CN106881124A - The catalyst and preparation method of a kind of hydrogenation of raffinating oil - Google Patents
The catalyst and preparation method of a kind of hydrogenation of raffinating oil Download PDFInfo
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- CN106881124A CN106881124A CN201710158347.2A CN201710158347A CN106881124A CN 106881124 A CN106881124 A CN 106881124A CN 201710158347 A CN201710158347 A CN 201710158347A CN 106881124 A CN106881124 A CN 106881124A
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- zinc oxide
- catalyst
- alumina
- hydrogenation
- zinc
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 19
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 84
- 239000011701 zinc Substances 0.000 claims description 73
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 71
- 229910052725 zinc Inorganic materials 0.000 claims description 71
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 57
- 239000011787 zinc oxide Substances 0.000 claims description 42
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 41
- 239000011591 potassium Substances 0.000 claims description 41
- 229910052700 potassium Inorganic materials 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 37
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 36
- 239000011777 magnesium Substances 0.000 claims description 36
- 229910052749 magnesium Inorganic materials 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 36
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 30
- 229910001676 gahnite Inorganic materials 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000004411 aluminium Substances 0.000 claims description 22
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 20
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000395 magnesium oxide Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 13
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002671 adjuvant Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000004448 titration Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000002803 maceration Methods 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 235000010333 potassium nitrate Nutrition 0.000 claims description 8
- 239000004323 potassium nitrate Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 241000219782 Sesbania Species 0.000 claims description 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 150000003751 zinc Chemical class 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 3
- 238000009938 salting Methods 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000000969 carrier Substances 0.000 claims 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 150000001336 alkenes Chemical class 0.000 abstract description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 5
- JODIJOMWCAXJJX-UHFFFAOYSA-N [O-2].[Al+3].[O-2].[Zn+2] Chemical compound [O-2].[Al+3].[O-2].[Zn+2] JODIJOMWCAXJJX-UHFFFAOYSA-N 0.000 abstract 1
- 230000002779 inactivation Effects 0.000 abstract 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 11
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- 239000012018 catalyst precursor Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002872 contrast media Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 2
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of catalyst and preparation method for hydrogenation of raffinating oil, the composition of catalyst is with oxidation material gauge, including following component：The 92wt% of complex carrier 80.0 containing zinc oxide aluminum oxide, the 20wt% of active component nickel oxide 8.Catalyst raffinate oil aromatic hydrocarbons and hydrogenation of olefins activity it is high, catalyst not easy in inactivation, with longer service cycle.
Description
Technical field
The invention belongs to hydrogenation catalyst technical field, more particularly to a kind of hydrogenation of raffinating oil catalyst and preparation side
Method, the catalyst and system of more specifically a kind of hydrogenation of raffinating oil with contained zinc oxide-alumina composite as carrier
Preparation Method.
Background technology
The solvent naphtha of various trades mark can be produced using refinery's hydrogenation of raffinating oil, solvent naphtha can refer to using petroleum refining and
Multiple product and the byproduct processing of petrochemical iy produced with a major class that its dissolubility and volatility are main application performance
Product.The solubility property of aliphatic hydrocarbon is not so good as aromatic hydrocarbons, but the toxicity of aromatic hydrocarbons is serious, and producing low virtue, the solvent naphtha without virtue turns into
The developing direction of solvent naphtha industry.The method of domestic more use at present has the de- virtue of sulfonation-oxidizing process, takes off alkene, the de- virtue of molecular sieve,
Desulfurization, the de- virtue of solvent extraction etc..And the predominant methods of external solvent refining are the de- virtue of deep hydrofinishing, desulfurization, de- alkene.It is refined
The gap of technology is that China's varsol unsaturated hydrocarbons and objectionable impurities content are high, smell is big, the master heavy to operating environment pollution
Want reason.Therefore advanced process for purification is used, environmental type solvent can be produced with competitive scale of investment construction
The processing unit (plant) of product, it has also become the task of top priority of China's solvent naphtha industry development, key technology therein is exactly high activity
The development of anti-impurity Hydrobon catalyst.
