CN1098915C - Hydrorefining catalyst and its preparing process - Google Patents
Hydrorefining catalyst and its preparing process Download PDFInfo
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- CN1098915C CN1098915C CN99113305A CN99113305A CN1098915C CN 1098915 C CN1098915 C CN 1098915C CN 99113305 A CN99113305 A CN 99113305A CN 99113305 A CN99113305 A CN 99113305A CN 1098915 C CN1098915 C CN 1098915C
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- solution
- nickel
- mixing solutions
- boron
- molybdenum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000008569 process Effects 0.000 title claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052796 boron Inorganic materials 0.000 claims abstract description 40
- 238000002360 preparation method Methods 0.000 claims abstract description 38
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 37
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 35
- 239000011733 molybdenum Substances 0.000 claims abstract description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 29
- 239000010937 tungsten Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 42
- 229910017262 Mo—B Inorganic materials 0.000 claims description 33
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 30
- 229910021529 ammonia Inorganic materials 0.000 claims description 15
- 238000007598 dipping method Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 12
- 150000002816 nickel compounds Chemical class 0.000 claims description 12
- 150000003658 tungsten compounds Chemical class 0.000 claims description 12
- 239000004480 active ingredient Substances 0.000 claims description 11
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 6
- 239000011609 ammonium molybdate Substances 0.000 claims description 6
- 229940010552 ammonium molybdate Drugs 0.000 claims description 6
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 6
- 150000001639 boron compounds Chemical class 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 5
- 239000011707 mineral Substances 0.000 claims description 5
- 235000010755 mineral Nutrition 0.000 claims description 5
- 239000005078 molybdenum compound Substances 0.000 claims description 5
- 150000002752 molybdenum compounds Chemical class 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 3
- 238000006424 Flood reaction Methods 0.000 claims description 2
- 229910021543 Nickel dioxide Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 238000007654 immersion Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 100
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- JINUODOULZQQEG-UHFFFAOYSA-N N.[B].[Mo] Chemical compound N.[B].[Mo] JINUODOULZQQEG-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- LGLOITKZTDVGOE-UHFFFAOYSA-N boranylidynemolybdenum Chemical compound [Mo]#B LGLOITKZTDVGOE-UHFFFAOYSA-N 0.000 description 4
- 229940063013 borate ion Drugs 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 235000012976 tarts Nutrition 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JCCZVLHHCNQSNM-UHFFFAOYSA-N [Na][Si] Chemical compound [Na][Si] JCCZVLHHCNQSNM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- -1 nickelous nitrate Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention discloses a preparation method for a hydrofining catalyst. In the catalyst, alumina containing silicon is used as a carrier, metallic elements of group VIII and group VIB are used as active components, and boron is added to be used as an auxiliary agent. The hydrofining catalyst mainly contains three active components of tungsten, molybdenum and nickel. In the preparation method for a hydrofining catalyst, the active components and the auxiliary agent are simultaneously loaded by the method of one-time immersion in solution., and the catalyst is manufactured after drying and burning.
Description
The present invention relates to a kind of Hydrobon Catalyst And Its Preparation Method, particularly fraction oil hydrodesulfurizing, hydrodenitrogenation catalyst and preparation method thereof.
Typical Hydrobon catalyst is carrier with the aluminum oxide, with VIII family and group vib metallic element is active ingredient, in order further to improve the active and stable of Hydrobon catalyst, various methods have been adopted, as carrier being carried out modification, improve preparation condition, adding auxiliary agent etc., wherein selected auxiliary agent often has P, F, B, Si, Ti, Zr etc.A certain amount of silicon is particularly introduced in the adding of silicon in alumina supporter, help improving the acidity of support of the catalyst.The adding of boron also can improve the acidity of carrier and catalyzer, but there is optimum value in the content of boron, too much boron exists makes acid (the Bulletin of the chemicalsociety of Japan of decline on the contrary, 37 (12), 1797-1809 (1964)), cause carrier hole distribution disperse if boron adds affiliation in the alumina supporter moulding process, add so boron is preferably in the process of dipping.
