CN115814787A - Metal loss resistant carbon five petroleum resin hydrogenation catalyst - Google Patents
Metal loss resistant carbon five petroleum resin hydrogenation catalyst Download PDFInfo
- Publication number
- CN115814787A CN115814787A CN202310001921.9A CN202310001921A CN115814787A CN 115814787 A CN115814787 A CN 115814787A CN 202310001921 A CN202310001921 A CN 202310001921A CN 115814787 A CN115814787 A CN 115814787A
- Authority
- CN
- China
- Prior art keywords
- sio
- beta
- composite carrier
- petroleum resin
- hydrogenation catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 239000011347 resin Substances 0.000 title claims abstract description 53
- 229920005989 resin Polymers 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 38
- 239000003208 petroleum Substances 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 73
- 239000002131 composite material Substances 0.000 claims abstract description 51
- 229910052796 boron Inorganic materials 0.000 claims abstract description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 71
- 239000000843 powder Substances 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 29
- 238000000227 grinding Methods 0.000 claims description 29
- 230000032683 aging Effects 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- -1 orthosilicic acid alcohol ester Chemical class 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- PRORZGWHZXZQMV-UHFFFAOYSA-N azane;nitric acid Chemical compound N.O[N+]([O-])=O PRORZGWHZXZQMV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 2
- 229930195733 hydrocarbon Natural products 0.000 claims 2
- 150000002430 hydrocarbons Chemical class 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 description 32
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 20
- 239000000460 chlorine Substances 0.000 description 16
- 238000007598 dipping method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-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
- 101150003085 Pdcl gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
Abstract
The invention discloses a metal loss resistant carbon five petroleum resin hydrogenation catalyst, which is prepared from Pt group active metal and beta-Mg 2 V 2 O 7 /SiO 2 The composite carrier and the auxiliary agent boron. The catalyst can improve the catalytic efficiency of the hydrocarbon-modified petroleum resin and ensure that the active metal is not easy to lose.
Description
Technical Field
The invention particularly relates to a metal loss resistant carbon five petroleum resin hydrogenation catalyst.
Background
The main chain of the carbon five petroleum resin is an aliphatic structure, and has the characteristics of low acid value, good miscibility, water resistance, ethanol resistance, chemical corrosion resistance and the like. However, the carbon-five petroleum resin has the defects of high brittleness, dark color, odor, lack of polar groups on the structure and the like due to unsaturated chemical bonds. Unsaturated carbon-carbon double bonds in the resin are subjected to hydrogenation saturation in a catalytic hydrogenation mode, so that the unsaturation degree of the resin can be reduced, and the performances of the resin such as stability, oxidation resistance and the like are improved. The hydrogenated carbon five petroleum resin is colorless, tasteless, high in light oxygen stability, and is an upgrade of common yellow resin additives used in specific fields, especially furniture binder, printing ink, high-grade paper, paint and other fields. With the requirement of human on health and environmental protection, the hydrogenated carbon five resin gradually replaces the carbon five petroleum resin to produce energy, and the hydrogenated carbon five petroleum resin can be applied to more fields.
C5 petroleum resin hydrogenation catalysts are mainly classified into Ni-based catalysts and noble metal-based catalysts, and although Ni-based catalysts have a cost advantage to facilitate industrialization, their activities are relatively low and require high reaction temperatures. In view of the above problems, the use of noble metal-based catalysts in the hydrogenation of hydrocarbon-modified petroleum resins has been increasing in recent years. The noble metal catalyst has higher hydrogenation performance and milder reaction conditions, but the noble metal has poorer dispersibility on the carrier, and chlorine element in resin often causes the loss of active metal in the hydrogenation catalyst. The patent CN 104525198B improves the catalytic activity of the catalyst by adding Ag or VB group elements, and simultaneously has better resistance to the toxicity of impurities such as sulfur, halogen, nitrogen and the like, thereby having longer service life. CN 106268725A uses gamma-alumina as carrier and adopts step-by-step method to load palladium, molybdenum, manganese and other metals, so that the catalyst has better hydrogenation activity. CN 102935367B provides a C5 petroleum resin hydrogenation catalyst, which comprises an alumina-titanium oxide composite carrier, metal palladium loaded on the composite carrier, and auxiliary agents of molybdenum and tungsten, and the catalyst has not only lower hydrogenation activity but also better impurity resistance and good stability when being used in a C5 petroleum resin hydrogenation process.
Disclosure of Invention
Aims to solve the problem that the noble metal catalyst reduces the loss of active metal while maintaining higher hydrogenation activity of the petroleum resin. The invention provides a metal loss resistant carbon five petroleum resin hydrogenation catalyst, which uses beta-Mg 2 V 2 O 7 And SiO 2 Hydrogenation for forming carbon-five petroleum resin by using noble metal loaded composite carrierThe catalyst can not only effectively hydrogenate the petroleum resin, but also utilize beta-Mg 2 V 2 O 7 More oxygen vacancies stabilize the active metal, reduce the loss of the active metal in the reaction, and utilize boron element for modification to help the dispersion of the active metal and reduce the particle size of the active metal.
In order to realize the purpose, the invention adopts the following technical scheme:
one of the purposes of the invention is to provide a metal loss resistant carbon five petroleum resin hydrogenation catalyst, which comprises the following components:
(a) A Pt group active metal;
（b）β-Mg 2 V 2 O 7 /SiO 2 a composite carrier;
(c) And (4) an auxiliary agent boron.
