CN115672333A - Ni-series eggshell-type catalyst, preparation method and method for selective hydrogenation and olefin removal of reformed oil - Google Patents
Ni-series eggshell-type catalyst, preparation method and method for selective hydrogenation and olefin removal of reformed oil Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 33
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 31
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 102000002322 Egg Proteins Human genes 0.000 claims abstract description 30
- 108010000912 Egg Proteins Proteins 0.000 claims abstract description 30
- 210000003278 egg shell Anatomy 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 238000005470 impregnation Methods 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 150000002815 nickel Chemical class 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 8
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 7
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 5
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 5
- 230000010355 oscillation Effects 0.000 claims description 5
- 239000003755 preservative agent Substances 0.000 claims description 5
- 230000002335 preservative effect Effects 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 2
- JVQOASIPRRGMOS-UHFFFAOYSA-M dodecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCC[N+](C)(C)C JVQOASIPRRGMOS-UHFFFAOYSA-M 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052794 bromium Inorganic materials 0.000 abstract description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 29
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004927 clay Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel 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 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- -1 hydrogen peroxide organic acid Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 210000004911 serous fluid Anatomy 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention belongs to the technical field of petrochemical industry, and relates to a Ni series eggshell type catalyst for selective hydrogenation and a preparation method thereof. The active component Ni of the Ni series eggshell type catalyst is distributed on the carrier in an eggshell type. And (3) distributing Ni on the carrier in an eggshell shape by a slurry state impregnation method to obtain the Ni series eggshell type catalyst. The Ni series eggshell type catalyst has good activity and selectivity, mild reaction conditions, and is practical and economical. The catalyst was evaluated using a real reformate with a bromine index of 4900mgBr/100g oil with 100% olefin removal and < 0.1wt% aromatics loss. The preparation method is simple and has mild conditions.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, relates to a Ni-series eggshell type catalyst and a preparation method thereof, and particularly relates to a Ni-series eggshell type catalyst for selective hydrogenation and olefin removal of reformate and a preparation method thereof.
Background
Catalytic reforming/aromatics extraction is an important process for producing chemical feedstocks such as benzene, toluene, and xylenes (BTX), but inevitably produces small amounts of olefins (around 3%). The presence of small amounts of olefin disqualifies the bromine index and acid wash color of the aromatic product and the bromine index of the mineral spirit and the copper corrosion test. Olefin is easy to polymerize in the extracted oil to pollute the extracted oil, and the polymer is adsorbed on the surface of the catalyst to deactivate the carbon deposition of the catalyst. The oxidation of olefins to organic acids also causes corrosion of the extraction system equipment.
At present, the reformate mainly has three modes of clay adsorption conversion, molecular sieve refining and selective hydrogenation. The advantages of clay adsorption and conversion are high strength, large specific surface area and good water resistance, but the process flow is complex, the energy consumption is high, the service life is short, and the clay needs to be frequently replaced and cannot be regenerated. The molecular sieve refining has the advantages of high olefin removal efficiency, high operation period and high cost. The selective hydrogenation refers to the selective hydrogenation of the olefin in the reformed oil or raffinate oil under the hydrogen condition, and the olefin in the reformed oil or raffinate oil is removed by deep hydrogenation under the condition that the aromatic hydrocarbon is not saturated by hydrogenation. The catalysts used for selective hydrogenation are divided into noble metal catalysts and non-noble metal catalysts. Representative processes of the noble metal catalysts Pd and Pt in the selective hydrogenation include ORP process of U.S. UOP company, arofining process of France IFP, and FHDO process of the Fushun petrochemical engineering science research institute (FRIPP). The advantage of the UOP ORP hydrodeolefination process is the elimination of the reformate separator and the clay treater behind each unit. The advantage of the Arofining olefin-removing process of IFP company is that the reaction condition is mild, the process is carried out under the liquid phase condition, the volume of the reactor of the Arofining process is only 25 percent of the clay tank of the particle clay process, and the investment cost and the operation space are greatly reduced. The domestic FHDO process has the advantage of adopting bottom feeding to better mix oil gas and hydrogen. The noble metal catalyst has the advantages of high selectivity, high cost, sensitivity to impurities in raw materials, and easy poisoning and inactivation. Typical non-noble metal catalysts are conventional Co-Mo, ni-Mo, sulfided hydrofinishing catalysts from UOP, USA. The non-noble metal catalyst has the advantages of low cost, good toxicity resistance, good stability and abundant active centers.
