CN1136298C - Catalyst for producing middle fraction from Fischer-Tropsch synthetic heavy hydrocarbon and its prepn and use - Google Patents
Catalyst for producing middle fraction from Fischer-Tropsch synthetic heavy hydrocarbon and its prepn and use Download PDFInfo
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- CN1136298C CN1136298C CNB01111438XA CN01111438A CN1136298C CN 1136298 C CN1136298 C CN 1136298C CN B01111438X A CNB01111438X A CN B01111438XA CN 01111438 A CN01111438 A CN 01111438A CN 1136298 C CN1136298 C CN 1136298C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 20
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 18
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 41
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000010457 zeolite Substances 0.000 claims abstract description 41
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 13
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 239000004411 aluminium Substances 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 33
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 206010013786 Dry skin Diseases 0.000 claims description 16
- 238000005342 ion exchange Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910021332 silicide Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000004913 activation Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 nickelous nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a catalyst used for preparing middle fraction from Fischer-Tropsch synthetic heavy hydrocarbons, which comprises (by weight percentage) 10 to 40% of Y zeolite, 0 to 40% of amorphous silica aluminium, 3 to 10% of nickel oxide and 20 to 70% of aluminum oxide. The specific surface area of the catalyst is from 300 to 600m<2>/g, the pore volume is from 0.30 to 0.70 ml/g, and the TPD acidity is from 0.75 to 1.5 mmol/g. The present invention can carry out selectivity chain breaking operation for heavy hydrocarbons in Fischer-Tropsch synthesis products and has good activity and good middle oil selectivity. The preparing process of the catalyst is simple and convenient, the operation is easy, and the present invention is suitable for industrial production.
Description
Catalysts and its preparation method and purposes
The present invention relates to a kind of hydrocracking catalyst, especially for the Fischer-Tropsch synthesis of heavy hydrocarbon material, the Catalysts and its preparation method and the purposes of system intermediate oil.
Since the World War II, the huge liquid fuel market of bringing in the face of economic growth reaches depleted day by day petroleum resources, energy consumption structure changes to oil, coal and Sweet natural gas alliance type gradually from oil dependent form, thereby make coal/Sweet natural gas indirect liquefaction technology (be the Fischer-Tropsch synthesis method, be called for short FT synthetic) become back petroleum industry epoch one of the most attractive approach.And China has high coal, oil starvation, have the fossil resource of gas to distribute, by FT synthetic with coal/conversion of natural gas be motor spirit be clean, efficiently utilize the important directions of resource.Recent FT synthesis technique more options cobalt series catalyst is as the co hydrogenation catalyzer.The maximum characteristics of cobalt series catalyst are: can make synthetic gas be converted into heavy hydrocarbon based on straight-chain paraffin to greatest extent, intermediate oil (comprising boat coal and diesel oil) is produced in the heavy hydrocarbon hydrocracking then.
In recent years, hydrocracking technology has become one of major technique of petroleum refining industry, especially for the secondary processing distillate, produces all kinds of petroleum productss, so the development of hydrocracking catalyst is more and more important with exploitation.The hydrogenation of hydrocracking catalyst and cracking function are to mate by the acidity of metal constituent element and carrier to form, and other auxiliary agents help out.For the hydrocracking catalyst of producing intermediate oil, except that considering activity of such catalysts, the selectivity of oil in also need considering, promptly catalyzer should have abundant big mesopore, high acid amount and in the strength of acid of weak degree.This just need handle through modification the acidic components Y zeolite in the catalyzer, is about to the raw material Y zeolite and carries out hydrothermal treatment consists and chemical after-treatment reason again after amine and acid treatment dealuminzation are taken off in roasting, and the silica alumina ratio of its modified Y zeolite improves, and the solid acid amount reduces.