Hydrobon catalyst is usually as carrier, with VIII and group vib metallic element as activearm with salic
Point, also have to improve the activity and stability of catalyst, carrier is improved.For example with aluminum oxide-silica as carrier
, or other auxiliary agents are added, general P, F, B, Si, Ti, Zr etc..And preceding use W-Mo-Ni-P/Al2O3Catalyst is carrying
High activity is widely used in the industrial catalyst of fraction oil hydrogenation refining.
Chinese patent：ZL03126138.8 discloses the catalyst used by a kind of kerosene type solvent naphtha.Institute in the method
Spent hydroprocessing catalyst is W-Ni/TiO2-Al2O3Or W-Mo-Ni/TiO2-Al2O3.Chinese patent：ZL200310112781.5 exists
It is right using cobalt molybdenum and nickel-alumina catalyst under conditions of 120 DEG C -280 DEG C of reaction temperature and hydrogen dividing potential drop 0.2-0.4MPa (gauge pressure)
Light oil products and oil plant the production light oil of natural gas processing carry out hydrofinishing, to produce high standard solvent naphtha.
At present, the catalyst of research and development be used for raffinate oil hydrogenation production aromatic solvent naphtha when, catalyst it is activity stabilized
Property it is good, the commercial Application cycle is more long.
The content of the invention
The present invention provides a kind of catalyst and preparation method for hydrogenation of raffinating oil, and the catalyst has more preferable raffinate
Oily hydrogenation activity and stability.The carrier of catalyst is the complex carrier containing zinc oxide-alumina, and active component is nickel.This is answered
Conjunction carrier zinc-aluminium is uniformly dispersed, specific surface area is high.Catalyst aromatic hydrogenation activity is high, and the anti-impurity ability of catalyst is strong, production
Service cycle is long.
A kind of catalyst for hydrogenation of raffinating oil of the present invention, it is composed of the following components：
Complex carrier 80.0-92wt% containing zinc oxide-alumina, active component nickel oxide 8-20wt%.
The described complex carrier containing zinc oxide-alumina, including the zinc oxide containing gahnite, aluminum oxide, and add
Enter phosphorus, potassium and magnesium as adjuvant component, the composition of complex carrier is with oxidation material gauge：Zinc oxide content containing gahnite
It is 5.0-40.0wt%, alumina content is 60.0-95.0wt%, and the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality
Percentage composition is respectively P2O50.2-1.2wt%, K2O 0.2-2.5wt%, MgO 2.0-5.5wt%, complex carrier specific surface
Product 200-300m2/g。
Preferably, a kind of described catalyst for hydrogenation of raffinating oil, composed of the following components：
Complex carrier 85.0-90.0wt% containing zinc oxide-alumina, active component nickel oxide 10-15wt%；
The described complex carrier containing zinc oxide-alumina, with oxidation material gauge：Zinc oxide containing gahnite contains
It is 10.0-35.0wt% to measure, and alumina content is 65.0-90.0wt%, and the content of adjuvant component phosphorus, potassium and magnesium accounts for carrier quality
Percentage composition be respectively P2O50.4-1.0wt%, K2O 0.2-2.5wt%, MgO 2.5-4.5wt%, complex carrier compare table
Area 200-300m2/g。
A kind of preparation method of catalyst for hydrogenation of raffinating oil of the present invention, comprises the following steps：
Nickeliferous soluble-salt is made into maceration extract, complex carrier of the dipping containing zinc oxide-alumina is dried, and roasting is obtained
Raffinate oil hydrogenation catalysts；
The described complex carrier containing zinc oxide-alumina, the method for being prepared by the following procedure is obtained：
Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, is prepared containing gahnite
Zinc oxide stratified material；Zinc oxide and boehmite containing gahnite are well mixed, sesbania powder, nitric acid is added
The acid solution containing Sodium Polyacrylate after acidification, and phosphoric acid, potassium nitrate and magnesium nitrate the aqueous solution, kneading, after shaping,
Dried process, calcination process is obtained containing zinc oxide-alumina composite carrier.