CN108192663A discloses a method for removing trace olefins in reformed oil by a combined catalytic method, which comprises the steps of adding ammonium persulfate into the reformed oil, then dropwise adding industrial hydrogen peroxide organic acid solution, heating and stirring for reaction, and removing the trace olefins in the reformed oil by carrying out oligomerization and epoxidation on the trace olefins in the reformed oil under the non-hydrogenation condition, wherein the subsequent separation process in the treatment process is complex, and the cost is increased.
CN106345499A, CN106076428A, and CN106268792A disclose preparation methods of attapulgite catalyst, which only have a catalyst life of more than 10 months, and compared with selective hydrogenation catalysts, the catalyst is replaced frequently.
CN101474568A discloses a preparation method of a selective hydrogenation and olefin removal bimetallic phosphide catalyst, which has high selectivity, but has a complex preparation process, and the catalyst needs to be heated to 300-500 ℃ at the speed of 1-10 ℃/min in a hydrogen atmosphere, reduced for 0-5 hours, heated to 500-800 ℃ at the speed of 1-5 ℃/min, reduced for 1-5 hours, and has high reaction energy consumption, the reaction temperature is 100-400 ℃, and the volume ratio of hydrogen to oil is 100-1000.
The preparation method and the application of the non-noble metal catalyst for olefin removal from reformate disclosed in CN110898846A and CN110841650A both need to add metal auxiliaries, and have the advantages of various raw material types required by preparation and difficulty increase in the preparation process.
The nickel-based catalyst has superior sulfur resistance and colloid resistance to the palladium catalyst. The nickel catalyst eggshell type catalyst is used for selective hydrogenation and olefin removal of the reformed oil, not only improves the selectivity of a reaction product, but also has high research value in the aspects of saving the preparation cost of the catalyst, reducing the energy consumption in the reaction process and the like.
Disclosure of Invention
In view of the above, the invention provides a Ni-based eggshell catalyst and a preparation method thereof, in order to solve the problems of complex preparation process, low selectivity and high reaction energy consumption of a nickel-based catalyst.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention provides a Ni-series eggshell-type catalyst, wherein the active component Ni of the catalyst is distributed on a carrier in an eggshell shape, the nickel content of the catalyst is 5-50% by weight percent of the catalyst, and more than 95% of nickel is distributed on the surface of the carrier to the depth of 0.5 mm.
In some embodiments, the catalyst has a nickel content of 5 to 15% and 95% or more of the nickel is distributed on the surface of the support to a depth of 0.5 mm.
In some embodiments, the support is selected from the group consisting of activated carbon, carbon fibers, carbon nanotubes, porous polymers, al 2 O 3 、MgO、ZnO、SiO 2 、SnO 2 、TiO 2 Or ZrO 2 One or more of them.
The invention also provides a preparation method of the Ni series eggshell type catalyst for selective hydrogenation, which comprises the steps of putting a carrier into a nickel salt suspension, adding an alkaline substance to adjust the pH value, dipping in a slurry state, separating the catalyst from the slurry, drying and roasting in a muffle furnace.
Further, in some embodiments, the method of making, comprises the steps of:
(1) Weighing a certain amount of carrier and putting the carrier into a beaker, weighing nickel salt according to the required load and putting the nickel salt into the beaker, and adding a proper amount of deionized water;
(2) Adding alkaline substances into the beaker in the step (1) to adjust the pH value, covering a layer of preservative film on the beaker, and then placing the beaker into a water bath constant temperature oscillator for oscillation so as to ensure that the thickness of the eggshell layer is thin and uniform, and dipping the eggshell layer in a slurry state;
(3) Taking the catalyst treated in the step (2) out of the slurry and drying;
(4) And (4) putting the catalyst treated in the step (3) into a muffle furnace for roasting to obtain the catalyst.
In some embodiments, the nickel salt is basic nickel carbonate, nickel hydroxide, nickel carbonate, or nickel oxalate.
In some embodiments, the mass ratio of the deionized water to the nickel salt is 15 to 30. Furthermore, the mass ratio of the deionized water to the nickel salt is 20-30.