Further, the Pt group active metal is one or more of Pt, pd, ir, ru and Rh.
Further, the loading amount of the Pt group active metal is 0.1-5% of the mass of the composite carrier.
Further, beta-Mg in the composite carrier 2 V 2 O 7 The content of (A) is 30-60% of the total mass of the composite carrier.
Further, the content of the boron additive accounts for 0.01-2% of the mass of the composite carrier.
The invention also aims to provide a preparation method of the carbon five petroleum resin hydrogenation catalyst, which comprises the following steps:
（1）β-Mg 2 V 2 O 7 preparation of
Reacting NH 4 VO 3 Dissolved in hot water at 85 ℃ according to NH 4 VO 3 And Mg (OH) 2 1, adding Mg (OH) 2 Stirring thoroughly, evaporating to remove water, drying the obtained solid powder at 120 deg.C for 12 hr, calcining at 550 deg.C for 6 hr, grinding thoroughly to obtain beta-Mg 2 V 2 O 7 A powder;
（2）β-Mg 2 V 2 O 7 /SiO 2 preparation of composite Carrier
40 ml of alcohol-water soluble solution was prepared in a volume ratio of 1Heating the solution to 40-90 ℃ under the condition of stirring, and then adding beta-Mg into the catalyst 2 V 2 O 7 And SiO 2 The dosage proportion is that a certain amount of orthosilicic acid alcohol ester and a certain amount of beta-Mg are dripped into the alcohol-water solution 2 V 2 O 7 Stirring and aging at 40-90 deg.C for 8 hr, gelatinizing and aging at room temperature for 24 hr, drying the gel at 120 deg.C for 36 hr, grinding the solid, and calcining at 450 deg.C for 6 hr to obtain beta-Mg 2 V 2 O 7 /SiO 2 A composite carrier;
(3) Preparation of the catalyst:
dissolving Pt group active metal precursor and boric acid in deionized water according to a certain proportion by adopting an impregnation method, and then adding the beta-Mg prepared in the step (2) 2 V 2 O 7 /SiO 2 And (3) stirring and soaking the composite carrier for 6 hours, drying the composite carrier in a water bath at 90 ℃, grinding the product into powder, and roasting the powder for 6 hours at 450 ℃ to obtain the hydrogenation catalyst.
Further, the Pt group active metal precursor in the step 3) is chloride, nitrate, hydrochloride, chloride ammonia complex or nitrate ammonia complex of Pt group active metal, such as PdCl 2 、Pd(NH 3 ) 2 Cl 2 、Pd(NH 3 ) 2 Cl 4 、Pd(NO 3 ) 2 、H 2 PtCl 6 、Pt(NH 3 ) 4 Cl 2 、Pt(NH 3 ) 4 (NO 3 ) 2 、[Pt(NH 3 ) 4 ][PtCl 4 ]。
The invention also aims to provide an application of the hydrogenation catalyst for the carbon five petroleum resin, namely the hydrogenation catalyst is applied to the hydrofining of the carbon five petroleum resin.
The invention has the following remarkable advantages:
the beta-Mg is used in the metal loss resistant carbon five petroleum resin hydrogenation catalyst provided by the invention 2 V 2 O 7 And SiO 2 As a composite carrier to load noble metal and boron, wherein, beta-Mg 2 V 2 O 7 More oxygen vacancies can stabilize the active metal and promoteAnchoring of the active metal in the support, thereby reducing loss of the active metal in the reaction, siO 2 The surface area of the catalyst can be increased, the adsorption and diffusion effects on raw material molecules are increased, the modification of the boron element is more beneficial to the dispersion of active metal, and the particle size of the active metal is reduced, so that the obtained catalyst has high-efficiency catalytic hydrogenation activity on the carbon five petroleum resin, and the loss of the active metal can be avoided.
Detailed Description
A preparation method of a carbon five petroleum resin hydrogenation catalyst comprises the following steps:
（1）β-Mg 2 V 2 O 7 preparation of (2)
Reacting NH 4 VO 3 Dissolved in hot water at 85 ℃ according to NH 4 VO 3 And Mg (OH) 2 1, adding Mg (OH) 2 Stirring thoroughly, evaporating to remove water, drying the obtained solid powder at 120 deg.C for 12 hr, calcining at 550 deg.C for 6 hr, and grinding thoroughly to obtain beta-Mg 2 V 2 O 7 A powder;
（2）β-Mg 2 V 2 O 7 /SiO 2 preparation of composite Carrier
Preparing 40 ml of alcohol-water solution according to a volume ratio of 1 2 V 2 O 7 And SiO 2 The dosage proportion is that a certain amount of orthosilicic acid alcohol ester and a certain amount of beta-Mg are dripped into the alcohol-water solution 2 V 2 O 7 Stirring and aging at 40-90 deg.C for 8 hr, gelatinizing and aging at room temperature for 24 hr, drying the gel at 120 deg.C for 36 hr, grinding the solid, and calcining at 450 deg.C for 6 hr to obtain beta-Mg 2 V 2 O 7 /SiO 2 A composite carrier;
(3) Preparation of the catalyst:
dissolving a Pt group active metal precursor and boric acid in deionized water according to a certain proportion by adopting an immersion method, and then adding the beta-Mg prepared in the step (2) 2 V 2 O 7 /SiO 2 The composite carrier is stirred, dipped for 6 hours, dried in water bath at 90 ℃, and the product is groundGrinding into powder, and roasting at 450 ℃ for 6 hours to obtain the hydrogenation catalyst.