It is generally acknowledged that tungsten nickel system discovers further that than the Hydrobon catalyst hydrogenation performance height of molybdenum nickel system tungsten, molybdenum, nickel three compositions system mix according to a certain percentage, its catalytic activity is higher than tungsten nickel system.In patent of invention CN1052501A and CN1086534A, select tungsten, molybdenum, nickel as active ingredient and boron as auxiliary agent, wherein silicon is to add in the process of aluminum oxide moulding, and tungsten, molybdenum, nickel and boron adopt secondary or spray (saturated dipping) three times, four times after, must make catalyzer through steps such as super-dry, roastings after spraying at every turn.The subject matter that these two pieces of patents exist is Preparation of catalysts process complexity, and through repeatedly dipping, drying and roasting the yield of catalyzer is descended, and cost rises.
The objective of the invention is to shortcoming at above-mentioned prior art, propose a kind of Hydrobon Catalyst And Its Preparation Method, molded siliceous alumina supporter is only passed through single-steeping, make active ingredient and auxiliary agent load on the carrier simultaneously, preparation flow obtains simplifying, and has reduced the catalyzer cost.
Catalyzer of the present invention and preparation method are as follows:
Catalyst for hydrorefining distillate oil of the present invention is an active ingredient with VIII family and group vib metallic element, adds boron additive, is carrier with siliceous aluminum oxide, is benchmark with the weight percent, and catalyzer comprises SiO
23～10%, MoO
35～10%, WO
310～25%, NiO2～5%, B
2O
32～5%; Described catalyzer is to make by in type carrier is only carried out single-steeping, drying and roasting with the mixing solutions that contains active ingredient and auxiliary agent.
The pore volume of described catalyzer is 0.20～0.50cm
3/ g, specific surface area is 100～200m
2/ g.
Silicon in the above-mentioned siliceous aluminum oxide preferably adds in the alumina supporter moulding process, and silica alumina ratio is 1: 5～25.
The preparation method of described Hydrobon catalyst comprises:
A. the moulding of siliceous alumina supporter;
B. prepare mixing solutions;
C. going on foot described mixing solutions with b floods a one-step forming alumina supporter;
D. dry, roasting makes catalyzer;
Described mixing solutions contains tungsten, molybdenum, nickel, boron component simultaneously, is disposable dipping to the dipping of formed alumina carrier.
Realize that active ingredient and auxiliary agent single-steeping load on the carrier, its gordian technique is to prepare a kind of mixing solutions that contains active ingredient and auxiliary agent.
The present invention proposes the stable molybdenum boron ammonia soln of preparation earlier, acidifying under certain condition, make the tart Mo-B solution after, add tungsten compound and nickel compound again, perhaps with the tungsten nickel solution mixed tungsten of the present invention, molybdenum, nickel, boron mixing solutions.
Molybdenum acid ion and borate ion all are easy to polymerization in the aqueous solution, enhancing along with solution acidic, molybdenum mainly exists with the form of polyacid radical ion, and boron not only easily forms the poly ion, and reduce with temperature, can from solution, separate out because of hydrogen bond action forms the associative structure body between the borate ion (or boric acid molecule).After molybdenum and boron compound dissolved in ammonia soln, if carry out acidifying immediately, molybdenum, boron in the solution separated out from solution with polymerization state separately.To effectively solve coagulation problem in the acidization, must try every possible means to make molybdenum acid ion and borate ion to be dispersed in the solution, promptly form boron molybdenum heteropoly compound, so just can be in acidic solution stable existence.In order to help forming molybdenum boron heteropoly compound in the molybdenum boron ammonia soln, if when adopting the heated and boiled method to form molybdenum boron heteropoly compound, this method improves equipment requirements in industrial applicability, energy expenditure increases, and higher when Mo-B solution concentration, when temperature drops to room temperature, because of difference variation is big, has molybdenum boron precipitation and separate out again.
The present invention adopts under different acidity values, places the method for Mo-B solution for some time.Because acidity is not simultaneously, the polymerization degree of molybdenum acid ion and borate ion is different, places solution for some time, more helps phase mutual diffusion and infiltration between the molecule.
This method is: after molybdenum boron ammonia soln forms, being to place solution 50～200 hours between 6～9 in the pH value earlier, is to place solution 50～300 hours between 3～6 in the pH value then; Again that tungsten compound and nickel compound and described molybdenum boron ammonia soln is mixed as to contain the mixing solutions of molybdenum, tungsten, nickel, boron.