In some embodiments, the mass ratio of the deionized water to the basic nickel carbonate is 30; in some embodiments, the mass ratio of the deionized water to the nickel hydroxide is 20; in some embodiments, the mass ratio of the deionized water to the nickel oxalate is 20.
In some embodiments, the basic material is at least one of potassium hydroxide, sodium hydroxide, ammonia, methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, ethylenediamine, propylamine, dipropylamine, tripropylamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium hydroxide, dodecyltrimethylammonium hydroxide, or benzyltrimethylammonium hydroxide, and ammonium salts.
In some embodiments, the pH is adjusted to be in the range of 9-12.
In some embodiments, concentrated ammonia is added dropwise to adjust the pH to 9. In some embodiments, sodium hydroxide is added dropwise to adjust the pH to 12. In some embodiments, tetrapropylammonium hydroxide is added dropwise to a pH of 11.
In some embodiments, the slurry is immersed in a water bath at a temperature of 20 to 100 ℃ for a period of 5 to 480min. Furthermore, the temperature of the water bath for dipping the serous fluid is 50-80 ℃, and the oscillation time is 150-480min.
In some embodiments, the temperature of the water bath is 80 ℃ and the shaking time is 480min; in some embodiments, the temperature of the water bath is 50 ℃ and the oscillation time is 240min; in some embodiments, the temperature of the water bath is 60 ℃ and the time of shaking is 180min.
In some embodiments, the catalyst is dried at a temperature of 80 to 150 ℃ for a time of 1 to 8 hours. Furthermore, the drying temperature of the catalyst is 80-120 ℃, and the drying time is 2-6h. In some embodiments, the catalyst is dried at 80 ℃ for 2 hours. In some embodiments, the catalyst is dried at 100 ℃ for 4 hours. In some embodiments, the catalyst is dried at 120 ℃ for 6 hours.
In some embodiments, the catalyst is calcined at a temperature of 200 to 500 ℃ for a time of 2 to 6 hours. Furthermore, the roasting temperature of the catalyst is 300-500 ℃, and the roasting time is 4-6h.
In some embodiments, the calcination temperature is 300 ℃ and the calcination time is 6 hours; in some embodiments, the roasting temperature is 500 ℃ and the roasting time is 6 hours; in some embodiments, the firing temperature is 450 ℃ and the firing time is 4 hours.
The invention also provides a method for selective hydrogenation and olefin removal of the reformed oil, which is characterized in that the Ni-series eggshell-type catalyst is filled in the fixed bed reactor and subjected to selective hydrogenation reaction after reduction.
In some embodiments, the catalyst has a reduction temperature of 200 to 700 ℃, a reduction pressure of 0.2 to 4MPa, a hydrogen flow rate of 1 to 100mL/min, and a reduction time of 2 to 10 hours. Furthermore, the reduction temperature of the catalyst is 400-600 ℃, the reduction pressure is 1-3MPa, the hydrogen flow is 30-60mL/min, and the reduction time is 2-6h.
In some embodiments, the reduction temperature is 400 ℃, the reduction pressure is 1MPa, the hydrogen flow rate is 30mL/min, and the reduction time is 3h; in some embodiments, the reduction temperature is 600 ℃, the reduction pressure is 1.5MPa, the hydrogen flow rate is 60mL/min, and the reduction time is 2h; in some embodiments, the reduction temperature is 550 ℃, the reduction pressure is 3MPa, the hydrogen flow is 40mL/min, and the reduction time is 6h.
In some embodiments, the reaction temperature of the selective hydrogenation reaction is 60-120 ℃, the reaction pressure is 1.0-3.0 MPa, the reaction hydrogen-oil ratio is 100-500, and the liquid volume space velocity is 1-3 h -1 The loading of the catalyst is 4-8 mL.