Wherein the Pt group active metal precursor is chloride, nitrate, hydrochloride, chloride ammonia complex or nitrate ammonia complex of at least one of Pt, pd, ir, ru and Rh, and the dosage of the Pt group active metal precursor is converted according to the load of the Pt group active metal and 0.1-5% of the mass of the composite carrier.
beta-Mg in the composite carrier 2 V 2 O 7 The content of (A) is 30-60% of the total mass of the composite carrier.
The content of the boron additive accounts for 0.01-2% of the mass of the composite carrier.
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1% Pd-0.03% B/50% beta-Mg 2 V 2 O 7 -50%SiO 2
(1) 17.9 g (0.15 mol) NH were weighed out 4 VO 3 Dissolved in hot water at 85 ℃ and then 8.9g (0.15 mol) of Mg (OH) are added 2 Stirring thoroughly, evaporating to remove water, drying the obtained solid powder at 120 deg.C for 12 hr, calcining at 550 deg.C for 6 hr, and grinding thoroughly to obtain beta-Mg 2 V 2 O 7 Powder for standby;
(2) Preparing 40 ml of alcohol-water solution according to a volume ratio of 1 2 V 2 O 7 And SiO 2 The mass ratio of (1) 2 V 2 O 7 Stirring and aging the powder at 85 ℃ for 8h, then gelling and aging at room temperature for 24h, drying the obtained gel in an oven at 120 ℃ for 36 h, grinding the obtained solid, and roasting at 450 ℃ for 6 h to obtain 50% beta-Mg 2 V 2 O 7 -50%SiO 2 A composite carrier;
(3) 0.199 g Pd (NH) was weighed out by the dipping method 3 ) 2 Cl 2 And 0.0172 g of boric acid was dissolved in 30 ml of deionized water, after which 10g of 50% beta-Mg was added 2 V 2 O 7 -50%SiO 2 The composite carrier is immersed under stirring for 6 hours, dried in a water bath at 90 ℃ and the product is ground to a powder and calcined at 450 ℃ for 6 hours to obtain 1% Pd-0.03% B/50% beta-Mg 2 V 2 O 7 -50%SiO 2 A catalyst.
1% of Pd-0.03% as described above, B/50% of beta-Mg 2 V 2 O 7 -50%SiO 2 After the catalyst is compacted and formed, the catalyst is crushed and sieved into 40-mesh granular catalyst for testing the catalytic performance. The test was carried out on a high-pressure fixed-bed reactor with a catalyst loading mass of 10.0 ml. Before reaction, the catalyst needs to be reduced for 2 hours at the temperature of 450 ℃ under normal pressure, so that the loaded active component exists in a simple substance form, and when the temperature is reduced to the reaction temperature, a solution containing 20 wt% of carbon penta resin-cyclohexane is introduced to react with hydrogen. The reaction conditions are as follows: the reaction temperature is 250 ℃, the reaction pressure is 8.0 MPa, and the mass space velocity of the raw material is 1.0 h -1 The molar ratio of hydrogen to carbon pentaresin-cyclohexane solution was 600. Bromine number analysis was performed by iodometry (SWB 2301-62) to calculate the conversion of petroleum resin hydrogenation (5 # resin for carbon five resin used in hydrogenation, bromine number 5.93 gBr/100 g), which is calculated as follows:
the active metal content in the catalyst was measured using ICP-MS. The dispersion degree of active metal in the catalyst is H 2 -O 2 And (4) testing a titration method. The reaction results are shown in Table 1.
Comparative example 1% Pd/50% beta-Mg 2 V 2 O 7 -50% SiO 2
(1) beta-Mg was prepared as in example 1 2 V 2 O 7 ；
(2) Preparing 40 ml of alcohol-water solution according to a volume ratio of 1 2 V 2 O 7 And SiO 2 The mass ratio of (1) 2 V 2 O 7 Powder, 85 deg.CStirring and aging for 8h, gelatinizing and aging at room temperature for 24h, drying the obtained gel in an oven at 120 ℃ for 36 h, grinding the obtained solid, and roasting at 450 ℃ for 6 h to obtain 50% beta-Mg 2 V 2 O 7 -50%SiO 2 A composite carrier;
(3) 0.199 g Pd (NH) was weighed out by the dipping method 3 ) 2 Cl 2 Dissolved in 30 ml of deionized water, followed by addition of 10g of 50% beta-Mg 2 V 2 O 7 -50%SiO 2 The composite carrier is stirred, dipped for 6 hours, dried in water bath at 90 ℃, ground into powder and roasted for 6 hours at 450 ℃ to obtain 1 percent Pd/50 percent beta-Mg 2 V 2 O 7 -50%SiO 2 A catalyst.
Mixing the above 1% Pd/50% beta-Mg 2 V 2 O 7 - 50%SiO 2 After the catalyst was compacted and molded, the catalyst was crushed and sieved to 40 mesh, and the catalytic performance of the catalyst in the carbon five resin hydrorefining reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Comparative example 2% Pd-0.03% 2
(1) Preparing 40 ml of alcohol-water solution according to a volume ratio of 1 2 A carrier;
(2) 0.199 g Pd (NH) was weighed out by the dipping method 3 ) 2 Cl 2 And 0.0172 g of boric acid was dissolved in 30 ml of deionized water, after which 10g of SiO was added 2 Stirring and immersing for 6 hours, drying in water bath at 90 ℃, grinding the product into powder, and roasting at 450 ℃ for 6 hours to obtain 1% Pd-0.03% B/SiO% 2 A catalyst.