At present, domestic and international many research units have developed dissimilar hydrocracking catalysts, disclose a kind of oil type hydrocracking catalyst that is used for crude oil processing as EP0028938A1, and characteristics have been to use a kind of y-type zeolite, and its preparation process comprises SiO
2/ Al
2O
3Mol ratio is 4.5～9, specific surface area 350m
2The raw material zeolite of/g, in 0.2～10 normal atmosphere, 725～870 ℃ of following hydrothermal treatment consists, because this zeolite water thermal treatment temp height, thereby the heatproof requirement to High Temperature Furnaces Heating Apparatus is very high in the preparation process, and the energy consumption height.From the Arabic VGO of the related hydrotreatment of embodiment, though middle distillates oil selectivity 86%, transformation efficiency has only 60v%, and temperature of reaction illustrates that but up to 407 ℃ activity of such catalysts and middle distillates oil selectivity can not be well balanced.Domestic research unit has also developed many hydrocracking catalyst kinds, but great majority are to handle light crude, high aromatic hydrocarbons heavy hydrocarbon (as gas oil, reduced pressure distillate wet goods), contain sulphur, nitrogen, naphthenic hydrocarbon and polycyclic aromatic hydrocarbons etc. in the stock oil.And heavy hydrocarbon belongs to the high carbon number aliphatic saturated hydrocarbon of straight chain class in the Fischer-Tropsch synthetic, and its carbon number distribution is very wide, can be from C
20～C
100, it contains side chain number seldom, and does not contain impurity such as Residual oil, sulphur and nitrogen.As middle oil type hydrocracking catalysts such as domestic commerce types 3903,3976, also be used to handle nitrogenous, contain the higher stock oil of aromatic hydrocarbons, the cracking performance of these catalyzer is stronger relatively, and when being applied to the hydrocracking process of heavy hydrocarbon in the Fischer-Tropsch synthetic, the intermediate oil selectivity is relatively poor.
The object of the present invention is to provide the hydrocracking catalyst that a kind of activity is good, selectivity is high, be used for the Fischer-Tropsch synthesis of heavy hydrocarbon material, the system intermediate oil.
Catalyst weight per-cent of the present invention consists of:
Y zeolite 10～40% amorphous aluminum silicides 0～40%
Nickel oxide 3～10% aluminum oxide 20～70%
Described catalyzer can also include the rare earth element that weight percent is 1-8%.
Hydrocracking catalyst of the present invention has specific surface area 300～600m
2/ g, pore volume 0.30～0.70ml/g, the feature of TPD acidity 0.75～1.5mmol/g.
Preparation of catalysts method of the present invention is as follows:
(1) is raw material with the NaY zeolite, uses NH
4NO
3Solution carries out ion-exchange under 90～100 ℃, filter then, wash, oven dry;
(2) with above-mentioned product normal pressure, 450～600 ℃, after the roasting, use NH again under 100% water vapour
4NO
3Solution carries out ion-exchange under 90～100 ℃, obtain Na
2O content is less than 0.2% Y zeolite;
(3) with Na
2O content places homemade high-temperature roasting stove less than 0.2% Y zeolite, feeds water vapour, handles after 2～4 hours down, obtains Y zeolite for 500～700 ℃.
(4) Y zeolite that step (3) is obtained contacts with the nitrate that contains metallic nickel, obtains being impregnated with the carrier of hydrogenation metal, 100～120 ℃ of dryings 3～5 hours, and 400～600 ℃ of roastings 2～6 hours make (A);
(5) (A) and aluminum oxide and amorphous silicon aluminium are mixed after, with the dilute nitric acid solution modulation, mediate, after Ф 2mm cylinder orifice plate extrusion, 100～120 ℃ of dryings 3～5 hours, 400～600 ℃ of roastings 2～6 hours make the catalyzer finished product.