Wherein tungsten compound and nickel compound and described molybdenum boron ammonia soln hybrid mode can be to take to prepare tungsten nickel solution and Mo-B solution blended mode; Also can adopt a kind of and Mo-B solution in tungsten compound and the nickel compound is mixed, treat that it dissolves fully after, add another kind ofly again, or tungsten compound and nickel compound directly mixed with Mo-B solution together.
The preparation of above-mentioned tungsten nickel solution can add water and make by getting tungsten compound and nickel compound.
The preparation of described molybdenum, tungsten, nickel, boron mixing solutions is preferably by following condition preparation:
(1) molybdenum compound and boron compound are added in the ammonia soln, regulate the pH value between 6～9 with ammoniacal liquor, keep the temperature of solution to descend 2～8 hours at 50～90 ℃, placed solution 50～200 hours (be preferably in 20～60 ℃ of temperature ranges and place), between 40～80 ℃ with mineral acid or/and the organic acid acidifying makes the pH value of solution value between 3～6, keep the temperature of solution to descend 2～8 hours at 40～80 ℃, place solution 50～300 hours (be preferably in 20～60 ℃ of temperature ranges and place), make Mo-B solution;
(2) between 20 ℃ to 80 ℃, Mo-B solution is mixed with tungsten compound and nickel compound, make and contain tungsten, molybdenum, nickel, boron mixing solutions;
After having prepared above-mentioned molybdenum, tungsten, nickel, boron mixing solutions, preferably adjust the mixing solutions temperature be made between 40～80 ℃, kept 1～4 hour.
Join tungsten, molybdenum, nickel, boron mixing solutions, in conjunction with the industrial application practical situation, the most effective source of boron compound is boric acid or ammonium borate, be dissolvable in water in the basic solution, and the heating more help the dissolving, the most effective source of molybdenum compound is ammonium molybdate or molybdic oxide, be dissolvable in water in the solution of alkalescence, nickel compound can be selected from the tart nickel salt such as nickelous nitrate, single nickel salt, nickelous chloride, nickel acetate, and the most effective source of tungsten compound is an ammonium metawolframate, is dissolvable in water in the tart solution.
Described certain density ammonia soln refers to concentration with NH
3Form is calculated as 2.0～9.0mol/dm
3Between the scope.The concentration of used ammonia soln is relevant with the pH value of desired Mo-B solution, if require the pH value of Mo-B solution higher, the concentration of corresponding ammonia soln is bigger, otherwise if require the pH value of Mo-B solution lower, the concentration of corresponding ammonia soln is less; And the concentration of ammonia soln also (or ammonium borate is with H with institute's dissolved ammonium molybdate (or molybdic oxide) and boric acid
3BO
3Form calculate) amount relevant, require ammonia (NH in the Mo-B solution
3) with boric acid (H
3BO
3) and ammonium molybdate (with MoO
3The ratio of amount of substance form calculating) is NH
3: (H
3BO
3+ MoO
3)=0.4～3.0: get final product within 1.0 scopes.
If selected ammonia concn is less in the preparation Mo-B solution process, and the amount of boric acid is when big, can prepare the Mo-B solution of pH value between 6～7.
According to above method, can prepare the mixing solutions MoO that comprises following component
30.3～1.5mol/dm
3, WO
30.4～1.8mol/dm
3, NiO 0.4～1.8mol/dm
-3, B
2O
30.3～1.5mol/dm
-3
The concrete preparation process of catalyzer of the present invention is:
(1) moulding of siliceous alumina supporter;
(2) contain the preparation of tungsten, molybdenum, nickel, boron mixing solutions;
(3) flood with the mixing solutions that contains tungsten, molybdenum, nickel, boron, between 100～130 ℃ dry 2～8 hours, roasting 2～6 hours between 400～550 ℃ and make catalyzer of the present invention.
The moulding of siliceous alumina supporter can be carried out as follows:
The preparation of spherical silicon-containing alumina carrier: aluminum hydroxide solid elastomer powder and the low sodium silicon sol (preferably sodium ions content is less than the silicon sol of 1000ppm) of getting aequum, mix earlier and afterwards use mineral acid and/or organic acid to be kneaded into false colloidal sol, again through oil ammonia column balling-up and curing, wet rubber ball makes 500～700 ℃ of roasting temperatures 2～6 hours through 90～130 ℃ of dryings 2～6 hours.