The above 1% Pd-0.03% 2 After the catalyst was compacted and molded, the catalyst was crushed and sieved to 40 mesh, and the catalytic performance of the catalyst in the carbon five resin hydrorefining reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Comparative example 3% Pd-0.03% 2 V 2 O 7
(1) 17.9 g NH were weighed 4 VO 3 Dissolved in hot water at 85 ℃ and then 8.9g of Mg (OH) were added 2 Stirring thoroughly, evaporating to remove water, drying the obtained solid powder at 120 deg.C for 12 hr, calcining at 550 deg.C for 6 hr, and grinding thoroughly to obtain beta-Mg 2 V 2 O 7 Powder for standby;
(2) 0.199 g Pd (NH) was weighed out by the dipping method 3 ) 2 Cl 2 And 0.0172 g of boric acid was dissolved in 30 ml of deionized water, after which 10g of beta-Mg was added 2 V 2 O 7 The composite carrier is stirred and dipped for 6 hours, then dried in water bath at 90 ℃, the product is ground into powder and roasted for 6 hours at 450 ℃, and the 1 percent Pd-0.03 percent B/beta-Mg is obtained 2 V 2 O 7 A catalyst.
1% of Pd-0.03% as described above B/beta-Mg 2 V 2 O 7 After the catalyst was compacted and molded, the catalyst was crushed and sieved to 40 mesh, and the catalytic performance of the catalyst in the carbon five resin hydrorefining reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Comparative example 4% Pd-0.12% 2 V 2 O 7 -50%SiO 2
(1) 17.9 g NH were weighed 4 VO 3 Dissolved in hot water at 85 ℃ and then 8.9g of Mg (OH) were added 2 Stirring thoroughly, evaporating to remove water, drying the obtained solid powder at 120 deg.C for 12 hr, calcining at 550 deg.C for 6 hr, and grinding thoroughly to obtain beta-Mg 2 V 2 O 7 Powder for standby;
(2) Preparing 40 ml of alcohol-water solution according to a volume ratio of 1 2 V 2 O 7 And SiO 2 The mass ratio of (1) 2 V 2 O 7 Stirring and aging the powder at 85 ℃ for 8h, then gelling and aging at room temperature for 24h, drying the obtained gel in an oven at 120 ℃ for 36 h, grinding the obtained solid, roasting at 450 ℃ for 6 h,obtaining 50% beta-Mg 2 V 2 O 7 -50%SiO 2 A composite carrier;
(3) By dipping method, 0.199 g Pd (NH) is weighed 3 ) 2 Cl 2 And 0.069 g of boric acid was dissolved in 30 ml of deionized water, followed by addition of 10g of 50% beta-Mg 2 V 2 O 7 -50%SiO 2 The composite carrier is immersed under stirring for 6 hours, dried in a water bath at 90 ℃ and the product is ground to a powder and calcined at 450 ℃ for 6 hours to obtain 1% Pd-0.12% B/50% beta-Mg 2 V 2 O 7 -50%SiO 2 A catalyst.
1% Pd-0.12% as described above B/50% beta-Mg 2 V 2 O 7 -50%SiO 2 After the catalyst was compacted and molded, the catalyst was crushed and sieved to 40 mesh, and the catalytic performance of the catalyst in the carbon five resin hydrorefining reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Example 2% Pt-0.03% B/50% beta-Mg 2 V 2 O 7 - 50%SiO 2
(1) 17.9 g NH were weighed 4 VO 3 Dissolved in hot water at 85 ℃ and then 8.9g of Mg (OH) were added 2 Stirring thoroughly, evaporating to remove water, drying the obtained solid powder at 120 deg.C for 12 hr, calcining at 550 deg.C for 6 hr, and grinding thoroughly to obtain beta-Mg 2 V 2 O 7 Powder for standby;
(2) Preparing 40 ml of alcohol-water solution according to a volume ratio of 1 2 V 2 O 7 And SiO 2 The mass ratio of (1) 2 V 2 O 7 Stirring and aging the powder at 85 ℃ for 8h, then gelling and aging at room temperature for 24h, drying the obtained gel in an oven at 120 ℃ for 36 h, grinding the obtained solid, and roasting at 450 ℃ for 6 h to obtain 50% beta-Mg 2 V 2 O 7 -50%SiO 2 A composite carrier;
(3) 0.181 g of Pt (NH) was weighed out by dipping method 3 ) 4 Cl 2 And 0.0172 g of boric acid was dissolved in 30 ml of deionized water, followed by addition10g 50%β-Mg 2 V 2 O 7 -50%SiO 2 The composite carrier is immersed under stirring for 6 hours, dried in a water bath at 90 ℃ and the product is ground to a powder and calcined at 450 ℃ for 6 hours to obtain a 1% Pt-0.03% B/50% beta-Mg 2 V 2 O 7 -50%SiO 2 A catalyst.