In some embodiments, the reaction temperature of the selective hydrogenation reaction is 120 ℃, the reaction pressure is 1.0MPa, the reaction hydrogen-oil ratio is 500, and the liquid volume space velocity is 2h -1 The catalyst loading was 4mL. In some embodiments, the reaction temperature of the selective hydrogenation reaction is 60 ℃, the reaction pressure is 3.0MPa, the reaction hydrogen-oil ratio is 100, and the liquid volume space velocity is 1h -1 The catalyst loading was 8mL. In some embodiments, the reaction temperature of the selective hydrogenation reaction is 100 ℃, the reaction pressure is 2.0MPa, the reaction hydrogen-oil ratio is 300, and the liquid volume space velocity is 3h -1 The catalyst loading was 6mL. According to the technical scheme, the invention provides the Ni eggshell type catalyst for selective hydrogenation and olefin removal of the reformate and the preparation method thereof. The active component Ni of the Ni series eggshell type catalyst is distributed on the carrier in an eggshell type. And distributing Ni on the carrier in an eggshell shape by a slurry impregnation method to obtain the Ni series eggshell-shaped catalyst. Compared with the prior art, the Ni series eggshell type catalyst has the following outstanding beneficial effects:
(1) The catalyst has good activity and selectivity, and is evaluated by adopting a reformed oil raw material with a bromine index of 4900mgBr/100g oil, the olefin removal rate is 100 percent, and the aromatic hydrocarbon loss rate is less than 0.5wt percent;
(2) The preparation method is simple and the reaction condition is mild.
Drawings
FIG. 1: the metallographic microscope characterization of the eggshell type catalyst prepared in example 1, wherein the metallographic microscope detection method is to adopt a DM-2500M type metallographic microscope produced by come card microscope company of germany to observe the particle section of the catalyst, the magnification is 50, and the metallographic microscope is combined with Getphase software to perform metallographic observation and geometric measurement; wherein the length of the ruler is 500 mu m;
FIG. 2 is a schematic diagram: the metallographic microscope characterization of the eggshell type catalyst prepared in example 2, wherein the metallographic microscope detection method is to adopt a DM-2500M type metallographic microscope produced by come card microscope company, germany, to observe the particle section of the catalyst, the magnification is 50, and the metallographic microscope is combined with Getphase software to perform metallographic observation and geometric measurement; wherein the length of the scale is 500 μm.
Detailed Description
The catalyst and the preparation method thereof according to the present invention will be further described with reference to specific examples to help those skilled in the art to more fully, accurately and deeply understand the inventive concept and technical scheme of the present invention; it should be noted that the descriptions of the process flow, the parameters, etc. in the embodiments are illustrative and are not meant to limit the scope of the invention. The test methods described in the following examples are all conventional methods unless otherwise specified; the apparatus and materials are commercially available, unless otherwise specified.
The metallographic microscope detection method is characterized in that a DM-2500M metallographic microscope produced by Leica microscope company of Germany is adopted to observe the cross section of catalyst particles, the magnification is 50, and the metallographic microscope is combined with Getphase software to carry out metallographic observation and geometric measurement.
Example 1
Weighing 10g of alumina pellets with the diameter of 2.5mm and 1.9g of basic nickel carbonate at room temperature, putting the alumina pellets and the basic nickel carbonate into a beaker, adding 57mL of deionized water, then dropwise adding 3mL of concentrated ammonia water, wherein the pH value of the slurry impregnation liquid is 9, covering a layer of preservative film on the beaker, then putting the beaker into a water bath constant temperature oscillator, setting the water bath temperature to be 80 ℃, and oscillating the beaker at constant temperature for 8 hours; separating the impregnated catalyst from the slurry, and drying in an oven at 80 ℃ for 2h; and taking out the dried catalyst from the oven, and roasting in a muffle furnace at 300 ℃ for 6h to obtain the Ni-series eggshell-shaped catalyst.
The prepared catalyst is characterized by a metallographic microscope, the result is shown in figure 1, a prepared sample is subjected to nickel content analysis by adopting a Varian inductively coupled plasma spectrometer ICP-OES 720ES, the nickel content of the catalyst is 10%, more than 95% of nickel can be adjusted to be distributed on the surface of a carrier within the range of 450 mu m of depth, and the edge of an active component is clear.
