of trace CO to below 3ppm at 80-140 ℃, and the catalyst can maintain higher activity along with the operation of the reaction; the activity of the catalyst of comparative example 1-2 is obviously lower than that of the catalyst of example 1-4 at 80-140 ℃, the purification and removal of CO can not be realized, and the CO removal effect gradually deteriorates along with the operation of the reaction. In summary, the method of the invention can effectively and effectively remove trace CO in the hydrogen-rich gas at a lower temperature, and the stability of the catalyst is higher.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or 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 various embodiments described.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (15)
1. A method for low temperature removal of trace CO, the method comprising: in a fixed bed reactor, contacting a hydrogen-rich gas containing carbon oxide with a supported catalyst at a reaction temperature of 80-140 ℃ and a pressure of 0.1-7.0 MPa, and a gas space velocity of not more than 6000h -1 Methanation reaction is carried out under the condition that the concentration of CO at the inlet is not more than 3000 ppm; wherein the supported catalyst comprises a matrix and ruthenium supported thereon, the matrix comprises nitrogen-doped carrier carbon and nickel, and a coordination bond is formed between at least part of nickel and lone pair electrons on nitrogen.
2. The method of claim 1, wherein the weight ratio of the matrix to ruthenium content in the supported catalyst is 100: (0.01-1.0); the nickel content of the matrix is 10 to 60 wt%.
3. The method of claim 1, wherein the matrix is formed by carbonization of a polymeric carrier that is a complex of a polymer containing imidazole side groups and a nickel precursor.
4. A method according to claim 3, wherein the polymer containing imidazole side groups is selected from a polyvinyl imidazole or a vinyl imidazole-divinylbenzene copolymer.
5. The method of claim 3 or 4, wherein the supported catalyst is prepared by a process comprising the steps of:
1) Adding an alcohol solution of a nickel precursor into an alcohol solution of a polymer containing imidazole side groups in a dropwise manner to carry out a coordination reaction, so as to obtain a reaction product of a complex of the polymer containing imidazole side groups and the nickel precursor;
2) Separating the reaction product to obtain the complex serving as a high molecular carrier;
3) Carbonizing the polymer carrier to generate nitrogen-doped carrier carbon combined with nickel oxide;
4) Hydrotreating the carrier carbon of the step 3) to obtain a reduced matrix;
5) And (3) enabling the aqueous solution of the ruthenium precursor to contact with the reduced matrix, and carrying out adsorption and displacement reaction to enable ruthenium to be loaded on the matrix, so as to obtain the supported catalyst.
6. The method of claim 5, wherein the imidazole-pendant group-containing polymer has an alcohol solution concentration of 0.01-0.1 g/mL, the nickel precursor has an alcohol solution concentration of 0.01-0.1 g/mL, and the volume ratio of the imidazole-pendant group-containing polymer alcohol solution to the nickel precursor alcohol solution is (0.2-20) to 1; the ruthenium precursor is used in such an amount that the weight ratio of the base to the ruthenium content in the resulting supported catalyst is 100:0.01-1.0.
7. The method according to claim 5, wherein in step 1), the coordination reaction is performed under stirring conditions including: the stirring speed is 50-600 rpm; the stirring time is 0.5-12 hours.
8. The method of claim 7, wherein the agitation conditions comprise: the stirring speed is 200-400 rpm, and the stirring time is 3-8 hours.
9. The method of claim 5, wherein in step 3), the carbonization conditions include: the temperature is 300-800 ℃; the time is 1-12 hours.
10. The method of claim 9, wherein the carbonization conditions comprise: the temperature is 400-600 ℃ and the time is 3-6 hours.
11. The process of claim 5, wherein in step 4), the hydrotreating conditions include: the temperature is 400-500 ℃ and the time is 2-24 hours.
12. The process of claim 11, wherein the hydrotreating time is from 4 to 12 hours.
13. The method of claim 5, wherein step 5) comprises: soaking the reduced matrix for 1-48 hours by using an aqueous solution of ruthenium precursor.
14. The method of claim 13, wherein the reduced substrate is immersed in an aqueous solution of ruthenium precursor for 12-36 hours.
15. The process according to 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 -1 The inlet CO concentration is no greater than 2000ppm.
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 CN114477089A (en) | 2022-05-13 |
| CN114477089B true 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) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (7)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10130783A1 (en) * | 2001-06-26 | 2003-01-02 | Basf Ag | fuel cell |
-
2020
- 2020-10-26 CN CN202011157519.2A patent/CN114477089B/en active Active
Patent Citations (7)
| 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 |
| 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 |
|---|
| Highly Selective, Iron-Driven CO2 Methanation;Williamson, DL et al.;《ENERGY TECHNOLOGY》;第7卷(第2期);第294-306页 * |
| 用于一氧化碳选择性甲烷化的钌、铼基催化剂;德国巴斯夫欧洲公司等;《齐鲁石油化工》;第46卷(第02期);第147页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114477089A (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111632596B (en) | High-dispersion metal-oxide bifunctional catalyst and preparation method and application thereof | |
| CA2470945A1 (en) | Regeneration of catalysts for carbon monoxide hydrogenation | |
| CN101982236A (en) | Hydrogenation catalyst and preparation method of 1,4-cyclohexanedimethanol | |
| CN103157471A (en) | Deoxidation catalyst for olefin gas, preparation method and application thereof | |
| CN103736487A (en) | Method for preparing supported metal catalyst through solvent-free mechanical mixing | |
| CN114477089B (en) | Method for removing trace CO at low temperature | |
| Choi et al. | XAFS study of tin modification of supported palladium catalyst for 1, 3-butadiene hydrogenation in the presence of 1-butene | |
| CN114497630A (en) | Organic liquid material for hydrogen storage, catalytic hydrogen storage system and hydrogen storage method | |
| CN102908957B (en) | Method for Fischer-Tropsch synthesis | |
| CN114477088B (en) | Method for removing CO | |
| CN105732260A (en) | Selective hydrogenation method for C2 fraction | |
| CN114345336B (en) | Transition metal molybdenum modified palladium silver-alumina catalyst, and preparation method and application thereof | |
| CN105732274A (en) | Method of purifying ethylene through selective hydrogenation | |
| CN112844398B (en) | Catalyst for hydrogenation of carbon four-superimposed product and preparation method thereof | |
| CN106928004B (en) | A kind of selective hydrogenation method of C 3 fractions | |
| CN105732281A (en) | Front-depropanization front-hydrogenation method for C2 fraction | |
| CN114471651A (en) | Supported catalyst and preparation method and application thereof | |
| CN114471608B (en) | Method for refining and purifying diethylene glycol through hydrofining | |
| CN113385187A (en) | Pyrolysis gas deoxidation catalyst and preparation method and application thereof | |
| CN108927146A (en) | A kind of inferior heavy oil hydrogenation catalyst and preparation method thereof | |
| CN1916121A (en) | Method for preparing diene selective hydrotreating catalyst for gasoline | |
| CN106927992A (en) | A kind of method that acetylene hydrogenation produces polymer grade ethylene | |
| GB2607490A (en) | Method for preparing a steam reforming catalyst, catalyst and related use | |
| CN106928001B (en) | A method of selection plus hydrogen produce polymer grade ethylene | |
| CN114477090B (en) | Method for removing carbon oxides in crude hydrogen gas |
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 |