The preparation of cylindrical, special-shaped alumina supporter: the aluminum hydroxide solid elastomer powder of getting aequum, low sodium silicon sol (preferably sodium ions content is less than the silicon sol of 1000ppm), with the mixed paste of pinching into of peptizing agent, water and extrusion aid, extruded moulding on banded extruder, the shape of carrier can be regulated with the mode of changing the banded extruder orifice plate, can be cylindrical, it also can be special-shaped bar, carrier after the moulding with ball-aluminium oxide carrier the same terms under drying and roasting, make the siliceous alumina supporter of bar shaped miscellaneous.Wherein peptizing agent can be mineral acid, organic acid, strongly-acid negatively charged ion aluminium salt etc., such as nitric acid, hydrochloric acid, oxalic acid, formic acid, acetate, aluminum nitrate etc., also can be the organic assembling of several peptizing agents wherein; The extrusion aid that is adopted can be the material that sesbania powder, starch, Mierocrystalline cellulose etc. can be burnt.
The ratio of sial amount of substance is 1: 5～25 in the siliceous alumina supporter that makes.The physico-chemical property of its pore structure is as follows: specific surface area is 200～300m
2/ g, pore volume 0.40～0.70cm
3/ g, average pore diameter is 4～14nm.
Wherein the pore structure character of carrier can be selected the condition of molding of different aluminum hydroxide solid elastomer powder and change carrier according to the requirement of finished catalyst, and such as the consumption of peptizing agent, factors such as maturing temperature and time are adjusted.
After finishing the body formed preparation with mixing solutions of siliceous carrying alumina, can carry out the load of active ingredient and auxiliary agent.Specifically can carry out as follows:
Flood siliceous alumina supporter with the mixing solutions that contains tungsten, molybdenum, nickel, boron, drying and roasting can make catalyzer of the present invention.Dipping wherein can be the supersaturation dipping, also can be saturated dipping.Saturated pickling process is meant puts into a rotating container (rotary drum) to siliceous alumina supporter, under rotating the dipping solution of carrier saturated extent of adsorption is vaporific and is sprayed onto on the carrier.Supersaturation dipping refers to the solution impregnation of 1.5～3.0 times of volumes of carrier saturated extent of adsorption 0.5～2.0 hour.
In a word, the present invention adopts the method for placing Mo-B solution for some time under different acidity, make the tart Mo-B solution earlier, get then tungsten compound and nickel compound and acidic Mo-B solution under certain condition the blended mode prepare to such an extent that contain the mixing solutions of tungsten, molybdenum, nickel, boron, this strength of solution is higher, good stability, and do not contain the alkalies and alkaline earth ion, preparing the selected raw material of this solution is easy to get, the working method simple possible of solution preparation, equipment is not had particular requirement, help industrial implementation.On the basis that has solved tungsten, molybdenum, nickel, the preparation of boron mixing solutions, further adopt this mixing solutions only to make Hydrobon catalyst of the present invention through single-steeping, drying and roasting, compare with the technology that just makes catalyzer through twice dipping, drying and roasting at least, activity of such catalysts is suitable, and simplified the Preparation of catalysts flow process, and reduced cost.
Further specify advantage of the present invention, technical characterictic and catalyst preparation process below by embodiment and Comparative Examples, but should not think that the present invention only was confined to this.
Embodiment 1
Present embodiment has been introduced the moulding process of siliceous alumina supporter.
(Fushun, Liaoning Province petrochemical corporation (complex) three factory's catalyst plants are produced, and contain Al to get aluminum hydroxide solid elastomer powder 1000g
2O
362.0m%) and 160cm
3(the new light remover in Shenyang City factory produces silicon sol, and the pH value is 9.3, contains SiO
2Be 30.0m%, Na
+Concentration is 300ppm) mix after, add 1800cm
3Concentration is 1.25mol/dm
3Salpeter solution in, stir and to make false colloidal sol, drip ball, be solidified into the ball-type carrier through oil ammonia column then, through 90 ℃ of dryings 4 hours, siliceous alumina supporter A was made in 550 ℃ of following roastings in 4 hours, its physico-chemical property is listed in the table 1.