1% of the above Pt-0.03% 2 V 2 O 7 -50%SiO 2 After the catalyst was compacted and molded, the catalyst was crushed and sieved to 40 mesh, and the catalytic performance of the catalyst in the carbon five resin hydrorefining reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Example 3% Pd-0.03% B/40% beta-Mg 2 V 2 O 7 -60%SiO 2
(1) 17.9 g NH were weighed 4 VO 3 Dissolved in hot water at 85 ℃ and then 8.9g of Mg (OH) were added 2 Stirring thoroughly, evaporating to remove water, drying the obtained solid powder at 120 deg.C for 12 hr, calcining at 550 deg.C for 6 hr, and grinding thoroughly to obtain beta-Mg 2 V 2 O 7 Powder for later use;
(2) Preparing 40 ml of alcohol-water solution according to a volume ratio of 1 2 V 2 O 7 And SiO 2 The mass ratio of (1) is 2 2 V 2 O 7 Stirring and aging the powder at 85 ℃ for 8h, then gelling and aging at room temperature for 24h, drying the obtained gel in an oven at 120 ℃ for 36 h, grinding the obtained solid, and roasting at 450 ℃ for 6 h to obtain 40% beta-Mg 2 V 2 O 7 -60%SiO 2 A composite carrier;
(3) 0.199 g Pd (NH) was weighed out by the dipping method 3 ) 2 Cl 2 And 0.0172 g of boric acid was dissolved in 30 ml of deionized water, after which 10g of 50% beta-Mg was added 2 V 2 O 7 -50%SiO 2 Composite carrier, stirring and immersing for 6 hours, drying in water bath at 90 ℃, grinding the product into powder and roasting at 450 ℃ for 6 hours, obtaining 1% Pd-0.03% B/40% beta-Mg% 2 V 2 O 7 -60%SiO 2 A catalyst.
1% of Pd-0.03% as described above, B/40% of beta-Mg 2 V 2 O 7 -60%SiO 2 After the catalyst was compacted and molded, the catalyst was crushed and sieved to 40 mesh, and the catalytic performance of the catalyst in the carbon five resin hydrorefining reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Example 4.5% Pd-0.03% 2 V 2 O 7 -70%SiO 2
(1) 17.9 g NH were weighed 4 VO 3 Dissolved in hot water at 85 ℃ and then 8.9g of Mg (OH) were added 2 Stirring thoroughly, evaporating to remove water, drying the obtained solid powder at 120 deg.C for 12 hr, calcining at 550 deg.C for 6 hr, and grinding thoroughly to obtain beta-Mg 2 V 2 O 7 Powder for standby;
(2) Preparing 40 ml of alcohol-water solution according to a volume ratio of 1 2 V 2 O 7 And SiO 2 The mass ratio of (1) to (7) is 3, 24.3 g of orthosilicic acid alcohol ester and 3.0 g of beta-Mg are dripped into the alcohol-water solution 2 V 2 O 7 Stirring and aging the powder at 85 ℃ for 8h, then gelling and aging at room temperature for 24h, drying the obtained gel in an oven at 120 ℃ for 36 h, grinding the obtained solid, and roasting at 450 ℃ for 6 h to obtain 30% beta-Mg 2 V 2 O 7 -70%SiO 2 A composite carrier;
(3) 0.199 g Pd (NH) was weighed out by the dipping method 3 ) 2 Cl 2 And 0.0172 g of boric acid was dissolved in 30 ml of deionized water, followed by addition of 10g of 30% beta-Mg 2 V 2 O 7 -70%SiO 2 The composite carrier is immersed under stirring for 6 hours, dried in a water bath at 90 ℃ and the product is ground to a powder and calcined at 450 ℃ for 6 hours to obtain 1% Pd-0.03% B/30% beta-Mg 2 V 2 O 7 -70%SiO 2 A catalyst.
1% of Pd-0.03% as described above, B/30% of beta-Mg 2 V 2 O 7 -70%SiO 2 After the catalyst was compacted and molded, the catalyst was crushed and sieved to 40 mesh granules, and the catalyst was evaluated on carbon in the same manner as in example 1Five catalytic performances in the resin hydrofining reaction. The reaction results are shown in Table 1.
Example 5.5% Pd-0.03% 2 V 2 O 7 -40%SiO 2
(1) 17.9 g NH were weighed 4 VO 3 Dissolved in hot water at 85 ℃ and then 8.9g of Mg (OH) were added 2 Stirring thoroughly, evaporating to remove water, drying the obtained solid powder at 120 deg.C for 12 hr, calcining at 550 deg.C for 6 hr, and grinding thoroughly to obtain beta-Mg 2 V 2 O 7 Powder for standby;
(2) Preparing 40 ml of alcohol-water solution according to a volume ratio of 1 2 V 2 O 7 And SiO 2 The mass ratio of (1) to (2) is 3, 13.9 g of orthosilicic acid alcohol ester and 6.0 g of beta-Mg are dripped into the alcohol-water solution 2 V 2 O 7 Stirring and aging the powder at 85 ℃ for 8h, then gelling and aging at room temperature for 24h, drying the obtained gel in an oven at 120 ℃ for 36 h, grinding the obtained solid, and roasting at 450 ℃ for 6 h to obtain 60% beta-Mg 2 V 2 O 7 -40%SiO 2 A composite carrier;
(3) 0.199 g Pd (NH) was weighed out by the dipping method 3 ) 2 Cl 2 And 0.0172 g of boric acid was dissolved in 30 ml of deionized water, after which 10g of 60% beta-Mg was added 2 V 2 O 7 -40%SiO 2 The composite carrier is immersed under stirring for 6 hours, dried in a water bath at 90 ℃ and the product is ground to a powder and calcined at 450 ℃ for 6 hours to obtain 1% Pd-0.03% B/60% beta-Mg 2 V 2 O 7 -40%SiO 2 A catalyst.