Wherein the weight percent of each component is:
Y zeolite 10～40% amorphous aluminum silicides 0～40%
Nickel oxide 3～10% aluminum oxide 20～70%
Preparation of catalysts method of the present invention can also be:
(1) is raw material with the NaY zeolite, uses NH
4NO
3Solution carries out ion-exchange under 90～100 ℃, filter then, wash, oven dry;
(2) with above-mentioned product normal pressure, 450～600 ℃, after the roasting, use NH again under 100% water vapour
4NO
3Solution carries out ion-exchange under 90～100 ℃, obtain Na
2O content is less than 0.2% Y zeolite;
(3) with Na
2O content places homemade high-temperature roasting stove less than 0.2% Y zeolite, feed water vapour, handle after 2～4 hours down for 500～700 ℃, add and contain in the earth solution of rare earth element, stirring, ion-exchange are filtered, and washing is to neutral, 400～600 ℃ of roastings obtain containing the Y zeolite of rare earth metal;
(4) Y zeolite that step (3) is obtained contacts with the nitrate that contains metallic nickel, obtains being impregnated with the carrier of hydrogenation metal, 100～120 ℃ of dryings 3～5 hours, and 400～600 ℃ of roastings 2～6 hours make (A);
(5) (A) and aluminum oxide and amorphous silicon aluminium are mixed after, with the dilute nitric acid solution modulation, mediate, after Ф 2mm cylinder orifice plate extrusion, 100～120 ℃ of dryings 3～5 hours, 400～600 ℃ of roastings 2～6 hours make the catalyzer finished product.
Wherein the weight percent of each component is:
Y zeolite 10～40% amorphous aluminum silicides 0～40%
Nickel oxide 3～10% aluminum oxide 20～70%
Rare earth element 1～8%
Two kinds of above-mentioned preparation methods can also be first extruded mouldings, back impregnating metal.
Catalyzer of the present invention is used for Fischer-Tropsch synthetic heavy hydrocarbon hydrocracking system intermediate oil processing condition: reaction pressure 1.5～8MPa depresses, 280～450 ℃ of temperature of reaction, reaction velocity 0.1～5.0h
-1, hydrogen-oil ratio 500～5000.
The present invention compared with prior art has following advantage:
1. catalyzer of the present invention can carry out the selectivity chain rupture to heavy hydrocarbon in the Fischer-Tropsch synthetic, is therefore obtaining the hydrocracking process of intermediate oil, has activity and middle distillates oil selectivity preferably.
2. catalyst preparation process of the present invention is simple, convenient, and easy handling is suitable for industrial production.
Embodiment one:
(1) gets 500gNaY zeolite (production of Wenzhou catalyst plant), be added to the NH that 2L concentration is 2M
4NO
3In the solution, stir down at 90 ℃, ion-exchange 2 hours exchanges 3 times altogether, filters then, washs to neutrality, and oven dry gets the product first.
(2) with the product first normal pressure, 500 ℃, under 100% water vapour, roasting 2 hours, product second.
(3) with (1) ion-exchange 3 times set by step of product second, obtain Na
2The zeolite product third of O＜0.2%.
(4) product third is inserted in the homemade stoving oven, feeds water vapour, 500 ℃ of following roastings 3 hours, the product fourth.
(5) get solid Ni (NO
3)
26H
2The O14.7 gram, with the less water dissolving, dropping ammonia is to forming the transparent nickel ammonia solution of mazarine (PH=12).Product fourth 30 grams that step (4) is obtained impregnated in the above-mentioned solution, stir and make it to form stable slurry, place more than 12 hours, 110 ℃ dry 4 hours down, 500 ℃ of following roastings 4 hours, product (A).
(6) 63.3 gram aluminum oxide and product (A) are mixed, with the modulation of 3% dilute nitric acid solution, mediate, behind Ф 2mm cylinder orifice plate extruded moulding, 110 ℃ of dryings 4 hours, through 500 ℃ of activation 3 hours, obtain the catalyst A that hydrocracking process of the present invention relates to.Catalyzer consists of: Y zeolite 30.8%, nickel oxide 3.81%, aluminum oxide 65%.
Embodiment two
(1) gets product that step among the embodiment one (3) obtains the third 25 grams, place homemade stoving oven, at 550 ℃, 100% water vapour is handled after 6 hours down, being added to 500ml contains in the earth solution of 10% rare-earth elements of lanthanum and cerium, stir down at 90 ℃, ion-exchange 2 hours is filtered then, washing is to neutral, oven dry, 500 ℃ of roastings 4 hours, product that obtains and 63.2 gram aluminum oxide mix, and the dilute nitric acid solution with 3% is modulated, mediate, behind Ф 2mm cylinder orifice plate extruded moulding, 110 ℃ of dryings 4 hours,, obtain support of the catalyst of the present invention through 500 ℃ of activation 3 hours.