(Shandong Province Chemical Fertilizer Factory No.1, Qilu Petrochemical Co. produces, and contains Al to get aluminum hydroxide solid elastomer powder 1000g
2O
366.0m%) and 250cm
3Silicon sol mixes earlier, adds 700cm again
3The mixing solutions that contains nitric acid and acetic acid, wherein concentration of nitric acid is 0.70mol/dm
3, the concentration of acetic acid is 0.40mol/dm
3, mix and pinch even one-tenth paste plastic, on banded extruder, be extruded into the cloverleaf pattern bar of 1.2mm, drying is 4 hours under 120 ℃, and 550 ℃ of following roastings made siliceous alumina supporter B in 4 hours, and its physico-chemical property is listed in the table 1.
The physico-chemical property of the siliceous alumina supporter of table 1
| Carrier | SiO 2 m％ | Specific surface area m 2/g | Pore volume cm 3/g | Mean pore size nm | Silica alumina ratio | Shape and diameter mm |
| A | 8.2 | 260 | 0.57 | 8.8 | 1∶13.2 | Spherical 1.5～2.5 |
| B | 12.6 | 220 | 0.60 | 11.0 | 1∶8.1 | Trifolium 1.2 |
Embodiment 2
Present embodiment has been introduced Mo-B solution process for preparation and method.
Measure ammonia soln, (technical grade contains MoO to add ammonium molybdate successively
382.7m%) and boric acid (technical grade), heating, place for some time, measure the pH value of solution value, prepare Mo-B solution D and E, preparation condition and SOLUTION PROPERTIES see Table 2.
Table 2
| Solution | Ammonia soln | Ammonium molybdate | Boric acid | The Heating temperature time | The laying temperature time | The pH value | Form (mol/dm 3) | ||||
| cm 3 | mol/l | g | g | ℃ | Hour | ℃ | Hour | MoO 3 | B 2O 3 | ||
| D | 840 | 6.70 | 280 | 203 | 60 | 4 | 30 | 80 | 9.0 | 1.59 | 1.64 |
| E | 800 | 3.43 | 331 | 183 | 70 | 6 | 40 | 150 | 6.5 | 1.90 | 1.48 |
Measure above-mentioned Mo-B solution, the pH value of solution value is measured in acidifying, heating under the temperature of regulation, places according to required time under the temperature of regulation, prepare acidifying Mo-B solution D
1And E
1, E
1', the results are shown in Table 3.
Table 3
| Solution | Mo-B solution cm 3 | Acidifying and heating | The acid kind | The acid consumption | Acid concentration | Place | The pH value | Form (mol/dm 3) | |||
| Temperature (℃) | Time (h) | cm 3 | mol/dm 3 | Temperature (℃) | Time (h) | MoO 3 | B 2O 3 | ||||
| D 1 | 800 | 50 | 3 | Nitric acid | 160 | 14.3 | 30 | 100 | 4.5 | 1.32 | 1.37 |
| E 1 | 500 | 60 | 6 | Nitric acid | 50 | 14.3 | 40 | 200 | 5.0 | 1.73 | 1.35 |
| E 1′ | 100 | 55 | 4 | Oxalic acid | 8g | - | 40 | 150 | 6.0 | 1.79 | 1.40 |
Embodiment 3
Present embodiment has been introduced the compound method of tungsten nickel solution.
Measure 225cm
3Water, (technical grade contains WO to add the 438g ammonium metawolframate successively
385.2m%) with 344g nickelous nitrate (Ni (NO
3)
26H
2O, Liaoning Province city's chemical reagent one factory that increases income produces), make tungsten nickel solution G after the stirring and dissolving, it consists of WO
33.22mol/dm
3, NiO 2.37mol/dm
3
Measure 373cm
3Water, (technical grade contains WO to add the 176g ammonium metawolframate successively
385.2m%) with 132g nickelous nitrate (Ni (NO
3)
26H
2O, Liaoning Province city's chemical reagent one factory that increases income produces), make tungsten nickel solution H after the stirring and dissolving, it consists of WO
31.29mol/dm
3, NiO 0.91mol/dm
3
Embodiment 4
Present embodiment 2 and 3 further specifies compound method and the process that contains tungsten, molybdenum, nickel, boron mixing solutions in conjunction with the embodiments.
Measure the Mo-B solution D among the embodiment 2
1300cm
3, add the 168g ammonium metawolframate earlier and heated 1 hour down at 70 ℃, add the 134g nickelous nitrate then, reheat 1 hour can make and contain tungsten, molybdenum, nickel, boron mixing solutions D
2, its composition is listed in the table 4.