The described zinc oxide stratified material prepared containing gahnite, is preferably prepared by the following preparation method：Will
Soluble Zn salting liquid is divided into 2-4 parts, under the conditions of 40-80 DEG C, and sodium metaaluminate and sodium carbonate are added in a zinc solution
Mixed solution containing aluminium, stops that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；Be further continued for be added dropwise another zinc salt it is molten
Liquid；After zinc solution is dripped, continue that mixed solution containing aluminium is added dropwise, stop being added dropwise containing aluminium mixing when pH value reaches 8.5-9.5
Solution；To contain aluminium mixed solution according to the above method and replace titration with zinc solution, until zinc solution whole completion of dropping, finally
Mixed solution containing aluminium is once added dropwise, when pH value reaches 8.5-9.5, the alternating titration process of non-constant pH value terminates, control drop
Determine process to be completed in 1-6h；After 80-95 DEG C of aging 2-8h, cooling washing dries 4-10h to neutrality at 80-140 DEG C,
450-550 DEG C of roasting 4-10h, obtains the dispersed zinc oxide stratified material containing gahnite.
The soluble zinc salt is zinc nitrate or zinc chloride.The acid containing Sodium Polyacrylate after described nitric acid acidification
Solution, is preferably prepared by the following preparation method：Deionized water is heated to 30-90 DEG C, nitric acid is then dissolved into deionization
In water, Sodium Polyacrylate is added, and dissolve complete, obtain the acid solution containing Sodium Polyacrylate.Described Sodium Polyacrylate
Addition is preferably the 0.6-12.0wt% of boehmite.The Sodium Polyacrylate of acidified treatment, its is uniformly dispersed more
Good, zinc oxide, alumina powder mixing are more uniform.
The addition of the sesbania powder is preferably the 0.2-7.0wt% of boehmite.
Described drying, roasting obtains raffinate oil hydrogenation catalysts, preferably 120 DEG C dried process 6 hours, 400 DEG C -500
Calcination process 5-8 hours at DEG C.Described dried process, calcination process, be 110-150 DEG C dried process 4-8 hours, 550 DEG C-
Calcination process 4.5-8 hours at 700 DEG C.
The complex carrier containing zinc oxide-alumina obtained using preparation method of the present invention, can also using potassium and
Magnesium is modified to the complex carrier surface containing zinc oxide-alumina, and the concentration of potassium and magnesium is unsuitable too high, preferably configuration concentration
Carrier surface is sprayed less than the potassium nitrate and magnesium nitrate aqueous solution when preparing complex carrier, carrier is preferably carried out as follows
Surface is modified：Aqueous solution spray complex carrier containing zinc oxide-alumina of the configuration containing potassium nitrate and magnesium nitrate, through drying, roasting
Burning obtains used additives potassium and magnesium carries out the modified zinc oxide-alumina complex carrier in surface, and control zinc oxide-alumina is compound to be carried
Potassium oxide and content of magnesia are respectively in the range of 0.2-2.5wt% and 2.5-5.5wt% in body, and make carrier external oxidation
The content of potassium and magnesia is 1.1-1.2 times of internal oxidation potassium and content of magnesia.
Compared with prior art, the present invention has advantages below：
1st, the zinc oxide containing gahnite of the invention is that alternately prepared by titration by non-constant pH, i.e., in non-constant pH
Prepared by the alternating titration of sodium carbonate liquor and zinc-containing solution under the conditions of value, containing aluminium, accordingly, it would be desirable to zinc-containing solution is divided into number
Part, the sodium carbonate liquor containing aluminium is strong alkali solution, and the strong acid weak base salting liquid containing zinc is acid solution, between aluminium zinc solution
Repeatedly alternately titration pH value is swung between soda acid, be conducive to aluminium zinc precursor thing can orderly accumulation be layer structure, through straight
Connect that low-temperature bake can be uniformly dispersed and specific surface area can be in 150-220m2The point containing zinc-aluminium regulated and controled between/g is brilliant
The zinc oxide material of stone, it is to avoid the precursor obtained using alkaline solution one step titration zinc-aluminium mixed solution needs high-temperature roasting
The problem of fixed zinc oxide, decreases hydrothermal treatment process.The material has larger specific surface area.