(2) get solid Ni (NO
3)
26H
2O 14.5 grams, with the less water dissolving, dropping ammonia is to forming the transparent nickel ammonia solution of mazarine (PH=12).The carrier impregnation that step (1) is obtained is placed more than 12 hours in above-mentioned solution.Drying is 4 hours under 110 ℃, and 500 ℃ of following roastings obtained the catalyst B that hydrocracking process of the present invention relates to after 4 hours.Catalyzer consists of: Y zeolite 27.2%, nickel oxide 4.1%, aluminum oxide 68.7%, Rare Earth Lanthanum and cerium 7.9% (atomic absorption method records).
Embodiment three
(1) get product that step among the embodiment one (3) obtains the third 100 grams and place homemade stoving oven, at 600 ℃, 100% water vapour was handled 6 hours down, obtained product (I).
(2) product (I) is added to 200ml and contains in the lanthanum nitrate hexahydrate of lanthanum 3%, stir down at 90 ℃, ion-exchange 2 hours is filtered then, is washed to neutrality, oven dry, 500 ℃ of roastings 4 hours, product (II).
(3) get product (II) 21.1g, add 36.7 gram amorphous aluminum silicide (SiO
2Content 40w%) and 39 gram aluminum oxide mix and to pinch into paste, extruded moulding, 110 ℃ of dryings 5 hours, 500 ℃ of activation 4 hours behind the carrier, flood this carrier with nickel nitrate solution, obtain the catalyzer C that hydrocracking process of the present invention relates to.Catalyzer consists of: Y zeolite 16.2%, nickel oxide 9.2%, amorphous silicon aluminium 28.2%, aluminum oxide 30%, Rare Earth Lanthanum 1.8%.
Embodiment four
(1) 10g oxalic acid is dissolved in the 100ml water, slowly drips the product (I) that obtains at 40 gram embodiment three and restrain in (adding 400ml water), handled 1 hour down, filter, wash to neutral, oven dry at 95 ℃.Get product I.
(2) get product I 25 grams, add 64.3 gram amorphous aluminum silicide (SiO
2Content 35w%) and 65.3 gram aluminum oxide mix and to pinch into paste, extruded moulding, 110 ℃ of dryings 5 hours, 500 ℃ of activation 4 hours behind the carrier, again with 46.1 gram nickel nitrate solutions dippings, 110 ℃ of dryings 5 hours, 500 ℃ activate 4 hours, obtain catalyzer D.Catalyzer consists of Y zeolite 15%, amorphous silicon aluminium 38.6%, nickel oxide 7.2%, aluminum oxide 39.2%.
Embodiment five
(1) get product (I) 30 gram among the embodiment three, be added to 300ml and contain in the earth solution of 8% rare-earth element cerium, 90 ℃ are stirred down, and ion-exchange 2 hours is filtered then, washed to neutrality, oven dry, 500 ℃ of roastings 4 hours.
(2) get product 20 grams that step (1) obtains, after the nickel ammonia solutions dipping of 10.8 gram nickelous nitrates, dry, roasting, with aluminum oxide 39.5 grams, dilute nitric acid solution modulation, kneading with 2%, behind Ф 2mm cylinder orifice plate extruded moulding, 120 ℃ of dryings 3 hours, 600 ℃ of activation 3 hours made the catalyzer E that hydrocracking process of the present invention relates to.Catalyzer consists of Y zeolite 32.1%, nickel oxide 4.5%, aluminum oxide 63.4%, rare earth cerium 5.3%.