Measure the Mo-B solution E among the embodiment 2
1200cm
3With the tungsten nickel solution G200cm among the embodiment 3
3, under stirring condition, add in the tungsten nickel solution at 60 ℃ of following Mo-B solutions, under this temperature, heated 2 hours then, make the mixing solutions E that contains tungsten, molybdenum, nickel, boron
2, its composition is listed in the table 4
Measure the Mo-B solution E among the embodiment 2
1200cm
3With the tungsten nickel solution G100cm among the embodiment 3
3, under stirring condition, add in the tungsten nickel solution at 50 ℃ of following Mo-B solutions, under this temperature, heated 3 hours then, make the mixing solutions G that contains tungsten, molybdenum, nickel, boron
1, its composition is listed in the table 4.
Measure the Mo-B solution D among the embodiment 2
1200cm
3With the tungsten nickel solution H200cm among the embodiment 3
3, under stirring condition, add in the Mo-B solution at 55 ℃ of following tungsten nickel solutions, under this temperature, heated 4 hours then, make and contain tungsten, the mixing solutions H of molybdenum, nickel, boron
1, its composition is listed in the table 4.
The composition of table 4 tungsten, molybdenum, nickel, boron mixing solutions
| Solution | Form (mol/dm 3) | |||
| WO 3 | MoO 3 | NiO | B 2O 3 | |
| D 2 | 1.58 | 1.02 | 1.18 | 1.05 |
| E 2 | 1.61 | 0.87 | 1.18 | 0.68 |
| G 1 | 1.07 | 1.15 | 0.79 | 0.90 |
| H 1 | 0.65 | 0.64 | 0.45 | 0.70 |
Embodiment 5
Present embodiment has been introduced active ingredient and auxiliary agent and has been joined method and process on the carrier.
Get siliceous alumina supporter A and B among the embodiment 1 respectively, place rotary container, get the mixing solutions D that contains tungsten, molybdenum, nickel, boron among the embodiment 4 by the saturated extent of adsorption of carrier
2, E
2, G
1And H
1Spray (saturated dipping) respectively, control sprays speed, makes solution be vaporific and is sprayed onto on the carrier, has sprayed the back and has taken out 120 ℃ of dryings 4 hours down, then 450 ℃ of roastings 3 hours, makes catalyzer J of the present invention
1, J
2, J
3And K
1, K
2, K
3, the character of concrete operations condition and catalyzer is listed in the table 5.
Table 5
| Catalyzer | Carrier g | Dipping solution cm 3 | Form (m%) | Pore volume cm 3/g | Specific surface area m 2/g | ||||
| SiO 2 | WO 3 | MoO 3 | NiO | B 2O 3 | |||||
| J 1 | A/200 | D 2/150 | 5.3 | 18.3 | 7.3 | 4.4 | 3.6 | 0.34 | 155 |
| J 2 | A/200 | E 2/150 | 5.5 | 19.0 | 6.4 | 4.5 | 2.4 | 0.35 | 160 |
| J 3 | A/200 | G 1/150 | 5.8 | 13.3 | 8.9 | 3.2 | 3.4 | 0.38 | 166 |
| K 1 | B/200 | D 2/160 | 7.9 | 19.1 | 7.6 | 4.6 | 3.8 | 0.35 | 127 |
| K 2 | B/200 | E 2/160 | 8.0 | 19.8 | 6.6 | 4.7 | 2.5 | 0.36 | 131 |
| K 3 | B/200 | H 1/160 | 10.0 | 9.6 | 5.8 | 2.1 | 3.1 | 0.42 | 187 |
Comparative Examples 1
This Comparative Examples has compared by the catalyzer of the present invention's preparation with by patent of invention CN1052501A, the activity of such catalysts of CN1086534A preparation.
Method according to Chinese invention patent CN1052501A makes catalyzer M, makes catalyst n by the described method of CN1086534A, and the physico-chemical property of this reference catalyst is listed in the table 6.