2nd, the present invention can also introduce phosphorus, potassium, magnesium and Sodium Polyacrylate, poly- third in zinc oxide-alumina complex carrier
Olefin(e) acid sodium can be repaired and improve catalytic inner pore passage structure, and diffusion effect is good in catalyst.The carrier is prepared into hydrogenation catalyst
Agent, such as nickel-base catalyst, are conducive to adjusting the acidity of catalyst, and finishing is improved catalytic inner pore passage structure, can be reduced
The polymerization of alkene in feedstock oil, improves the stability of hydrogenation catalyst.
3rd, the present invention obtain containing zinc oxide-alumina composite carrier, after surface is through potassium and magnesium modification, make carrier table
The content of the concentration formation concentration difference of the potassium in face and the concentration of magnesium and carrier inside potassium and magnesium, carrier surface potassium and magnesium is higher than carrier
The molar content or mass content of the content of internal potassium and magnesium, i.e., outside potassium and magnesium can be the 1.1- of the content of internal potassium and magnesium
1.2 times, carrier surface is tended to equally distributed state, reduce the acidity of carrier surface, the carrier can be improved
The specific surface area of catalyst.Improvement to carrier surface should not use dipping method, and impregnated carrier surface can enter large quantity of moisture
Carrier, intensity is deteriorated, and does not reach the purpose for improving carrier surface Jie-macropore ratio.To complex carrier table by the way of spray
Face is modified, and is capable of the partial pore on effective peptization complex carrier surface, so advantageously reduces the micro- of complex carrier surface
Boring ratio example, improves complex carrier surface Jie-macropore ratio, and promotion complex carrier surface is produced in more active sites loads
The heart, effectively improves catalyst activity.
4th, through potassium and magnesium modification, the complex carrier containing zinc oxide-alumina can be made carrier surface of the present invention
To be used for hydrogenation reaction of raffinating oil after the carrier loaded active component of hydrogenation catalyst.
Specific embodiment
A kind of catalyst and preparation method for hydrogenation of raffinating oil of the invention is entered with comparative example by the following examples
The detailed description of one step.But these embodiments are not regarded as limiting of the invention.
Prepare primary raw material source used by catalyst：Reagent of the present invention is commercially available prod.
Feedstock oil is reforming raffinate oil, and arene content 2.0% represents olefin(e) centent 12.4gBr2/100gOil with bromine valency,
Iodine number 6.4gI2/100gOil.
Embodiment 1
1.2kg zinc nitrates are dissolved in 6L water and are made into zinc-containing solution, by 0.24kg sodium metaaluminates and 0.30kg sodium carbonate
It is dissolved in 4L water and is made into containing aluminum solutions.Zinc-containing solution is divided into 3 parts, every part of 2L.2L zinc-containing solutions are taken, temperature keeps 80
DEG C, mixed solution containing aluminium to pH value is added dropwise thereto and reaches 9.0；Stop that mixed solution containing aluminium is added dropwise, then 2L zinc-containing solutions are added dropwise
To in hybrid system, continue dropwise addition mixed solution containing aluminium to pH value and reach 9.0；Mixed solution containing aluminium and zinc-containing solution alternately drip
Fixed, until zinc-containing solution is all added, last time is added dropwise mixed solution containing aluminium and reaches 9.0 to pH, and titration time amounts to 3h.
After 80 DEG C of aging 4h, cooling washing dries 3h to the mixture for arriving to neutrality in 135 DEG C of air atmospheres, in 500 DEG C of roastings
9h, obtains the dispersed zinc oxide stratified material containing gahnite, and in terms of oxide, the content of zinc oxide is 65%；
Specific surface area is 196m2/g。
Weigh phosphatase 11 .04g, potassium nitrate 1.03g respectively, magnesium nitrate 17.76g is dissolved completely in 60g distilled water to be made into and contains
Phosphorus, potassium, the aqueous solution of magnesium.6.0g Sodium Polyacrylates are dissolved in 70g distilled water, add the nitre that 3.8g mass concentrations are 65%
Acid.By 40g, zinc oxide and 164.3g boehmites ground and mixed containing gahnite are uniform, add 6.0g sesbania powders,
Sodium Polyacrylate acid solution, phosphorous, potassium, the aqueous solution of magnesium, kneading, after shaping, 125 DEG C of dried process 7 hours are roasted at 580 DEG C
Burn treatment and obtain within 7 hours the complex carrier containing zinc oxide-alumina.Complex carrier specific surface area 276m2/g.Complex carrier includes
Zinc oxide 25.0wt% containing gahnite, aluminum oxide is 70.4wt%, and adjuvant component phosphorus, potassium, content of magnesium are respectively P2O5
0.4wt%, K2O 1.2wt%, MgO 3.0wt%.
