CN1088092C - Hydrorefining catalyst for hydrocarbons - Google Patents
Hydrorefining catalyst for hydrocarbons Download PDFInfo
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- CN1088092C CN1088092C CN99112939A CN99112939A CN1088092C CN 1088092 C CN1088092 C CN 1088092C CN 99112939 A CN99112939 A CN 99112939A CN 99112939 A CN99112939 A CN 99112939A CN 1088092 C CN1088092 C CN 1088092C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 229930195733 hydrocarbon Natural products 0.000 title abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 75
- 238000002360 preparation method Methods 0.000 claims abstract description 73
- 239000000243 solution Substances 0.000 claims abstract description 59
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 23
- 239000010936 titanium Substances 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 19
- 150000003608 titanium Chemical class 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000000975 co-precipitation Methods 0.000 claims abstract description 7
- 229910004349 Ti-Al Inorganic materials 0.000 claims description 49
- 229910004692 Ti—Al Inorganic materials 0.000 claims description 49
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 38
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 36
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 18
- 238000005470 impregnation Methods 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 16
- 239000004480 active ingredient Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 14
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 13
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 12
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 238000010009 beating Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 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 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 206010013786 Dry skin Diseases 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- -1 metal oxide compound Chemical class 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 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 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 54
- 229910052757 nitrogen Inorganic materials 0.000 description 27
- 239000011148 porous material Substances 0.000 description 22
- 238000001179 sorption measurement Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000004411 aluminium Substances 0.000 description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 8
- 229910015234 MoCo Inorganic materials 0.000 description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 8
- 229910052794 bromium Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000008030 elimination Effects 0.000 description 6
- 238000003379 elimination reaction Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000001246 bromo group Chemical class Br* 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a hydrofining catalyst. Gamma-Al2O3 containing titanium is used as a carrier, and one or the combination of the elements of group VIII and one or the combination of the elements of group VIB are used as active components. The gamma-Al2O3 carrier containing titanium is prepared by a parallel-flow coprecipitation method using the mixed solution of a soluble titanium salt and an aluminum soluble salt and an NaAlO2 solution. The active components are added by a step-by-step immersion method with equal quantity or a co-immersion method. The catalyst is particularly suitable for hydrotreating hydrocarbon containing high sulfur; in addition, the catalyst has the advantages of simple preparation method, easy obtainment of raw materials, high activity and high stability, and does not need to be precured before being used.
Description
The present invention relates to a kind of hydrorefining catalyst for hydrocarbon.More specifically to a kind of TiO that contains
2-Al
2O
3Two-pack is the Hydrobon catalyst of carrier.
Hydrocarbons hydrogenation is made with extra care the important process process that is absolutely necessary in petrochemical complex, its objective is in order to remove organic sulfide contained in the stock oil and organic nitrogen compound, to satisfy requirement on environmental protection.Need a kind of effective catalyzer in this process, used catalyzer is the catalyzer that is loaded with molybdenum or tungsten, cobalt or nickel isoreactivity component on the aluminum oxide in the traditional technology.
United States Patent (USP) 4,206,036 discloses a kind of catalyzer, its carrier is pure titanium dioxide, active ingredient still as previously mentioned, the characteristics of this catalyzer are that hydrodesulfurization activity is very high, and do not need prevulcanized before using.But this catalyzer also has its weak point, and promptly specific surface area is little, and physical strength is low, and the life-span is short, is unsuitable for industrial application.