1% of Pd-0.03% of B/60% of beta-Mg 2 V 2 O 7 -40%SiO 2 After the catalyst was compacted and molded, the catalyst was crushed and sieved to 40 mesh, and the catalytic performance of the catalyst in the carbon five resin hydrorefining reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Example 6.5% Pd-0.03% 2 V 2 O 7 -50%SiO 2
(1) 17.9 g of NH were weighed 4 VO 3 Dissolved in hot water at 85 ℃ and then 8.9g of Mg (OH) were added 2 Stirring thoroughly, evaporating to remove water, drying the obtained solid powder at 120 deg.C for 12 hr, calcining at 550 deg.C for 6 hr, and grinding thoroughly to obtain beta-Mg 2 V 2 O 7 Powder for standby;
(2) Preparing 40 ml of alcohol-water solution according to a volume ratio of 1 2 V 2 O 7 And SiO 2 The mass ratio of (1) 2 V 2 O 7 Stirring and aging the powder at 85 ℃ for 8h, then gelling and aging at room temperature for 24h, drying the obtained gel in an oven at 120 ℃ for 36 h, grinding the obtained solid, and roasting at 450 ℃ for 6 h to obtain 50% beta-Mg 2 V 2 O 7 -50%SiO 2 A composite carrier;
(3) 0.0995 g Pd (NH) was weighed by dipping method 3 ) 2 Cl 2 And 0.0172 g of boric acid was dissolved in 30 ml of deionized water, after which 10g of 50% beta-Mg was added 2 V 2 O 7 -50%SiO 2 The composite carrier was immersed under stirring for 6 hours, dried in a water bath at 90 ℃ and the resultant was pulverized and then calcined at 450 ℃ for 6 hours to obtain a content of 0.5% Pd-0.03% B/50% beta-Mg 2 V 2 O 7 -50%SiO 2 A catalyst.
Pd-0.03% by weight of the above-mentioned 0.5%/50% beta-Mg 2 V 2 O 7 -50%SiO 2 After the catalyst was compacted and molded, the catalyst was crushed and sieved to 40 mesh, and the catalytic performance of the catalyst in the carbon five resin hydrorefining reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
Example 7.5% Pd-0.5% Pt-0.03% 2 V 2 O 7 -50%SiO 2
(1) 17.9 g NH were weighed 4 VO 3 Dissolved in hot water at 85 ℃ and then 8.9g of Mg (OH) were added 2 Stirring thoroughly, evaporating to remove water, drying the obtained solid powder at 120 deg.C for 12 hr, calcining at 550 deg.C for 6 hr, and grinding thoroughly to obtain beta-Mg 2 V 2 O 7 Powder for standby;
(2) Preparing 40 ml of alcohol-water solution according to a volume ratio of 1 2 V 2 O 7 And SiO 2 The mass ratio of (1) 2 V 2 O 7 Stirring and aging the powder at 85 ℃ for 8h, then gelling and aging at room temperature for 24h, drying the obtained gel in an oven at 120 ℃ for 36 h, grinding the obtained solid, and roasting at 450 ℃ for 6 h to obtain 50% beta-Mg 2 V 2 O 7 -50%SiO 2 A composite carrier;
(3) 0.0995 g Pd (NH) was weighed by dipping method 3 ) 2 Cl 2 、0.0855 g Pt(NH 3 ) 4 Cl 2 And 0.0172 g of boric acid was dissolved in 30 ml of deionized water, after which 10g of 50% beta-Mg was added 2 V 2 O 7 -50%SiO 2 Composite carrier, stirring and immersing for 6 hours, drying in 90 ℃ water bath, grinding the product to powder and roasting at 450 ℃ for 6 hours, obtaining 0.5% Pd-0.5% Pt-0.03% B/50% beta-Mg 2 V 2 O 7 -50%SiO 2 A catalyst.
Pd-0.5% of the above-mentioned 0.5% Pt-0.03% 2 V 2 O 7 -50%SiO 2 After the catalyst was compacted and molded, the catalyst was crushed and sieved to 40 mesh, and the catalytic performance of the catalyst in the carbon five resin hydrorefining reaction was evaluated in the same manner as in example 1. The reaction results are shown in Table 1.
TABLE 1
As can be seen from the comparison between example 1 and comparative examples 1 and 4, the modification of a proper amount of B element can improve the dispersion of the active metal in the catalyst, which is advantageous for improving the hydrogenation activity of the resin.
As can be seen from a comparison of example 1 with comparative examples 2 and 3, β -Mg 2 V 2 O 7 And SiO 2 The composite carrier can give consideration to both the surface area of the catalyst and the active metalDispersing, thereby reducing the loss of active metal.
As can be seen from comparison of examples 1 and 3 to 5, when beta-Mg 2 V 2 O 7 When the catalyst accounts for 30-60% of the mass of the catalyst, the catalyst has high hydrogenation activity and less loss of active metal after reaction, wherein 50% of beta-Mg is used 2 V 2 O 7 -50%SiO 2 The effect is the best for the composite carrier.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (9)
1. A metal loss resistant C-V petroleum resin hydrogenation catalyst is characterized in that: comprises the following components:
(a) A Pt group active metal;
（b）β-Mg 2 V 2 O 7 /SiO 2 a composite carrier;
(c) And (4) an auxiliary agent boron.
2. The carbon five petroleum resin hydrogenation catalyst according to claim 1, characterized in that: the Pt group active metal is one or more of Pt, pd, ir, ru and Rh.
3. The carbon five petroleum resin hydrogenation catalyst according to claim 1, characterized in that: the load capacity of the Pt group active metal is 0.1-5% of the mass of the composite carrier.