Take 25.6g nickel formates to be added in 30ml distilled water, then diluted with deionized water, be made into maceration extract and impregnate spherical containing
The complex carrier 100g of zinc oxide-alumina, the catalyst precursor for obtaining is calcined 6h after drying 6h at 120 DEG C at 400 DEG C, obtains
To raffinate oil hydrogenation catalysts 1.Catalyst 1 is mainly constituted：Nickel oxide 13wt%, the complex carrier containing zinc oxide-alumina
87wt%.
Comparative example 1
The zinc nitrate solution of amount same as Example 1, sodium metaaluminate and sodium carbonate liquor are well mixed by blending method, with reality
Apply that the zinc-aluminium mol ratio of example 1 is identical, similarity condition is aging, washing, dry, roasting obtains the oxide material containing zinc-aluminium.Zinc oxide
Content be 65%；Specific surface area is 141m2/g.Compared with comparative example 1, embodiment 1 is using pH swing methods zinc, the friendship of aluminum solutions
For titration, zinc-aluminium stratified material can be obtained, under the conditions of two kinds of material zinc-aluminium mol ratio identicals, embodiment 1 is containing zinc-aluminium point
The specific surface area of the zinc oxide stratified material of spar is higher.
Weigh phosphatase 11 .04g, potassium nitrate 1.03g respectively, magnesium nitrate 17.66g is dissolved completely in 60g distilled water to be made into and contains
Phosphorus, potassium, the aqueous solution of magnesium.6.0g Sodium Polyacrylates are dissolved in 70g distilled water, add the nitre that 3.8g mass concentrations are 65%
Acid.By 40g, oxide material and 164.3g boehmites ground and mixed containing zinc-aluminium are uniform, add 6.0g sesbania powders, gather
PAA acid solution, phosphorous, potassium, the aqueous solution of magnesium, kneading, after shaping, 125 DEG C of dried process 7 hours are calcined at 580 DEG C
Treatment obtains carrier in 7 hours.
Take 25.6g nickel formates to be added in 30ml distilled water, then diluted with deionized water, be made into maceration extract and impregnate spherical containing
The complex carrier 100g of zinc oxide-alumina, the catalyst precursor for obtaining is calcined 6h after drying 6h at 120 DEG C at 400 DEG C, obtains
To comparative catalyst 1.Main composition：Nickel oxide 13wt%, the complex carrier 87wt% containing zinc oxide-alumina.
Embodiment 2
The preparation method and step of the complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1
Zinc oxide, pH value is adjusted to 8.7.In terms of oxide, the content of zinc oxide is 70%；Specific surface area is 191m2/g。
Complex carrier includes the zinc oxide 30wt% containing gahnite, and aluminum oxide is 67wt%, adjuvant component phosphorus, potassium,
Content of magnesium is respectively P2O50.6wt%, K2O 0.8wt%, MgO 1.6wt%.
Except that after obtaining complex carrier, table is carried out to the complex carrier containing zinc oxide-alumina using potassium and magnesium
Face is modified, and detailed process comprises the following steps：Configuration, as maceration extract, weighs nitric acid respectively containing potassium nitrate and magnesium nitrate aqueous solution
Potassium, magnesium nitrate is dissolved completely in 30ml distilled water, then is diluted with deionized water, wiring solution-forming spray zinc oxide-alumina
Complex carrier so that the content of carrier outside potassium and magnesium is 1.1 times of the content of internal potassium and magnesium, is used through drying, roasting
Auxiliary agent potassium and magnesium carry out the zinc oxide-alumina complex carrier of surface modification.Complex carrier specific surface area 238m2/g。
Take 21.66g nickel formates to be added in 30ml distilled water, then diluted with deionized water, be made into maceration extract dipping spherical
Complex carrier 100g containing zinc oxide-alumina, the catalyst precursor for obtaining is calcined 6h after drying 6h at 120 DEG C at 450 DEG C,
Obtain catalyst 2.Catalyst 2 is mainly constituted：Nickel oxide 11wt%, the complex carrier 89wt% containing zinc oxide-alumina.