The physico-chemical property of table 6 reference catalyst
| Catalyzer | Form (m%) | Pore volume cm 3/g | Specific surface area m 2/g | ||||
| SiO 2 | WO 3 | MoO 3 | NiO | B 2O 3 | |||
| M | 4.7 | 19.8 | 7.8 | 5.0 | 3.5 | 0.30 | 150 |
| N | 10.5 | 18.0 | 8.0 | 4.1 | 3.8 | 0.37 | 131 |
Get catalyzer J of the present invention
1With reference catalyst M at 100cm
3After carrying out prevulcanized respectively on the small hydrogenation device, be raw material with the triumph catalytic diesel oil, character is listed in the table 7, and at 340 ℃, hydrogen-oil ratio (v/v) is 600, and volume space velocity is 1.0h
-1, total pressure is under the condition of 3.0Mpa catalyzer to be carried out activity rating, the results are shown in Table 8.
Get catalyzer K of the present invention
1With reference catalyst N at 100cm
3After carrying out prevulcanized respectively on the small hydrogenation device, be raw material with triumph wax tailings (CGO), character is listed in the table 7, and at 370 ℃, hydrogen-oil ratio (v/v) is 800, and volume space velocity is 1.0h
-1, total pressure is under the condition of 8.0Mpa catalyzer to be carried out activity rating, the results are shown in Table 8.
Table 7 stock oil character
| The stock oil title | The triumph catalytic diesel oil | Triumph CGO |
| Density, (20 ℃) kg.m -3 | 875 | 913 |
| Boiling range, ℃ | ||
| Initial boiling point | 190 | 258 |
| 10％ | 223 | 374 |
| 50％ | 279 | 412 |
| 90％ | 335 | 476 |
| 95％ | 342 | 512 |
| Sulphur, ppm | 2970 | 9800 |
| Nitrogen, ppm | 591 | 6600 |
Table 8 catalyst activity evaluation result
By catalyst activity evaluation result in the table 8 as can be seen, catalyzer of the present invention is compared with reference catalyst, desulfurization under the identical operations condition, denitrification activity are suitable, and among the present invention owing to solved the preparation that contains tungsten, molybdenum, nickel, boron mixing solutions, adopt this mixing solutions only through single-steeping, drying and roasting and make catalyzer.Therefore the catalyst flow path of the present invention's preparation is simplified than the catalyst flow path with prior art for preparing, thereby has reduced the catalyzer cost.
| Catalyzer | Desulfurization degree, % | Denitrification percent, % |
| J 1 | 92.7 | 70.8 |
| M (reference) | 92.4 | 70.6 |
| K 1 | 93.0 | 51.2 |
| N (reference) | 92.5 | 50.0 |
Claims (8)
1, a kind of catalyst for hydrorefining distillate oil is an active ingredient with VIII family and group vib metallic element, adds boron additive, is carrier with siliceous aluminum oxide, it is characterized in that with the weight percent being benchmark, and catalyzer comprises SiO
23～10%, MoO
35～10%, WO
310～25%, NiO2～5%, B
2O
32～5%; Described catalyzer is to make by in type carrier is only carried out single-steeping, drying and roasting with the mixing solutions that contains active ingredient and auxiliary agent.
2, according to the described catalyst for hydrorefining distillate oil of claim 1, the pore volume that it is characterized in that described catalyzer is 0.20～0.50cm
3/ g, specific surface area is 100～200m
2/ g.
3, according to the described catalyzer of claim 1, it is characterized in that the silicon in the described siliceous aluminum oxide adds in the alumina supporter moulding process, silica alumina ratio is 1: 5～25.
4, a kind of preparation method of Hydrobon catalyst comprises:
A. the moulding of siliceous alumina supporter;
B. prepare mixing solutions;
C. going on foot described mixing solutions with b floods a one-step forming alumina supporter;
D. dry, roasting makes catalyzer;
It is characterized in that described mixing solutions contains tungsten, molybdenum, nickel, boron component simultaneously, is disposable dipping to the dipping of formed alumina carrier, and wherein the preparation process of mixing solutions is:
(1) molybdenum compound and boron compound are added in the ammonia soln, regulate pH value between 6～9 with ammoniacal liquor, placement solution 50～200 hours, with mineral acid or/and the organic acid acidifying makes the pH value of solution value between 3～6, place solution 50～300 hours, and made Mo-B solution;
(2) Mo-B solution is mixed with tungsten compound and nickel compound, make and contain tungsten, molybdenum, nickel, boron mixing solutions.