Titanium-containing catalyst is carrying out many work around aspect the increasing specific surface area.As European patent prospectus (publication number 0,199,399) mixture that discloses in aluminum oxide and titanium oxide is the catalyzer of carrier, the method for making of carrier mainly is a certain proportion of aluminum oxide, titanium oxide, acetate and water to be added to mix pinching molded together in this catalyzer, and high-temperature roasting makes again.Active ingredient still as previously mentioned.The characteristics of this catalyzer are the initial activity height, but physical strength and life-span are still undesirable.Also having a few thing is to utilize γ-Al
2O
3Be the carrier skeleton, the acidic solution of dipping titanium salt, postheating is decomposed titanium salt and is become titanium oxide.Active ingredient still as previously mentioned.Although this method is being of great benefit to aspect the specific surface area that improves carrier, but the carrier material for preparing high-content titanium (greater than 5wt%) acquires a certain degree of difficulty, its reason be most of titanium oxide to change into the crystalline phase inactive, that dispersity is relatively poor be the rutile titanium oxide, thereby catalyzer will to keep its highly active life-span shorter.Other example is at first to make titanium aluminium carrier with water-soluble titanium salt and sodium aluminate solution co-precipitation, floods foregoing active ingredient then.As European patent prospectus (publication number 0,339,640) disclose in titanous chloride or titanyl sulfate or dichloro oxygen titanium and sodium aluminate solution coprecipitation method and prepared titanium aluminium carrier, flooded foregoing active ingredient then and prepare corresponding Hydrobon catalyst.This Hydrobon catalyst has characteristics such as active height, good stability.But the place that this catalyzer also haves much room for improvement.1, its titanium source price is higher, and it does not adopt the high titanium tetrachloride of relative low price purity as the titanium source, and its reason is that titanium tetrachloride and water reaction are too violent, is difficult to control its speed of response.2, adopt the reaction of titanium salt and sodium aluminate solution to adopt titanium aluminium mixing solutions and sodium aluminate solution reaction, the amount of the titanium aluminium carrier that generates in unit time, unit volume is less, and the industrial production cost is higher.3, the specific surface area of Ti-Al carrier can also further improve, with the further raising of activity of the hydrorefining catalyst for hydrocarbon of this carrier preparation.
Purpose of the present invention is just in order to solve above-mentioned three aspect problems.The catalyzer that does not need prevulcanized, big, the active height of specific surface area and good stability before a kind of the use is provided.A kind of Preparation of catalysts method is provided simultaneously, and this method is simple, raw material is easy to get, low production cost.
One aspect of the present invention utilizes the high titanium tetrachloride of relative low price purity as the titanium source, mix with the aluminum soluble salt crystal, titanium tetrachloride is adsorbed onto on the aluminum soluble salt crystal, can avoids the reaction of titanium tetrachloride and water too violent like this, thereby reach the purpose of controls reaction speed.On the other hand, utilize titanium aluminum solutions and sodium aluminate solution co-precipitation, can improve the amount of the Ti-Al carrier that generates in unit time, the unit volume greatly, thereby reduce production costs greatly.At last, adopt the specific surface area of Ti-Al carrier of the identical titanium oxide content of this method preparation to be greatly improved, the activity of the hydrorefining catalyst for hydrocarbon for preparing with this carrier has obtained further raising.
According to the titanium aluminium carrier that present method is produced, its production cost cost by the production of method described in the above-mentioned European patent prospectus (publication number 0,339,640) titanium aluminium carrier is low more than 30%.Its hydrofining activity is better than similar Hydrobon catalyst.
The carrier of catalyzer of the present invention is the γ-Al that is loaded with titanium
2O
3(being expressed as the Ti-Al carrier), active ingredient are one of one of VIII family or its combination, group vib or its combination.It consists of vib metal oxide compound 5wt%～30wt%, group VIII metal oxide 2wt%～8wt%, and titanium oxide 0.5wt%～50wt%, all the other are aluminum oxide.
Preparation of catalysts method of the present invention is:
1.Ti-Al the preparation of the preparation of carrier (1) titanium aluminum solutions: with solubility titanium salt and soluble aluminum salt crystal by weight 5 * 10
-3～0.7, preferred 0.04～0.5, best 0.05～0.3 mixes, and progressively drips deionized water then, dissolving under agitation, and the elimination insolubles obtains the titanium aluminum solutions.Wherein water-soluble titanium salt can be TiCl
4, TiCl
3, TiOCl
2Or Ti (SO
4)
2Deng, preferred TiCl
4, water-soluble aluminium salt crystal can be AlCl
3, Al
2(SO
4)
3, Al (NO
3)
3Deng, preferred AlCl
3(2) preparation of sodium aluminate solution: the sodium metaaluminate solid is soluble in water, stirring and dissolving, the elimination insolubles obtains the sodium aluminate solution that concentration is 5wt%～20wt%.(3) under agitation, above-mentioned titanium aluminum solutions and sodium aluminate solution are 20 ℃～70 ℃ and flow co-precipitation in temperature of reaction, after reacting 1～3 hour under this temperature of reaction, regulate pH value to 8.5～10 with ammoniacal liquor, placement is spent the night, suction filtration, washing, making beating back obtains the dry sample of Ti-Al 80 ℃～150 ℃ spraying dryings 2～8 hours.(4) press W
HNO3/ W
The dry sample of Ti-Al=0.010～0.025, W
H2O/ W
The dry sample of Ti-Al=0.50～1.0 are extruded into various suitable shapes (as cloverleaf pattern, bar shaped, sphere etc.) after pinching with dry sample of Ti-Al and aqueous nitric acid are fully mixed; Dry in the shade in room temperature, 100～150 ℃ of oven dry 2～8 hours, progressively be warming up to 450～650 ℃, roasting 4～8 hours makes the Ti-Al roasting sample that is loaded with titanium oxide 0.5wt%～50wt%.The specific surface area that records this roasting sample with nitrogen adsorption method (BET) method is 200～400m
2/ g, recording total pore volume with nitrogen adsorption method is 0.1～1.5ml/g, mean pore size is 2～15nm.