Embodiment six
Get the product fourth 20g among the embodiment one, add 18.9 gram amorphous aluminum silicide (SiO
2Content 40w%) and 10.7 the gram aluminum oxide, dilute nitric acid solution modulation, kneading with 2%, extruded moulding, 110 ℃ of dryings 5 hours, 500 ℃ of activation 4 hours behind the carrier, again with the steeping fluid impregnation catalyst agent carrier of nickelous nitrate 11.8 gram preparations, 110 ℃ of dryings 5 hours, 550 ℃ activate 4 hours, obtain catalyzer F.Catalyzer consists of: Y zeolite 38%, nickel oxide 5.8%, amorphous silicon aluminium 35.9%, aluminum oxide 20.3%.
The physico-chemical property of related catalyzer sees Table 1 among the above embodiment.
Catalyzer involved in the present invention is used for the reaction evaluating that the Fischer-Tropsch synthetic heavy hydrocarbon carries out hydrocracking system intermediate oil, and evaluation result sees Table 2.The evaluation processing condition are: reaction pressure 4.0MPa, liquid air speed 1.0h
-1, hydrogen-oil ratio 1000.Middle distillates oil selectivity calculates by " (boat yield of coal+diesel yield)/＜370 ℃ of product yields " and calculates.Find out that from table 2 data the catalyzer that intermediate oil is produced in hydrocracking involved in the present invention has active preferably and higher selectivity.
The physico-chemical property of table 1 catalyzer
| Catalyzer | A | B | C | D | E | F |
| Specific surface (m 2/g) | 337 | 262 | 359 | 397 | 305 | 245 |
| Pore volume (ml/g) | 0.45 | 0.39 | 0.52 | 0.63 | 0.38 | 0.30 |
| ＞2.0nm pore distribution, % | 43 | 62 | 71 | 68 | 50 | 65 |
| TPD acidity, mmol/g | 1.2 | 0.7 | 0.8 | 0.9 | 1.15 | 0.95 |
The reaction evaluating result of table 2 catalyzer
| The catalyzer numbering | A | B | C | D | E | F |
| Temperature of reaction, ℃ | 300 | 310 | 300 | 305 | 310 | 320 |
| Transformation efficiency, w% | 70 | 50 | 60 | 60 | 70 | 65 |
| Middle distillates oil selectivity, % | 79.1 | 90.2 | 84.6 | 83.7 | 78.3 | 80.1 |
Claims (6)
1. catalyzer that is used for Fischer-Tropsch synthesis of heavy hydrocarbon system intermediate oil is characterized in that the weight percent of catalyzer consists of:
Y zeolite 10～40% amorphous aluminum silicides 0～40%
Nickel oxide 3～10% aluminum oxide 20～70%;
Specific surface area of catalyst 300～600m
2/ g, pore volume 0.30～0.70ml/g, TPD acidity 0.75～
1.5mmol/g。
2. a kind of catalyzer that is used for Fischer-Tropsch synthesis of heavy hydrocarbon system intermediate oil according to claim 1 is characterized in that catalyzer also includes the rare earth element that weight percent is 1-8%.
3. a Preparation of catalysts method that is used for Fischer-Tropsch synthesis of heavy hydrocarbon system intermediate oil is characterized in that the Preparation of catalysts method comprises the steps:
(1) is raw material with the NaY zeolite, uses NH
4NO
3Solution carries out ion-exchange under 90～100 ℃, filter then, wash, oven dry;
(2) with above-mentioned product normal pressure, 450～600 ℃, after the roasting, use NH again under 100% water vapour
4NO
3Solution carries out ion-exchange under 90～100 ℃, obtain Na
2O content is less than 0.2% Y zeolite;
(3) with Na
2O content places homemade high-temperature roasting stove less than 0.2% Y zeolite, feeds water vapour, handles after 2～4 hours down, obtains Y zeolite for 500～700 ℃;
(4) Y zeolite that step (3) is obtained contacts with the nitrate that contains metallic nickel, obtains being impregnated with the carrier of hydrogenation metal, 100～120 ℃ of dryings 3～5 hours, and 400～600 ℃ of roastings 2～6 hours make (A);
(5) (A) and aluminum oxide and amorphous silicon aluminium are mixed after, with the dilute nitric acid solution modulation, mediate, after Ф 2mm cylinder orifice plate extrusion, 100～120 ℃ of dryings 3～5 hours, 400～600 ℃ of roastings 2～6 hours make the catalyzer finished product;