Example 2
Weighing 15g of silicon dioxide pellets with the diameter of 3.0mm and 3g of nickel hydroxide at room temperature, putting the silicon dioxide pellets and the nickel hydroxide into a beaker, adding 60mL of deionized water, then dropwise adding 2g of sodium hydroxide, enabling the pH of the slurry impregnation liquid to be 12, covering a layer of preservative film on the beaker, then putting the beaker into a water bath constant temperature oscillator, setting the water bath temperature to be 50 ℃, and oscillating the beaker at constant temperature for 4 hours; after the impregnation is finished, separating the catalyst from the slurry, and drying in an oven at 100 ℃ for 4h; and taking out the dried catalyst from the oven, and roasting in a muffle furnace at 500 ℃ for 6h to obtain the Ni eggshell type catalyst.
The prepared catalyst is characterized by a metallographic microscope, the result is shown in figure 2, a prepared sample is subjected to nickel content analysis by adopting a Varian inductively coupled plasma spectrometer ICP-OES 720ES, the nickel content of the catalyst is 15%, more than 95% of nickel can be adjusted to be distributed on the surface of a carrier within the range of the depth of 160 mu m, and the edge of an active component is clear.
Example 3
Weighing 8g of active carbon and 1g of nickel oxalate at room temperature, putting the active carbon and the nickel oxalate into a beaker, adding 20mL of deionized water, and then dropwise adding 1.5mL of tetrapropylammonium hydroxide, wherein the pH value of the slurry impregnation liquid is 11; covering a layer of preservative film on a beaker, putting the beaker into a water bath constant temperature oscillator, setting the water bath temperature to be 60 ℃, and oscillating for 3 hours at constant temperature; after the impregnation is finished, separating the catalyst from the slurry, and drying in a 120 ℃ drying oven for 6h; and taking out the dried catalyst from the oven, and roasting the catalyst in a muffle furnace at 450 ℃ for 4 hours to obtain the Ni-series eggshell-shaped catalyst.
The prepared catalyst is characterized by a metallographic microscope, and the result shows that the nickel content of the catalyst is 5.5%, more than 95% of nickel can be adjusted to be distributed on the surface of the carrier within the range of 0.5mm of depth, and the edge of the active component is clear.
Test examples: test for catalytic Performance
Test example 1
A fixed bed reactor is adopted, the inner diameter of the reactor is 25 mm, the length of the reactor is 1000 mm, and the reactor is made of stainless steel. The catalyst bed layer is vertically distributedFilling quartz sand to play roles in heat dissipation, airflow distribution and support, filling 6mL of the catalyst prepared in the embodiment 1 in a reactor, and introducing hydrogen to reduce, wherein the reduction conditions are as follows: the temperature is 400 ℃, the pressure is 1MPa, the hydrogen flow is 30mL/min, and the reduction is carried out for 3h under the conditions. Then the reformed oil raw material and hydrogen are mixed and then pass through a catalyst bed layer from top to bottom to carry out olefin selective hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 120 ℃, the reaction pressure is 1.0MPa, the reaction hydrogen-oil ratio is 500, and the liquid volume space velocity is 2h -1 The catalyst loading was 4mL.
The bromine index of the raw material of the reformate is 4900mgBr/100g oil, and the mass fraction of the aromatic hydrocarbon is 83 percent. When the catalyst prepared in the embodiment 1 of the application is adopted, the olefin removal rate reaches 100 percent, and the aromatic hydrocarbon loss rate is less than 0.1wt percent. Wherein, the olefin removal rate of the selective hydrogenation olefin removal reaction is analyzed by an Agilent-7890 gas chromatograph of America, a PONA column (30 m multiplied by 0.32nm multiplied by 0.5 mu m) is adopted as a chromatographic column, and the method parameters are as follows: the initial temperature is 50 ℃, the heating rate is 10 ℃/min, the temperature is raised to 280 ℃, the feeding amount is 0.2 mu L, and the carrier gas is nitrogen. The aromatic hydrocarbon loss in the selective hydrodeolefination reaction was analyzed by using a BR-1 bromine number/bromine index meter of taizhou large-scale analytical instruments ltd.
Test example 2
A fixed bed reactor is adopted, the inner diameter of the reactor is 20 mm, the length of the reactor is 80 mm, and the reactor is made of stainless steel. Quartz sand is filled above and below a catalyst bed layer to play roles in heat dissipation, airflow distribution and support, 4mL of the catalyst prepared in the embodiment 2 is filled in a reactor, and hydrogen is introduced for reduction under the reduction conditions: the temperature is 600 ℃, the pressure is 1.5MPa, and the hydrogen flow is 60mL/min, and the reduction is carried out for 2h under the conditions. Then the reformed oil raw material and hydrogen are mixed and then pass through a catalyst bed layer from top to bottom to carry out olefin selective hydrogenation reaction, and the reaction conditions are as follows: the reaction temperature is 60 ℃, the reaction pressure is 3.0MPa, the reaction hydrogen-oil ratio is 100, and the liquid volume space velocity is 1h -1 The catalyst loading was 8mL.