2. Preparation of catalysts method
Active ingredient is added on the carrier by step impregnation method.(1) solubility group vib metal salt solution dipping: solubility group vib metal salt solution is sprayed on the above-mentioned carrier with the equivalent impregnation method, 100 ℃～150 ℃ oven dry 2～8 hours, 450 ℃～650 ℃ roastings 4～8 hours can make and be loaded with the catalyst precursor that the group vib metal oxide content is 6wt%～35wt%.Wherein solubility group vib metal salt solution can be the salts solution of molybdenum and/or tungsten, preferably ammonium molybdate and/or ammonium metawolframate.(2) group VIII metal salt solution dipping: solubility group VIII metal salt solution is sprayed on the above-mentioned catalyst precursor with the equivalent impregnation method, in 100 ℃～150 ℃ oven dry 2～8 hours, 450 ℃～650 ℃ roastings 4～8 hours can make and contain the catalyzer that the group VIII metal oxide is 1wt%～10wt%.Wherein solubility group VIII metal salt solution can be the salts solution of cobalt and/or nickel, preferably Xiao Suangu and/or nickelous nitrate.
Catalyzer also can adopt the preparation of following leaching method altogether: the VIB and the group VIII metal-salt of (1) preparation solubility soak solution altogether: the VIB and the group VIII metal-salt of solubility are put into same beaker, add deionized water, dissolving back elimination mechanical impurity, be mixed with contain group vib metal-salt 5～18wt% and contain group VIII metal-salt 1～10wt% soak solution altogether.Wherein the vib metal of solubility can be molybdenum and/or tungsten, and the group VIII metal can be cobalt and/or nickel.Preferably ammonium molybdate and/or ammonium metawolframate and nickelous nitrate and/or Xiao Suangu.
(2) VIB and group VIII metal-salt soak solution impregnation altogether: with the equivalent impregnation method with the above-mentioned solution spraying that soaks altogether to above-mentioned carrier, in 100 ℃～150 ℃ oven dry 2～8 hours, 450 ℃～650 ℃ roastings 4～8 hours, can make the catalyzer that contains titanium oxide, wherein the VIB oxide content is 5wt%～30wt%, the group VIII metal oxide content is 2wt%～8wt%, and titanium oxide content is 0.5wt%～50wt%, and all the other are aluminum oxide.The vib metal oxide compound is preferably molybdenum oxide and/or Tungsten oxide 99.999, and the group VIII metal oxide is preferably cobalt oxide and/or nickel oxide.
Produce the catalyzer that contains titanium aluminium carrier according to present method, the preparation route is simple, and raw material is easy to get, and its production cost cost by the production of method described in the above-mentioned European patent prospectus (publication number 0,339,640) titanium aluminium carrier is low more than 30%.The activity of this Hydrobon catalyst is better than similar Hydrobon catalyst.
The purposes of catalyzer of the present invention is in the light oil hydrocracking HDN and HDS process to be played katalysis simultaneously.This catalyzer does not need prevulcanized in hydrogenator.Operational condition is: temperature is risen to 200 ℃, feed stock oil (boiling range is within 80 ℃～200 ℃, sulphur content 5 μ g/g～1000 μ g/g, nitrogen content 5 μ g/g～500 μ g/g, bromine valency 20 gram bromines/100 gram oil).255～300 ℃ of temperature, the hydrogen flow is 12 a ml/min grams catalyzer, and air speed is 2～4/ o'clock, and pressure is 5MPa, and hydrogen-oil ratio (volume) is to react under 400: 1 the condition.Product sulfur-bearing, nitrogen amount all are less than or equal to 0.5 μ g/g, and the bromine valency is less than or equal to 0.1 gram bromine/100 gram oil.