Wherein the weight percent of each component is:
Y zeolite 10～40% amorphous aluminum silicides 0～40%
Nickel oxide 3～10% aluminum oxide 20～70%
4. a Preparation of catalysts method that is used for Fischer-Tropsch synthesis of heavy hydrocarbon system intermediate oil is characterized in that the Preparation of catalysts method comprises the steps:
(1) is raw material with the NaY zeolite, uses NH
4NO
3Solution carries out ion-exchange under 90～100 ℃, filter then, wash, oven dry;
(2) with above-mentioned product normal pressure, 450～600 ℃, after the roasting, use NH again under 100% water vapour
4NO
3Solution carries out ion-exchange under 90～100 ℃, obtain Na
2O content is less than 0.2% Y zeolite;
(3) with Na
2O content places homemade high-temperature roasting stove less than 0.2% Y zeolite, feed water vapour, handle after 2～4 hours down for 500～700 ℃, add and contain in the earth solution of rare earth element, stirring, ion-exchange are filtered, and washing is to neutral, 400～600 ℃ of roastings obtain containing the Y zeolite of rare earth metal;
(4) Y zeolite that step (3) is obtained contacts with the nitrate that contains metallic nickel, obtains being impregnated with the carrier of hydrogenation metal, 100～120 ℃ of dryings 3～5 hours, and 400～600 ℃ of roastings 2～6 hours make (A);
(5) (A) and aluminum oxide and amorphous silicon aluminium are mixed after, with the dilute nitric acid solution modulation, mediate, after Ф 2mm cylinder orifice plate extrusion, 100～120 ℃ of dryings 3～5 hours, 400～600 ℃ of roastings 2～6 hours make the catalyzer finished product;
Wherein the weight percent of each component is:
Y zeolite 10～40% amorphous aluminum silicides 0～40%
Nickel oxide 3～10% aluminum oxide 20～70%
Rare earth element 1～8%.
5. according to claim 3 or 4 described Preparation of catalysts methods, it is characterized in that two kinds of above-mentioned preparation methods can also be first extruded mouldings, back impregnating metal.
6. an Application of Catalyst method that is used for Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking system intermediate oil is characterized in that processing condition are: reaction pressure 1.5～8MPa, 280～450 ℃ of temperature of reaction, reaction velocity 0.1～5.0h
-1, hydrogen-oil ratio 500～5000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01111438XA CN1136298C (en) | 2001-03-09 | 2001-03-09 | Catalyst for producing middle fraction from Fischer-Tropsch synthetic heavy hydrocarbon and its prepn and use |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01111438XA CN1136298C (en) | 2001-03-09 | 2001-03-09 | Catalyst for producing middle fraction from Fischer-Tropsch synthetic heavy hydrocarbon and its prepn and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1374375A CN1374375A (en) | 2002-10-16 |
| CN1136298C true CN1136298C (en) | 2004-01-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB01111438XA Expired - Lifetime CN1136298C (en) | 2001-03-09 | 2001-03-09 | Catalyst for producing middle fraction from Fischer-Tropsch synthetic heavy hydrocarbon and its prepn and use |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2850393B1 (en) * | 2003-01-27 | 2005-03-04 | Inst Francais Du Petrole | PROCESS FOR THE PRODUCTION OF MEDIUM DISTILLATES BY HYDROISOMERIZATION AND HYDROCRACKING OF FISCHER-TROPSCH PROCESS |
| CN102041067B (en) * | 2009-10-16 | 2014-07-23 | 中国石油化工股份有限公司 | Hydrofining method for Fischer-Tropsch oil |
| CN102441403B (en) * | 2010-10-13 | 2013-07-24 | 中国石油化工股份有限公司 | Method for preparing cobalt-based Fischer-Tropsch synthetic catalyst |
| CN103301872B (en) * | 2013-07-11 | 2015-08-05 | 中科合成油内蒙古有限公司 | A kind of unsulfided catalyst and preparation method thereof and application |
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