The bromine index of the reformate raw material is 4900mgBr/100g oil, and the mass fraction of aromatic hydrocarbon is 83%. When the catalyst prepared in the embodiment 2 is used, the olefin removal rate reaches 100%, and the aromatic hydrocarbon loss rate is less than 0.05wt%. Wherein, the olefin removal rate of the selective hydrogenation olefin removal reaction is analyzed by an Agilent-7890 gas chromatograph of America, the chromatographic column is a PONA column (30 m multiplied by 0.32nm multiplied by 0.5 mu m), and the method parameters are as follows: the initial temperature is 50 ℃, the heating rate is 10 ℃/min, the temperature is raised to 280 ℃, the feeding amount is 0.2 mu L, and the carrier gas is nitrogen. The aromatics loss in the selective hydrodeolefination reaction was analyzed using a BR-1 bromine number/bromine index meter, a texas large-scale analytical instruments ltd.
Test example 3
A fixed bed reactor is adopted, the inner diameter of the reactor is 30 mm, the length of the reactor is 1200 mm, and the reactor is made of stainless steel. Quartz sand is filled above and below a catalyst bed layer to play roles in heat dissipation, airflow distribution and support, 10mL of the catalyst prepared in the embodiment 3 is filled in a reactor, and hydrogen is introduced for reduction under the reduction conditions: the temperature is 550 ℃, the pressure is 3MPa, and the hydrogen flow is 40mL/min, and the reduction is carried out for 6h under the conditions. Then the raw material of the reformed oil and hydrogen are mixed and then pass through a catalyst bed layer from top to bottom to carry out the selective hydrogenation reaction of olefin, and the reaction conditions are as follows: the reaction temperature is 100 ℃, the reaction pressure is 2.0MPa, the reaction hydrogen-oil ratio is 300, and the liquid volume space velocity is 3h -1 The catalyst loading was 6mL.
The bromine index of the reformate raw material is 4900mgBr/100g oil, and the mass fraction of aromatic hydrocarbon is 83%. When the catalyst prepared in the embodiment 3 is adopted, the olefin removal rate reaches 100%, and the aromatic hydrocarbon loss rate is less than 0.2wt%. Wherein, the olefin removal rate of the selective hydrogenation olefin removal reaction is analyzed by an Agilent-7890 gas chromatograph of America, the chromatographic column is a PONA column (30 m multiplied by 0.32nm multiplied by 0.5 mu m), and the method parameters are as follows: the initial temperature is 50 ℃, the heating rate is 10 ℃/min, the temperature rises to 280 ℃, the feeding amount is 0.2 mu L, and the carrier gas is nitrogen. The aromatic hydrocarbon loss in the selective hydrodeolefination reaction was analyzed by using a BR-1 bromine number/bromine index meter of taizhou large-scale analytical instruments ltd.
It is obvious to those skilled in the art that the present invention is not limited to the above embodiments, and it is within the scope of the present invention to adopt various insubstantial modifications of the method concept and technical scheme of the present invention, or to directly apply the concept and technical scheme of the present invention to other occasions without modification.
Claims (10)
1. The Ni-series eggshell catalyst is characterized in that the active component Ni of the catalyst is distributed on a carrier in an eggshell shape, the nickel content of the catalyst is 5-50% by weight percent, and more than 95% of nickel is distributed on the surface of the carrier to the depth of 0.5 mm.
2. The catalyst according to claim 1, wherein the support is selected from the group consisting of activated carbon, carbon fibers, carbon nanotubes, porous polymers, al 2 O 3 、MgO、ZnO、SiO 2 、SnO 2 、TiO 2 Or ZrO 2 One or more of them.