In order to further specify the present invention, enumerate following examples and Comparative Examples, but it does not limit the defined invention scope of each accessory claim.
Example I
1, the preparation of carrier
(1) preparation of titanium aluminum solutions: with the TiCl of 11ml
4(density is 1.726g/ml) joins the AlCl of 360 grams
36H
2In the O xln, progressively drip deionized water then, dissolving under agitation, last thin up is to 1000ml, and the elimination insolubles obtains the titanium aluminum solutions.(2) preparation of sodium aluminate solution: 500ml water is joined in the sodium metaaluminate solid of 110 grams, stirring and dissolving, last thin up is to 1000ml, and the elimination insolubles obtains sodium aluminate solution.(3) under agitation, with above-mentioned titanium aluminum solutions and sodium aluminate solution with 55 ℃ of flow velocity, the temperature of reaction of 17ml/min. and flow co-precipitation, reaction is 2 hours under this temperature of reaction, last mother liquor pH value is 6, regulate pH value to 9.5 with ammoniacal liquor, placement is spent the night, suction filtration, washing, making beating back obtains the dried glue of titanium aluminium (the dried glue of Ti-Al) 110 ℃ of spraying dryings 4 hours.(4) restrain the dried glue of above-mentioned Ti-Al and contain HNO 133
32.5 the 100ml aqueous solution of gram fully mixes and pinches, and is extruded into cloverleaf pattern with banded extruder; Dry in the shade in room temperature, 120 ℃ of oven dry 4 hours, progressively be warming up to 550 ℃, roasting 5 hours makes the γ-Al that is loaded with titanium oxide 5% (weight)
2O
3Carrier (Ti-Al carrier).The specific surface area that records this carrier with nitrogen absorption (BET) method is 345m
2/ g, recording total pore volume with nitrogen adsorption method is 0.504ml/g, mean pore size is 5.84nm.
2, Preparation of catalysts method
The active ingredient molybdenum is added on the carrier at twice by step impregnation method.(1) Ammoniun Heptamolybdate Solution dipping: the solution that will contain Ammonium Heptamolybdate 30 grams with the equivalent impregnation method sprays on the above-mentioned 100 gram carriers at twice, 120 ℃ of oven dry 4 hours, 550 ℃ of roastings 5 hours can make and be loaded with the catalyst precursor MoO that molybdenum oxide content is 18.2% (weight)
3/ Ti-Al.(2) cobalt salt solution dipping: the aqueous solution that will contain Xiao Suangu 11.2 grams with the equivalent impregnation method sprays on the above-mentioned catalyst precursor, in 120 ℃ of oven dry 4 hours, 550 ℃ of roastings 5 hours, can make that to contain molybdenum oxide content be 18% (weight), cobalt oxide content is 3.5% (weight), and titanium oxide is the catalyzer of 4% (weight).This catalyzer is represented with A.
The preparation of the preparation of example II 1, carrier (1), titanium aluminum solutions: same example I, wherein TiCl
4Add-on be 22.5ml.(2), the preparation of sodium aluminate solution: same example I.(3), same example I, wherein making beating back obtains the dry sample of Ti-Al 120 ℃ of spraying dryings 3 hours.(4), same example I, wherein should the drying sample at 500 ℃, roasting 4 hours makes the Ti-Al roasting sample that is loaded with titanium oxide 10wt%.The specific surface area that records this roasting sample with nitrogen absorption (BET) method is 355m
2/ g, recording total pore volume with nitrogen adsorption method is 0.535ml/g, mean pore size is 6.03nm.2, Preparation of catalysts method
The same example I of Preparation of catalysts method, just in the oxidized catalyst that makes [MoCo/Ti-Al], molybdenum oxide content is 18% (weight), and cobalt oxide content is 3.5% (weight), and titanium oxide is 9.2% (weight).This catalyzer is represented with B.