Embodiment 3
The preparation method and step of the complex carrier containing zinc oxide-alumina are with embodiment 1.Prepare containing gahnite
Zinc oxide, pH value is adjusted to 9.3.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 63%；Compare table
Area is 214m2/g。
Complex carrier includes the zinc oxide 18.3wt% containing gahnite, and aluminum oxide is 77.5wt%, adjuvant component phosphorus,
Potassium, content of magnesium are respectively P2O50.9wt%, K2O 0.8wt%, MgO 3.5wt%.Complex carrier specific surface area 242m2/g。
Take 27.56g nickel formates to be added in 30ml distilled water, then diluted with deionized water, be made into maceration extract dipping spherical
Complex carrier 100g containing zinc oxide-alumina, the catalyst precursor for obtaining is calcined 7h after drying 6h at 120 DEG C at 500 DEG C,
Obtain catalyst 3.Catalyst 3 is mainly constituted：Nickel oxide 14wt%, the complex carrier 86wt% containing zinc oxide-alumina.
Embodiment 4
The preparation method and step of the complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1
Zinc oxide, pH value is adjusted to 8.6.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 75%；Compare table
Area is 213m2/g。
Complex carrier includes the zinc oxide 22.0wt% containing gahnite, and aluminum oxide is 72.5wt%, adjuvant component phosphorus,
Potassium, content of magnesium are respectively P2O51.1wt%, K2O 0.4wt%, MgO 4.0wt%.Complex carrier specific surface area 256m2/g。
Take 23.63g nickel formates to be added in 30ml distilled water, then diluted with deionized water, be made into maceration extract dipping spherical
Complex carrier 100g containing zinc oxide-alumina, the catalyst precursor for obtaining is calcined 4h after drying 6h at 120 DEG C at 550 DEG C,
Obtain catalyst 4.Catalyst 4 is mainly constituted：Nickel oxide 12wt%, the complex carrier 88wt% containing zinc oxide-alumina.
Embodiment 5
The preparation method and step of the complex carrier containing zinc oxide-alumina are prepared containing gahnite with embodiment 1
Zinc oxide, pH value is adjusted to 8.7.Zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 67%；Compare table
Area is 191m2/g。
Complex carrier includes the zinc oxide 30wt% containing gahnite, and aluminum oxide is 66.6wt%, adjuvant component phosphorus,
Potassium, content of magnesium are respectively P2O50.6wt%, K2O 1.0wt%, MgO 1.8wt%.Complex carrier specific surface area 279m2/g。
Except that after obtaining complex carrier, table is carried out to the complex carrier containing zinc oxide-alumina using potassium and magnesium
Face is modified, and detailed process comprises the following steps：Configuration is containing potassium nitrate and magnesium nitrate aqueous solution as solution spraying zinc oxide-oxidation
Aluminium complex carrier so that the content of carrier outside potassium and magnesium is 1.2 times of the content of internal potassium and magnesium.Obtained through drying, roasting
Used additives potassium and magnesium carry out the zinc oxide-alumina complex carrier of surface modification.
Take 23.63g nickel formates to be added in 30ml distilled water, then diluted with deionized water, be made into maceration extract dipping spherical
Complex carrier 100g containing zinc oxide-alumina, the catalyst precursor for obtaining is calcined 8h after drying 6h at 120 DEG C at 400 DEG C,
Obtain catalyst 5.Catalyst 5 is mainly constituted：Nickel oxide 12wt%, the complex carrier 88wt% containing zinc oxide-alumina.
Catalyst 1-5, comparative catalyst 1 are respectively charged into 100ml fixed bed reactors, catalyst reaction performance is carried out
Evaluate.Use H2It is activated, activation condition pressure 2.0MPa, 280 DEG C of temperature, under conditions of hydrogen flowing quantity 400mL/min
Constant temperature 12h.Activation starts, into reforming raffinate oil, to be adjusted to reaction process condition after terminating.Reaction process condition is：Reaction temperature
178 DEG C, reaction pressure 1.7MPa, volume space velocity 2.5h-1, hydrogen to oil volume ratio 500.Sampling analysis after stable reaction 48h, catalyst
And contrast medium reactor product property analysis are shown in Table 1.Study on the stability is carried out to catalyst 1,2,5 and contrast medium, reaction condition is same
On, reaction operation 2000h, the arene engaging scraping rate of catalyst 1,2,5 and contrast medium be respectively 96.4%, 98.7%, 98.2% and
92.2%, olefin removal rate 100%, 100%, 100%, 93.8%.