3. The method for preparing the Ni-based eggshell catalyst of claim 1 or 2, wherein the Ni-based eggshell catalyst is obtained by placing a carrier into a nickel salt suspension, adding an alkaline substance to adjust the pH, dipping in a slurry state, separating the catalyst from the slurry, drying, and calcining in a muffle furnace.
4. The method of claim 3, comprising the steps of:
(1) Weighing a certain amount of carrier and putting the carrier into a beaker, weighing nickel salt according to the required load and putting the nickel salt into the beaker, and adding a proper amount of deionized water;
(2) Adding alkaline substances into the beaker in the step (1) to adjust the pH value, covering a layer of preservative film on the beaker, and then placing the beaker into a water bath constant temperature oscillator for oscillation so as to ensure that the thickness of the eggshell layer is thin and uniform, and dipping the eggshell layer in a slurry state;
(3) Taking out the catalyst treated in the step (2) from the slurry and drying;
(4) And (4) putting the catalyst treated in the step (3) into a muffle furnace for roasting to obtain the catalyst.
5. The production method according to claim 3 or 4, characterized in that the nickel salt is basic nickel carbonate, nickel hydroxide, nickel carbonate or nickel oxalate; the mass ratio of the deionized water to the nickel salt is 15-30.
6. The production method according to claim 3 or 4, characterized in that the basic substance is at least one of potassium hydroxide, sodium hydroxide, aqueous ammonia, methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, ethylenediamine, propylamine, dipropylamine, tripropylamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetramethylammonium hydroxide, dodecyltrimethylammonium hydroxide or benzyltrimethylammonium hydroxide and ammonium salts; adjusting the pH value to be within the range of 9-12; the temperature of the water bath during slurry state impregnation is 20-100 ℃, and the oscillation time is 5-480min.
7. The method according to claim 3 or 4, wherein the drying temperature is 80 to 150 ℃ and the drying time is 1 to 8 hours.
8. A method as claimed in claim 3 or 4, wherein the calcination temperature is 200-500 ℃ and the calcination time is 2-6h.
9. A method for selective hydrogenation and olefin removal of reformate, characterized in that the Ni-based eggshell catalyst as defined in claim 1 or 2 is packed in a fixed bed reactor and subjected to selective hydrogenation after reduction.
10. The method according to claim 9, wherein the reduction temperature is 200-700 ℃, the reduction pressure is 0.2-4MPa, the hydrogen flow rate is 1-100mL/min, and the reduction time is 2-10h; the reaction temperature of the selective hydrogenation reaction is 60-120 ℃, the reaction pressure is 1.0-3.0 MPa, the reaction hydrogen-oil ratio is 100-500, and the liquid volume space velocity is 1-3 h -1 The loading of the catalyst is 4-8 mL.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9603728D0 (en) * | 1993-05-21 | 1996-04-24 | Chinese Petroleum Co | Eggshell catalyst and process for preparation of the same |
| CN1736604A (en) * | 2005-07-27 | 2006-02-22 | 北京化工大学 | Egg shell type metal catalyst, its preparing process and application method |
| CN101890351A (en) * | 2009-05-21 | 2010-11-24 | 中国石油化工股份有限公司 | Eggshell type nickel-based catalyst |
| CN103223342A (en) * | 2013-05-22 | 2013-07-31 | 北京化工大学 | Preparation method and application of eggshell-type nickel-based catalyst |
| CN112691672A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Eggshell catalyst and preparation method and application thereof |
-
2022
- 2022-10-12 CN CN202211250862.0A patent/CN115672333A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9603728D0 (en) * | 1993-05-21 | 1996-04-24 | Chinese Petroleum Co | Eggshell catalyst and process for preparation of the same |
| CN1736604A (en) * | 2005-07-27 | 2006-02-22 | 北京化工大学 | Egg shell type metal catalyst, its preparing process and application method |
| CN101890351A (en) * | 2009-05-21 | 2010-11-24 | 中国石油化工股份有限公司 | Eggshell type nickel-based catalyst |
| CN103223342A (en) * | 2013-05-22 | 2013-07-31 | 北京化工大学 | Preparation method and application of eggshell-type nickel-based catalyst |
| CN112691672A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Eggshell catalyst and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王丹;周清华;宋金鹤;徐伟池;: "Ni系催化剂用于重整生成油选择性加氢的研究", 石油炼制与化工, no. 05, pages 2 * |
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