The preparation of the preparation of EXAMPLE III 1, carrier (1), titanium aluminum solutions: same example I, wherein TiCl
4Add-on be 35.5ml.(2), the preparation of sodium aluminate solution: same example I.(3), same example I, wherein making beating back obtains the dry sample of Ti-Al 120 ℃ of spraying dryings 3 hours.(4), same example I, wherein should the drying sample 550 ℃ of roastings 6 hours, make the Ti-Al roasting sample that is loaded with titanium oxide 15wt%.The specific surface area that records this roasting sample with nitrogen absorption (BET) method is 330m
2/ g, recording total pore volume with nitrogen adsorption method is 0.540ml/g, mean pore size is 6.54nm.2, Preparation of catalysts method
The same example I of Preparation of catalysts method, just in the oxidized catalyst that makes [MoCo/Ti-Al], molybdenum oxide content is 18% (weight), and cobalt oxide content is 3.5% (weight), and titanium oxide is 14% (weight).This catalyzer is represented with C.
The preparation of the preparation of EXAMPLE IV 1, carrier (1), titanium aluminum solutions: same example I, wherein TiCl
4Add-on is 50ml.(2), the preparation of sodium aluminate solution: same example I.(3), same example I, make the dry sample of Ti-Al.(4), same example I, wherein should the drying sample 600 ℃ of roastings 2.5 hours, make the Ti-Al roasting sample that is loaded with titanium oxide 20wt%.The specific surface area that records this roasting sample with nitrogen absorption (BET) method is 320m
2/ g, recording total pore volume with nitrogen adsorption method is 0.520ml/g, mean pore size is 6.50nm.2, Preparation of catalysts method
The same example I of Preparation of catalysts method, just in the oxidized catalyst MoCo/Ti-Al that makes, molybdenum oxide content is 18% (weight), and cobalt oxide content is 3.5% (weight), and titanium oxide is 18.5% (weight).This catalyzer is represented with D.
The preparation of the preparation of EXAMPLE V 1, carrier (1), titanium aluminum solutions: same example I, wherein TiCl
4Add-on is 66.5ml.(2), the preparation of sodium aluminate solution: same example I.(3), same example I, make the dry sample of Ti-Al.(4), same example I, wherein should the drying sample 500 ℃ of roastings 4 hours, make the Ti-Al roasting sample that is loaded with titanium oxide 25wt%.The specific surface area that records this roasting sample with nitrogen absorption (BET) method is 315m
2/ g, recording total pore volume with nitrogen adsorption method is 0.500ml/g, mean pore size is 6.35nm.2, Preparation of catalysts
The same example I of Preparation of catalysts method, just in the oxidized catalyst MoCo/Ti-Al that makes, molybdenum oxide content is 18% (weight), and cobalt oxide content is 3.5% (weight), and titanium oxide is 23.4% (weight).This catalyzer is represented with E.
The preparation of the preparation of example VI 1, carrier (1), titanium aluminum solutions: same example I, wherein TiCl
4Add-on is 85.5ml.(2), the preparation of sodium aluminate solution: same example I.(3), same example I, make the dry sample of Ti-Al.(4), same example I, wherein should the drying sample 500 ℃ of following roastings 4 hours, make the Ti-Al roasting sample that is loaded with titanium oxide 30wt%.The specific surface area that records this roasting sample with nitrogen absorption (BET) method is 300m
2/ g, recording total pore volume with nitrogen adsorption method is 0.485ml/g, mean pore size is 6.47nm.2, Preparation of catalysts
The same example I of Preparation of catalysts method, just in the oxidized catalyst MoCo/Ti-Al that makes, molybdenum oxide content is 18% (weight), and cobalt oxide content is 3.5% (weight), and titanium oxide is 28% (weight).This catalyzer is represented with F.
The preparation of the preparation of example VII A 1, carrier (1), titanium aluminum solutions: same example I, wherein TiCl
4Add-on is 107.5ml.(2), the preparation of sodium aluminate solution: same example I.(3), same example I, make the dry sample of Ti-Al.(4), same example I, wherein should the drying sample 490 ℃ of roastings 4 hours, make the Ti-Al roasting sample that is loaded with titanium oxide 35wt%.The specific surface area that records this roasting sample with nitrogen absorption (BET) method is 285m
2/ g, recording total pore volume with nitrogen adsorption method is 0.475ml/g, mean pore size is 6.67nm.2, Preparation of catalysts
The same example I of Preparation of catalysts method, just in the oxidized catalyst MoCo/Ti-Al that makes, molybdenum oxide content is 18% (weight), and cobalt oxide content is 3.5% (weight), and titanium oxide is 32% (weight).This catalyzer is represented with G.