The hydrogenation activity of raffinating oil that can be seen that catalyst 1,2,5 by table 1 and catalyst stability evaluating data is high, warp
The catalyst for crossing surface modification shows more activity stability in long-term operation.
The catalyst of table 1 and contrast medium reactor product property
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Knowing those skilled in the art can make various corresponding changes and deformation, but these corresponding changes and deformation according to the present invention
Protection scope of the present invention should all be belonged to.
Claims (10)
1. a kind of catalyst for hydrogenation of raffinating oil, it is characterised in that composed of the following components：
Complex carrier 80.0-92wt% containing zinc oxide-alumina, active component nickel oxide 8-20wt%；
The described complex carrier containing zinc oxide-alumina, including the zinc oxide containing gahnite, aluminum oxide, and add phosphorus,
, used as adjuvant component, the composition of complex carrier is with oxidation material gauge for potassium and magnesium：Zinc oxide content containing gahnite is
5.0-40.0wt%, alumina content is 60.0-95.0wt%, and the content of adjuvant component phosphorus, potassium and magnesium accounts for the hundred of carrier quality
Point content is respectively P2O50.2-1.2wt%, K2O 0.2-2.5wt%, MgO 2.0-5.5wt%, complex carrier specific surface area
200-300m2/g。
2. a kind of catalyst for hydrogenation of raffinating oil according to claim 1, it is characterised in that by following components group
Into：
Complex carrier 85.0-90.0wt% containing zinc oxide-alumina, active component nickel oxide 10-15wt%；
The described complex carrier containing zinc oxide-alumina, with oxidation material gauge：Zinc oxide content containing gahnite is
10.0-35.0wt%, alumina content is 65.0-90.0wt%, and the content of adjuvant component phosphorus, potassium and magnesium accounts for the hundred of carrier quality
Point content is respectively P2O50.4-1.0wt%, K2O 0.2-2.5wt%, MgO 2.5-4.5wt%, complex carrier specific surface area
200-300m2/g。
3. the preparation method of a kind of catalyst for hydrogenation of raffinating oil described in claim 1 or 2, it is characterised in that including
Following steps：
Nickeliferous soluble-salt is made into maceration extract, complex carrier of the dipping containing zinc oxide-alumina is dried, and roasting is taken out
Excess oil hydrogenation catalyst；
The soluble-salt of described nickel is nickel nitrate, nickelous carbonate or nickel formate.
The described complex carrier containing zinc oxide-alumina, the method for being prepared by the following procedure is obtained：
Soluble salt solutions and zinc-containing solution containing aluminium are alternately titrated by non-constant pH, the oxygen containing gahnite is prepared
Change zinc stratified material；Zinc oxide and boehmite containing gahnite are well mixed, sesbania powder, nitric acid acidifying is added
The acid solution containing Sodium Polyacrylate after treatment, and phosphoric acid, potassium nitrate and magnesium nitrate the aqueous solution, kneading, after shaping, dry
Treatment, calcination process is obtained containing zinc oxide-alumina composite carrier.