5. according to the preparation method of the described Hydrobon catalyst of claim 4, it is characterized in that described molybdenum, tungsten, nickel, boron mixing solutions make by the following method:
(1) molybdenum compound and boron compound are added in the ammonia soln, regulate the pH value between 6～9 with ammoniacal liquor, keep the temperature of solution to descend 2～8 hours at 50～90 ℃, in 20～60 ℃ of scopes, placed solution 50～200 hours, between 40～80 ℃ with mineral acid or/and the organic acid acidifying makes the pH value of solution value between 3～6, the temperature that keeps mixing solutions in 40～80 ℃ of scopes 2～8 hours was placed solution 50～300 hours again in 20～60 ℃ of scopes, make Mo-B solution;
(2) between 20 ℃ to 80 ℃, Mo-B solution is mixed with tungsten compound and nickel compound, make and contain tungsten, molybdenum, nickel, boron mixing solutions.
6,, it is characterized in that described molybdenum compound is one or both in ammonium molybdate and the molybdic oxide according to the preparation method of the described Hydrobon catalyst of claim 5; Boron compound is one or both in boric acid and the ammonium borate; Tungsten compound is an ammonium metawolframate; Nickel compound is one or more in nickelous nitrate, nickelous chloride, the nickel acetate.
7,, it is characterized in that described mixing solutions comprises following component: MoO according to the preparation method of the described Hydrobon catalyst of claim 4
30.3～1.5mol/dm
3, WO
30.4～1.8mol/dm
3, NiO0.4～1.8mol/dm
3, B
2O
30.3～1.5mol/dm
3
8, according to the preparation method of the described Hydrobon catalyst of claim 5, it is characterized in that described preparation intact (2) goes on foot described molybdenum, tungsten, nickel, boron mixing solutions after, adjust the mixing solutions temperature that is made between 40～80 ℃, kept 1～4 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113305A CN1098915C (en) | 1999-09-29 | 1999-09-29 | Hydrorefining catalyst and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113305A CN1098915C (en) | 1999-09-29 | 1999-09-29 | Hydrorefining catalyst and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1289830A CN1289830A (en) | 2001-04-04 |
| CN1098915C true CN1098915C (en) | 2003-01-15 |
Family
ID=5276511
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113305A Expired - Lifetime CN1098915C (en) | 1999-09-29 | 1999-09-29 | Hydrorefining catalyst and its preparing process |
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| Country | Link |
|---|---|
| CN (1) | CN1098915C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2463025A1 (en) | 2005-04-21 | 2012-06-13 | China Petroleum & Chemical Corporation | Ni/Mo/W supported hydrogenation catalyst containing P or F and process for hydrocarbon hydrogenation |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441272C (en) * | 2002-11-06 | 2008-12-10 | 中国石油化工股份有限公司 | Catalyzer for hydrogenation on tail gas of sulphur and its prepn. method |
| CN1872961B (en) * | 2005-05-31 | 2010-05-12 | 中国石油化工股份有限公司 | A kind of hydrocarbon oil hydrotreating method |
| EP2586527A1 (en) * | 2011-10-31 | 2013-05-01 | Bharat Petroleum Corporation Limited | Catalyst compositions for conversion of vegetable oils to hydrocarbon products in the diesel boiling range and process of preparation thereof |
| CN102806062B (en) * | 2012-08-27 | 2014-05-21 | 傅骐 | Preparation method of palladium adsorbent for benzene refining desulfurization as well as product and application of palladium adsorbent |
| CN103623834B (en) * | 2012-08-29 | 2016-03-23 | 中国石油化工股份有限公司 | There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and hydrofinishing process |
| PL2906344T3 (en) * | 2012-10-10 | 2023-03-13 | Albemarle Europe Sprl. | Supported hydrotreating catalysts having enhanced activity |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052501A (en) * | 1989-12-11 | 1991-06-26 | 中国石油化工总公司抚顺石油化工研究院 | Hydrobon catalyst and method for making |
-
1999
- 1999-09-29 CN CN99113305A patent/CN1098915C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052501A (en) * | 1989-12-11 | 1991-06-26 | 中国石油化工总公司抚顺石油化工研究院 | Hydrobon catalyst and method for making |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2463025A1 (en) | 2005-04-21 | 2012-06-13 | China Petroleum & Chemical Corporation | Ni/Mo/W supported hydrogenation catalyst containing P or F and process for hydrocarbon hydrogenation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1289830A (en) | 2001-04-04 |
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