The preparation of the preparation of example VII A I1, carrier (1), titanium aluminum solutions: same example I, wherein TiCl
4Add-on is 133ml.(2), the preparation of sodium aluminate solution: same example I.(3), same example I, make the dry sample of Ti-Al.(4), same example I, wherein should the drying sample 460 ℃ of roastings 4 hours, make the Ti-Al roasting sample that is loaded with titanium oxide 40wt%.The specific surface area that records this roasting sample with nitrogen absorption (BET) method is 270m
2/ g, recording total pore volume with nitrogen adsorption method is 0.470ml/g, mean pore size is 6.96nm.2, Preparation of catalysts
The same example I of Preparation of catalysts method, just in the oxidized catalyst MoCo/Ti-Al that makes, molybdenum oxide content is 18% (weight), and cobalt oxide content is 3.5% (weight), and titanium oxide is 37.5% (weight).This catalyzer is represented with H.
The preparation of the preparation of example I X1, carrier (1), titanium aluminum solutions: same example I, wherein TiCl
4Add-on is 158ml.(2), the preparation of sodium aluminate solution: same example I.(3), same example I, make the dry sample of Ti-Al.(4), same example I, wherein should the drying sample 460 ℃ of roastings 7 hours, make the Ti-Al roasting sample that is loaded with titanium oxide 45wt%.The specific surface area that records this roasting sample with nitrogen absorption (BET) method is 240m
2/ g, recording total pore volume with nitrogen adsorption method is 0.450ml/g, mean pore size is 7.50nm.2, Preparation of catalysts
The same example I of Preparation of catalysts method, just in the oxidized catalyst MoCo/Ti-Al that makes, molybdenum oxide content is 18% (weight), and cobalt oxide content is 3.5% (weight), and titanium oxide is 42.5% (weight).This catalyzer is represented with I.
Comparative Examples I
Press in the European patent prospectus (publication number 0,339,640) that disclosed method prepares carrier and catalyzer is as follows: with 243 gram NaAlO
2Be dissolved in the 1000ml water, the elimination insolubles makes NaAlO
2Solution.To contain TiOCl
2The aqueous solution of 41 grams is diluted to 1000ml, makes TiOCl
2The aqueous solution.Above-mentioned two kinds of solution are reacted in the speed adding reactor with 125ml/min. simultaneously.Temperature of reaction is controlled at 55 ℃, and reacting last mother liquor pH value is 6, regulates pH value to 9.5 with ammoniacal liquor, and placement is spent the night, suction filtration, washing, and making beating back spraying drying obtains the dried glue of titanium aluminium (the dried glue of Ti-Al).Restrain the dried glue of above-mentioned Ti-Al and contain HNO 133
32.5 the 100ml aqueous solution of gram fully mixes and pinches, and is extruded into cloverleaf pattern with banded extruder; Dry in the shade in room temperature, 120 ℃ of oven dry 4 hours, progressively be warming up to 550 ℃, roasting 5 hours makes the γ-Al that is loaded with titanium oxide 15wt%
2O
3Carrier (Ti-Al carrier).The specific surface area that records this roasting sample with nitrogen absorption (BET) method is 260m
2/ g, recording total pore volume with nitrogen adsorption method is 0.520ml/g, mean pore size is 8.00nm.
The Preparation of catalysts method: the active ingredient molybdenum is added on the carrier by step impregnation method.(1) Ammoniun Heptamolybdate Solution dipping: the ammonia soln that will contain Ammonium Heptamolybdate 30 grams with the equivalent impregnation method sprays on the above-mentioned 100 gram carriers, 120 ℃ of oven dry 4 hours, 538 ℃ of roastings 5 hours can make and be loaded with the catalyst precursor MoO that molybdenum oxide content is 18.2% (weight)
3/ Ti-Al.(2) cobalt salt solution dipping: the aqueous solution that will contain Xiao Suangu 11.2 grams with the equivalent impregnation method sprays on the above-mentioned catalyst precursor, in 120 ℃ of oven dry 4 hours, 538 ℃ of roastings 5 hours, can make that to contain molybdenum oxide content be 18% (weight), cobalt oxide content is 3.5% (weight), and titanium oxide is the catalyzer of 14% (weight).This catalyzer is represented with J.
The application of embodiment X catalyzer in the hydrocarbon conversion
Catalyst A, B, C, D, E, F, G, H, I and J are tested as hydrogenating desulfurization and denitrogenation.Catalyzer J is as the contrast experiment.Catalyst A, B, C, D, E, F, G, H, I and J operation condition are identical.