4. The carbon five petroleum resin hydrogenation catalyst according to claim 1, characterized in that: beta-Mg in the composite carrier 2 V 2 O 7 The content of (A) is 30-60% of the total mass of the composite carrier.
5. The carbon five petroleum resin hydrogenation catalyst according to claim 1, characterized in that: the content of the boron additive is 0.01-2% of the mass of the composite carrier.
6. A method for preparing the carbon five petroleum resin hydrogenation catalyst according to claim 1, which is characterized in that: the method comprises the following steps:
（1）β-Mg 2 V 2 O 7 preparation of
Reacting NH 4 VO 3 Dissolving in hot water of 85 deg.C, adding Mg (OH) 2 Stirring thoroughly, evaporating to remove water, drying the obtained solid powder at 120 deg.C for 12 hr, calcining at 550 deg.C for 6 hr, and grinding thoroughly to obtain beta-Mg 2 V 2 O 7 Powder;
（2）β-Mg 2 V 2 O 7 /SiO 2 preparation of composite Carrier
Preparing 40 ml of alcohol-water solution according to a volume ratio of 1 2 V 2 O 7 And SiO 2 The dosage proportion is that a certain amount of orthosilicic acid alcohol ester and a certain amount of beta-Mg are dripped into the alcohol-water solution 2 V 2 O 7 Stirring and aging at 40-90 deg.C for 8 hr, gelatinizing and aging at room temperature for 24 hr, drying the gel at 120 deg.C for 36 hr, grinding the solid, and calcining at 450 deg.C for 6 hr to obtain beta-Mg 2 V 2 O 7 /SiO 2 A composite carrier;
(3) Preparation of the catalyst:
dissolving a Pt group active metal precursor and boric acid in deionized water according to a certain proportion by adopting an immersion method, and then adding the beta-Mg prepared in the step (2) 2 V 2 O 7 /SiO 2 And (3) stirring and soaking the composite carrier for 6 hours, drying the composite carrier in a water bath at 90 ℃, grinding the product into powder, and roasting the powder for 6 hours at 450 ℃ to obtain the hydrogenation catalyst.
7. The method for preparing a hydrocarbon five petroleum resin hydrogenation catalyst according to claim 6, wherein: NH used in step 1) 4 VO 3 And Mg (OH) 2 1 is 1.
8. The method for preparing a hydrocarbon five petroleum resin hydrogenation catalyst according to claim 6, wherein: the Pt group active metal precursor in the step 3) is chloride, nitrate, hydrochloride, chloride ammonia complex or nitrate ammonia complex of Pt group active metal.
9. Use of the hydrogenation catalyst of claim 1 in the hydrofinishing of carbon five petroleum resins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310001921.9A CN115814787A (en) | 2023-01-03 | 2023-01-03 | Metal loss resistant carbon five petroleum resin hydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310001921.9A CN115814787A (en) | 2023-01-03 | 2023-01-03 | Metal loss resistant carbon five petroleum resin hydrogenation catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115814787A true CN115814787A (en) | 2023-03-21 |
Family
ID=85520009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310001921.9A Pending CN115814787A (en) | 2023-01-03 | 2023-01-03 | Metal loss resistant carbon five petroleum resin hydrogenation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115814787A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012012497A (en) * | 2010-06-30 | 2012-01-19 | Basf Coatings Japan Ltd | Undercoat paint composition excellent in corrosion resistance |
| KR101341242B1 (en) * | 2012-08-08 | 2013-12-12 | 삼성토탈 주식회사 | Magnesium orthovanadate-magnesia-zirconia catalyst prepared by a single-step sol-gel method for oxidative dehydrogenation of n-butane, preparation method thereof, and method for producing n-butene and 1,3-butadiene using said catalyst |
| CN105413676A (en) * | 2015-11-06 | 2016-03-23 | 中国科学院山西煤炭化学研究所 | Method for preparing three-dimensional ordered macroporous V-Mg oxide materials and application thereof |
| CN105727980A (en) * | 2014-12-06 | 2016-07-06 | 中国石油化工股份有限公司 | Preparation method of catalyst for propane oxidative dehydrogenation to propylene |
| CN109529858A (en) * | 2018-12-19 | 2019-03-29 | 山西大学 | A kind of Modified Nickel Si catalyst and its application in gamma-butyrolacton is prepared in catalysis maleic anhydride hydrogenation |
| CN111732123A (en) * | 2020-06-11 | 2020-10-02 | 北京华电光大环境股份有限公司 | Method for preparing magnesium metavanadate from waste SCR denitration catalyst |
| CN112723980A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Method for producing styrene by ethylbenzene oxidative dehydrogenation |
| CN113748170A (en) * | 2019-02-11 | 2021-12-03 | 应用石墨烯材料英国有限公司 | Corrosion protection of metal substrates |
| CN114570363A (en) * | 2022-03-03 | 2022-06-03 | 中化泉州能源科技有限责任公司 | Noble metal-based carbon-five petroleum resin hydrogenation catalyst, and preparation method and application thereof |
| CN114602464A (en) * | 2022-04-25 | 2022-06-10 | 中化泉州能源科技有限责任公司 | Hydrocatalyst for C-V petroleum resin and its preparing process |
-
2023