4. the preparation method of a kind of catalyst for hydrogenation of raffinating oil according to claim 3, it is characterised in that：
The described zinc oxide containing gahnite, in terms of oxide, the content of zinc oxide is 60-90wt%, and specific surface area is
160-220m2/ g, when controlling the content of zinc oxide in 65-80wt%, specific surface area 170-200m2/g；In control zinc oxide
Content in 70-80wt%, specific surface area 190-220m2/g。
5. the preparation method of a kind of catalyst for hydrogenation of raffinating oil according to claim 3, it is characterised in that：It is described
The zinc oxide stratified material prepared containing gahnite, be prepared by the following preparation method：By soluble Zn salting liquid point
It is 2-4 parts, under the conditions of 40-80 DEG C, the mixed solution containing aluminium of sodium metaaluminate and sodium carbonate is added in a zinc solution, works as pH
Value stops that mixed solution containing aluminium is added dropwise when reaching 8.5-9.5；It is further continued for that another zinc solution is added dropwise；Zinc solution is dripped
Afterwards, continue that mixed solution containing aluminium is added dropwise, stop that mixed solution containing aluminium is added dropwise when pH value reaches 8.5-9.5；Will according to the above method
Mixed solution containing aluminium replaces titration with zinc solution, until zinc solution whole completion of dropping, last time dropwise addition is containing aluminium mixing
Solution, when pH value reaches 8.5-9.5, the alternating titration process of non-constant pH value terminates, and control titration process is complete in 1-6h
Into；After 80-95 DEG C of aging 2-8h, cooling washing dries 4-10h, 450-550 DEG C of roasting 4-10h at 80-140 DEG C to neutrality,
Obtain the dispersed zinc oxide stratified material containing gahnite.
6. the preparation method of a kind of catalyst for hydrogenation of raffinating oil according to claim 5, it is characterised in that：It is described
Soluble zinc salt is zinc nitrate or zinc chloride.
7. the preparation method of a kind of catalyst for hydrogenation of raffinating oil according to claim 3, it is characterised in that：It is described
Nitric acid acidification after the acid solution containing Sodium Polyacrylate, be prepared by the following preparation method：Deionized water is heated to
30-90 DEG C, then nitric acid is dissolved into deionized water, adds Sodium Polyacrylate, and dissolve complete, obtained containing polyacrylic acid
The acid solution of sodium.The Sodium Polyacrylate of acidified treatment, the addition of described Sodium Polyacrylate is boehmite
0.6-12wt%.
8. the preparation method of a kind of catalyst for hydrogenation of raffinating oil according to claim 3, it is characterised in that：It is described
The addition of sesbania powder is the 0.2-7wt% of boehmite.
9. the preparation method of a kind of catalyst for hydrogenation of raffinating oil according to claim 3, it is characterised in that：It is described
Drying, roasting obtains raffinate oil hydrogenation catalysts, refers to 120 DEG C of dried process 6 hours, calcination process at 400 DEG C -600 DEG C
5-8 hours；Described dried process, calcination process, be 110-150 DEG C dried process 4-8 hours, at 550 DEG C -700 DEG C be calcined
Treatment 4.5-8 hours.
10. the preparation method of the catalyst of a kind of hydrogenation of raffinating oil according to claim 3, it is characterised in that：To right
It is required that 3 complex carriers containing zinc oxide-alumina for obtaining, carry out carrier surface modification as follows：Configuration contains nitric acid
The aqueous solution complex carrier of the spray containing zinc oxide-alumina of potassium and magnesium nitrate, through drying, roasting obtains used additives potassium and magnesium enters
The modified zinc oxide-alumina complex carrier in row surface, potassium oxide and magnesia contain in control zinc oxide-alumina complex carrier
Amount makes the content of carrier external oxidation potassium and magnesia be interior respectively in the range of 0.2-2.5wt% and 2.5-5.5wt%
1.1-1.2 times of portion's potassium oxide and content of magnesia.
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| CN104525207A (en) * | 2014-12-18 | 2015-04-22 | 山东玉皇化工有限公司 | Preparation of saturated hydrogenation Ni catalyst and method of Ni catalyst in catalyzing C5 hydrogenation |
| CN104588024A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Preparation method for hydrogenation catalyst |
| CN104927915A (en) * | 2014-03-18 | 2015-09-23 | 中国石油化工股份有限公司 | Method for producing olefins and aromatic hydrocarbons with naphtha as raw material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103721693A (en) * | 2012-10-10 | 2014-04-16 | 中国石油化工股份有限公司 | Titanium oxide-aluminum oxide compound as well as preparation method and application thereof |
| CN104588024A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Preparation method for hydrogenation catalyst |
| CN104927915A (en) * | 2014-03-18 | 2015-09-23 | 中国石油化工股份有限公司 | Method for producing olefins and aromatic hydrocarbons with naphtha as raw material |
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