Get catalyzer 5.0 gram and pack in the fixed-bed reactor, cool the temperature to 200 ℃, feed stock oil (boiling range is 80～300 ℃, sulphur content 1000 μ g/g, nitrogen content 500 μ g/g, bromine valency 20 gram bromines/100 gram oil).300 ℃ of temperature, the hydrogen flow is 12 a ml/min grams catalyzer, and air speed is 2.5/ o'clock, and reaction pressure is 5MPa, and hydrogen-oil ratio (volume) is to react under 400: 1 the condition.Active comparing result is as shown in table 1.
The active comparing result of table 1
Table 1 is the result show, under the identical situation of active ingredient, titanium oxide content, this invention activity of such catalysts comparison is than activity of such catalysts height.
| Catalyzer | Reaction times (hour) | Product nitrogen content (μ g/g) | Product sulphur content (μ g/g) | Product bromine valency (gram bromine/100 gram oil) |
| A | 200 | ＜1.0 | ＜1.0 | ＜0.1 |
| B | 200 | ＜0.50 | ＜0.50 | ＜0.05 |
| C | 200 | ＜1.0 | ＜0.50 | ＜0.1 |
| D | 200 | ＜1.0 | ＜0.50 | ＜0.1 |
| E | 200 | ＜2.0 | ＜1.0 | ＜0.2 |
| F | 200 | ＜5.0 | ＜1.0 | ＜0.2 |
| G | 200 | ＜5.0 | ＜2.0 | ＜0.2 |
| H | 200 | ＜5.0 | ＜2.0 | ＜0.2 |
| I | 200 | ＜7.0 | ＜3.0 | ＜0.5 |
| J | 200 | ＜5.0 | ＜2.0 | ＜0.2 |
Table 2 stability experiment
Table 2 is the result show, under the identical situation of active ingredient, titanium oxide content, this invention catalyzer is high than comparative catalyst's stability.
| Catalyzer | Reaction times (hour) | Product nitrogen content (μ g/g) | Product sulphur content (μ g/g) | Product bromine valency (gram bromine/100 gram oil) |
| C | 1000 | ＜1.0 | ＜1.0 | ＜0.1 |
| J | 1000 | ＜7.0 | ＜4.0 | ＜0.2 |
Claims (11)
1. a Hydrobon catalyst is characterized in that carrier is the γ-Al that is loaded with titanium
2O
3, active ingredient is VIII family metal and/or group vib metal, it consists of vib metal oxide compound 5wt%～30wt%, and group VIII metal oxide 2wt%～8wt%, titanium oxide 0.5wt%～50wt%, all the other are aluminum oxide.
2. according to the described Hydrobon catalyst of claim 1, it is characterized in that said vib metal oxide compound is molybdenum oxide and/or Tungsten oxide 99.999, the group VIII metal oxide is cobalt oxide and/or nickel oxide.
3. one kind is carrier with the Ti-Al two-pack, is the preparation method of the Hydrobon catalyst of active ingredient with group vib and/or group VIII metal, it is characterized in that preparation process is as follows: the preparation of (1), Ti-Al carrier
1., the preparation of titanium aluminum solutions: but with solubility titanium salt and property aluminium salt crystal by weight 5 * 10
-3～0.7 mixes, and progressively drips deionized water then, obtains the titanium aluminum solutions;
2., the preparation of sodium aluminate solution: the sodium metaaluminate solid is soluble in water, obtain the sodium aluminate solution that concentration is 5wt%～20wt%;
3., under agitation, above-mentioned titanium aluminum solutions and sodium aluminate solution are 20 ℃～70 ℃ and flow co-precipitation in temperature of reaction, after reacting 1～3 hour under this temperature of reaction, regulate pH value to 8.5～10 with ammoniacal liquor, placement is spent the night, suction filtration, washing, making beating back obtains the dry sample of Ti-Al 80 ℃～150 ℃ spraying dryings 2～8 hours;
4., press W
HNO3/ W
The dry sample of Ti-Al=0.010～0.025, W
H2O/ W
The dry sample of Ti-Al=0.50～1.0 are extruded into various suitable shapes after pinching with dry sample of Ti-Al and aqueous nitric acid are fully mixed, dry in the shade in room temperature,, progressively be warming up to 450～650 ℃ 100～150 ℃ of oven dry 2～8 hours, roasting 4～8 hours makes the Ti-Al roasting sample that is loaded with titanium oxide 0.5wt%～50wt%; (2), the Preparation of catalysts method: active ingredient is added on the carrier by step impregnation method,
1., solubility group vib metal salt solution dipping: solubility group vib metal salt solution is sprayed on the above-mentioned carrier with the equivalent impregnation method, 100 ℃～150 ℃ oven dry 2～8 hours, 450 ℃～650 ℃ roastings 4～8 hours make the catalyst precursor that the group vib metal oxide content is 6wt%～35wt%;
2., group VIII metal salt solution dipping: solubility group VIII metal salt solution is sprayed on the above-mentioned catalyst precursor with the equivalent impregnation method, in 100 ℃～150 ℃ oven dry 2～8 hours, 450 ℃～650 ℃ roastings 4～8 hours make the catalyzer that the group VIII metal oxide content is 1wt%～10wt%.
