CN1204230C - Irregular hydrofining catalyst and its prepn - Google Patents
Irregular hydrofining catalyst and its prepn Download PDFInfo
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- CN1204230C CN1204230C CN 03149862 CN03149862A CN1204230C CN 1204230 C CN1204230 C CN 1204230C CN 03149862 CN03149862 CN 03149862 CN 03149862 A CN03149862 A CN 03149862A CN 1204230 C CN1204230 C CN 1204230C
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- hydrobon catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 230000001788 irregular Effects 0.000 title 1
- 229910052751 metal Inorganic materials 0.000 claims abstract description 57
- 239000002184 metal Substances 0.000 claims abstract description 57
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010937 tungsten Substances 0.000 claims abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 10
- 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 abstract description 10
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 10
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 9
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 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 5
- 239000002243 precursor Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 206010013786 Dry skin Diseases 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
- -1 aluminum alkoxide Chemical class 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910001648 diaspore Inorganic materials 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 1
- 229910001679 gibbsite Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005470 impregnation Methods 0.000 abstract description 3
- 239000000084 colloidal system Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 14
- 229910052794 bromium Inorganic materials 0.000 description 14
- 150000001993 dienes Chemical class 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000004480 active ingredient Substances 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 238000012913 prioritisation Methods 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000863032 Trieres Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a special-shaped hydrorefining catalyst and a preparation method thereof. The catalyst is prepared from 8 to 25% of molybdenum oxide, 1 to 9% of cobalt oxide, 1 to 5% of nickel oxide, 0.5 to 3% of tungsten oxide, 7 to 22% of subgroup IV metal, 0.1 to 5.0% of group IIIB metal, and an aluminum oxide carrier as the rest. The catalyst modifies aluminum oxide by leading in the subgroup IV metal and the group IIIB metal during carrier colloid forming, the aluminum oxide is dried and calcined in an air atmosphere to obtain the carrier containing the subgroup IV metal, and the catalyst is obtained through steps, such as impregnation in co-impregnation liquid of molybdenum, cobalt, nickel and tungsten as metals, etc. Compared with the prior art, the present invention has the characteristics of large catalyst specific surface area, high catalyst activity (high selectivity to monoene), low stacking density, bed layer pressure reduction, simple preparation process, etc. The present invention is suitable for the hydrorefining process of fractions of C6 to C8.
Description
Technical field:
The present invention relates to a kind of special-shaped Hydrobon Catalyst And Its Preparation Method, more particularly, it relates generally to and is used for pyrolysis gasoline secondary hydrogenation purified Catalysts and its preparation method.
Background technology:
In the last few years, along with the continuous progress of petroleum refining technology, hydrogen addition technology be applied in continuous expansion, as the core-catalyzer of hydrogen addition technology, the raising of its performance is the problem that oil refining enterprise is extremely paid close attention to.Be badly in need of developing the C of excellent property at present
6-C
8Cut fraction pyrolysis gasoline secondary hydrogenation catalyst for refining.
USP4059504 discloses and has been mixed with co-impregnated solution in the nickel nitrate aqueous solution a kind of Tungsten oxide 99.999 is added, and loads on specific surface area greater than 150 meters
2On/gram the aluminum oxide,, 457 ℃ of roastings 3 hours, obtain cobalt 2.5%, tungsten 8.0% through dry air.The specific surface area of this catalyzer is low to have caused catalyst activity low, and therefore, when handling pyrolysis gasoline, colloid is easily attached on the catalyzer, coking easily, and catalyst life is shorter.
The document that one piece of introduction " pyrolysis gasoline two sections LY-8602 catalyzer industrial production and application " arranged in " Chinese Appropriate technology achievement storehouse ", this catalyzer adopts γ-Al
2O
3Be carrier, MoO
3With CoO be active ingredient, this catalyzer have lower physical strength (≮ 40N/mm), impacted by hydrogen or during the oil-feed fluctuation, cause the broken and active of catalyzer to descend easily.
The document of another piece introduction " pyrolysis gasoline one, secondary hydrogenation cobalt Mo-Ni catalyst " is arranged in " in because of Appropriate technology achievement storehouse ", and this secondary hydrogenation catalyzer is with γ-Al
2O
3+ TiO
2Be carrier, this TiO
2When becoming glue, introduces in aluminum oxide, with MoO
3, CoO and NiO be active ingredient, but the bulk density of this catalyzer (＞1.0) is higher relatively, increases the expense of one-time pad catalyzer; Adopt the two-step approach dipping during metal impregnation, make the step of preparation catalyzer complicated more, manufacturing cost strengthens.