- 2023-01-03 CN CN202310001921.9A patent/CN115814787A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012012497A (en) * | 2010-06-30 | 2012-01-19 | Basf Coatings Japan Ltd | Undercoat paint composition excellent in corrosion resistance |
| KR101341242B1 (en) * | 2012-08-08 | 2013-12-12 | 삼성토탈 주식회사 | Magnesium orthovanadate-magnesia-zirconia catalyst prepared by a single-step sol-gel method for oxidative dehydrogenation of n-butane, preparation method thereof, and method for producing n-butene and 1,3-butadiene using said catalyst |
| CN105727980A (en) * | 2014-12-06 | 2016-07-06 | 中国石油化工股份有限公司 | Preparation method of catalyst for propane oxidative dehydrogenation to propylene |
| CN105413676A (en) * | 2015-11-06 | 2016-03-23 | 中国科学院山西煤炭化学研究所 | Method for preparing three-dimensional ordered macroporous V-Mg oxide materials and application thereof |
| CN109529858A (en) * | 2018-12-19 | 2019-03-29 | 山西大学 | A kind of Modified Nickel Si catalyst and its application in gamma-butyrolacton is prepared in catalysis maleic anhydride hydrogenation |
| CN113748170A (en) * | 2019-02-11 | 2021-12-03 | 应用石墨烯材料英国有限公司 | Corrosion protection of metal substrates |
| CN112723980A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Method for producing styrene by ethylbenzene oxidative dehydrogenation |
| CN111732123A (en) * | 2020-06-11 | 2020-10-02 | 北京华电光大环境股份有限公司 | Method for preparing magnesium metavanadate from waste SCR denitration catalyst |
| CN114570363A (en) * | 2022-03-03 | 2022-06-03 | 中化泉州能源科技有限责任公司 | Noble metal-based carbon-five petroleum resin hydrogenation catalyst, and preparation method and application thereof |
| CN114602464A (en) * | 2022-04-25 | 2022-06-10 | 中化泉州能源科技有限责任公司 | Hydrocatalyst for C-V petroleum resin and its preparing process |
Non-Patent Citations (5)
| Title |
|---|
| ZHANG SH ET AL.: "Preparation of SBA-15-supported β-Mg2V2O7 catalysts and their properties in oxidative dehydrogenation of propane", 《CHINESE JOURNAL OF CATALYSIS》, vol. 31, no. 11, pages 1374 - 1380 * |
| 计宝峰等: "丙烷氧化脱氢反应中Mg2V2O7催化剂氧活度的原位监测", 《催化学报》, vol. 30, no. 5, pages 375 - 377 * |
| 许翠红等: "石油树脂加氢催化剂的活性研究", 《甘肃科技》, vol. 25, no. 7, pages 39 - 40 * |
| 高宽: "以CeO2为载体铜基催化剂的制备及其催化糠醛加氢性能研究", 《中国优秀硕士学位全文数据库 工程科技I辑》, no. 12, pages 016 - 181 * |
| 魏璨等: "石油树脂应用于改性研究进展", 《工业催化》, vol. 23, no. 11, pages 866 - 873 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109305918B (en) | Synthesis method of halogenated aniline | |
| EP1812160B1 (en) | A process for preparing a noble metal-based alloy catalyst on a carbon support material. | |
| CN115228477B (en) | Carbon-coated copper-zinc-aluminum catalyst and preparation method and application thereof | |
| US11342565B2 (en) | Fuel cell catalyst and manufacturing method thereof | |
| CN111686721A (en) | Palladium ruthenium alloy catalyst and preparation method and application thereof | |
| CN114570363A (en) | Noble metal-based carbon-five petroleum resin hydrogenation catalyst, and preparation method and application thereof | |
| CN114345324A (en) | Biomass carbon-based metal single-atom composite catalyst, preparation method and application thereof | |
| CN113769739A (en) | Hydrocatalyst for C-V petroleum resin | |
| CN112186199B (en) | Catalyst for solid polymer fuel cell and preparation method thereof | |
| CN115814787A (en) | Metal loss resistant carbon five petroleum resin hydrogenation catalyst | |
| CN114602464A (en) | Hydrocatalyst for C-V petroleum resin and its preparing process | |
| CN113952957A (en) | Nickel series hydrogenation catalyst and preparation method and application thereof | |
| CN107570157B (en) | Preparation method of ordered mesoporous carbon catalyst for preparing p-aminophenol | |
| CN111659390A (en) | Platinum-based catalyst containing promethium or compound thereof | |
| CN111659384A (en) | Platinum-based catalyst containing plutonium or plutonium compound | |
| CN107308937B (en) | Application of carbon-based catalyst in catalytic hydrogenation reaction of p-nitrophenol | |
| CN115555017B (en) | Dechlorination type carbon five petroleum resin hydrogenation catalyst and preparation method thereof | |
| CN117839743A (en) | Low-chroma high-transparency carbon five petroleum resin hydrogenation catalyst and preparation method thereof | |
| CN112490452B (en) | Fuel cell anode catalyst and preparation method and application thereof | |
| CN114471608B (en) | Method for refining and purifying diethylene glycol through hydrofining | |
| CN113368870B (en) | Sulfur ligand modified monoatomic catalyst and preparation method and application thereof | |
| CN113680375B (en) | Carbon five petroleum resin hydrogenation catalyst and preparation method thereof | |
| CN102441392B (en) | Method for preparing low-cost high-activity cobalt-based Fischer-Tropsch synthetic catalyst | |
| CN113941327A (en) | Palladium-based catalyst and preparation method and application thereof | |
| CN116742014A (en) | Fuel cell catalyst using anion resin as carrier precursor and preparation method and application thereof |
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 |