4. according to the described preparation method of claim 3, it is characterized in that the Preparation of catalysts method adopts leaching method preparation altogether in the step (2): the VIB and the group VIII metal-salt of (1) preparation solubility soak solution altogether: with the VIB of solubility and the
VIII family metal-salt is put into same beaker, adds deionized water, is mixed with to contain the group vib metal
Salt 5～18wt% and contain group VIII metal-salt 1～10wt% soak solution altogether; (2) VIB and group VIII metal-salt soak solution impregnation altogether: with the equivalent impregnation method with the above-mentioned solution that soaks altogether
Spray on the above-mentioned carrier, in 100 ℃～150 ℃ oven dry 2～8 hours, 450 ℃～650 ℃ roastings
Burnt 4～8 hours, and can make the catalyzer that contains titanium oxide.
5. according to the described preparation method of claim 3, it is characterized in that the solubility titanium salt mixes by weight 0.04～0.5 with the soluble aluminum salt crystal in the step (1)-1..
6. according to the described preparation method of claim 5, it is characterized in that the solubility titanium salt mixes by weight 0.05～0.3 with the soluble aluminum salt crystal.
7. according to the described preparation method of claim 3, it is characterized in that said solubility titanium salt is TiCl in the step (1)-1.
4, TiCl
3, TiOCl
2Or Ti (SO
4)
2, the soluble aluminum salt crystal is AlCl
3, Al
2(SO
4)
3Or Al (NO
3)
3
8. according to the preparation method described in the claim 7, it is characterized in that said solubility titanium salt is TiCl
4, the soluble aluminum salt crystal is AlCl
3
9. according to the described preparation method of claim 3, it is characterized in that said solubility group vib metal salt solution is the salts solution of molybdenum and/or tungsten in the step (2)-1., said solubility group VIII metal salt solution is the salts solution of cobalt and/or nickel in the step (2)-2..
10. according to the described preparation method of claim 9, it is characterized in that solubility group vib metal salt solution is ammonium molybdate and/or ammonium metawolframate, solubility group VIII metal salt solution is Xiao Suangu and/or nickelous nitrate.
11. the application of catalyzer in HDN and HDS process according to claim 1 is characterized in that operational condition is: 255～300 ℃ of temperature, hydrogen flow are 12 ml/min gram catalyzer, and air speed is 2～4/ o'clock, and pressure is 5MPa, and hydrogen to oil volume ratio is 400: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112939A CN1088092C (en) | 1999-05-18 | 1999-05-18 | Hydrorefining catalyst for hydrocarbons |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99112939A CN1088092C (en) | 1999-05-18 | 1999-05-18 | Hydrorefining catalyst for hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
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| CN1088092C true CN1088092C (en) | 2002-07-24 |
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| CN111282560A (en) * | 2020-03-26 | 2020-06-16 | 中国石油大学(北京) | A kind of coking wax oil hydrogenation catalyst and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0339640A1 (en) * | 1988-04-28 | 1989-11-02 | The Harshaw Chemical Company | Alumina-titania composition |
| CN1110304A (en) * | 1994-04-13 | 1995-10-18 | 中国石油化工总公司 | Heavy oil hydrotreatment catalyst |
-
1999
- 1999-05-18 CN CN99112939A patent/CN1088092C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0339640A1 (en) * | 1988-04-28 | 1989-11-02 | The Harshaw Chemical Company | Alumina-titania composition |
| CN1110304A (en) * | 1994-04-13 | 1995-10-18 | 中国石油化工总公司 | Heavy oil hydrotreatment catalyst |
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