Summary of the invention:
The objective of the invention is to overcome the shortcoming of prior art, a kind of special-shaped Hydrobon catalyst is provided.
Another object of the present invention is for providing a kind of preparation method of special-shaped Hydrobon catalyst.
First purpose of the present invention is achieved in that a kind of special-shaped Hydrobon catalyst, form by the carrier that contains IV subgroup metal and IIIB family metal and molybdenum, cobalt, nickel, tungsten active constituent, each component content weight percent is: molybdenum oxide 8～25%, oxidation bores 1～9%, nickel oxide 1～5%, Tungsten oxide 99.999 0.5～3%, IV subgroup metal 7～22%, IIIB family metal 0.1～5.0%, all the other are alumina supporters.
First purpose of the present invention can also realize with such prioritization scheme: molybdenum oxide 10～23%, cobalt oxide 2～5%, nickel oxide 1.5～3.5%, Tungsten oxide 99.999 0.5～3%, IV subgroup metal 10～17%, the IIIB family metal 0.2～3.0%, all the other are carrier.
First purpose of the present invention can also realize with such prioritization scheme: described IV subgroup metal can be a kind of or certain two kinds the mixture among Ti, Zr, the Hf.
First purpose of the present invention can also realize with such prioritization scheme: described IIIB family metal can be a kind of or certain two kinds the mixture among Sc, Y, the La.
Second purpose of the present invention is achieved in that a kind of preparation method of special-shaped Hydrobon catalyst, and its preparation process is:
(1) when preparation aluminum oxide precursor, introduces superpolymer, IV subgroup metal and IIIB family metal, and add extrusion aid therein;
(2) material that (1) is obtained places kneading machine, do and mix, add the aqueous solution that contains materials such as peptizing agent, expanding agent then, carry out wet mixing, mixed material is put into the forcing machine hopper, can obtain containing of different shape of wet carrier by special orifice plate;
(3), obtain containing the carrier of IV subgroup metal and IIIB family metal with dry 2～14 hours, 400～700 ℃ following roastings 2～8 hours in air atmosphere of the carrier that is shaped;
(4) (3) are obtained containing the carrier of IV subgroup metal and IIIB family metal, through containing the ammonia co-impregnated solution dipping of molybdenum, cobalt, nickel and tungsten active constituent, at room temperature carry out health, 100～120 ℃ of dryings, 400～700 ℃ of air activate 2.5～8.5 hours down, obtain catalyzer.
Second purpose of the present invention can also adopt such prioritization scheme to realize; The hole of described special orifice plate is the tooth sphere.
Described superpolymer may be Mierocrystalline cellulose, polyacrylamide, polyoxyethylene glycol, polyvinyl alcohol one or more a mixture wherein, divides after dry in air atmosphere, the roasting and takes off; The precursor of described aluminum oxide can be the purity for preparing with sodium metaaluminate one carbonic acid gas or aluminum alkoxide hydrolysis method greater than 60% book diaspore, pseudo-boehmite, the most handy sodium metaaluminate one carbonic acid gas be prepared into and purity greater than 65% boehmite, pseudo-boehmite; Described co-impregnated solution is meant the ammonia soln that contains molybdenum, cobalt, nickel, tungsten, normally makes co-impregnated solution by ammonium molybdate and Xiao Suangu, cobaltous acetate, cobaltous dihydroxycarbonate and nickelous nitrate, nickelous acetate, basic nickel carbonate, wolframic acid etc. with ammoniacal liquor.The method that is shaped in the supported catalyst preparation process with compressing tablet, balling-up or method such as extrude.The IV subgroup metal and the IIIB family metal of above-mentioned introducing support of the catalyst are referred to as properties-correcting agent.So-called tooth sphere is meant the sphere that is shaped as of carrier, and the surface has several teeth.
The beneficial effect of special-shaped Hydrobon catalyst of the present invention is: specific surface area is big, activity is high, physical strength is high, bulk density is low, the preparation method is simple.
Table 1 has provided the comparative analysis data of three kinds of shape catalyzer, wherein is respectively cylindrical, the cloverleaf pattern of industrial general usefulness for 1～No. 2, No. 3 tooth ball shapes for the present invention's employing.The evaluation of catalyzer is carried out on the 100ml small hydrogenation device.Adopting pyrolysis gasoline to generate oil for one section be raw material, and the catalyzer hydrogenated gasoline (bromine valency＜0.5gBr/100g oil) that at first usefulness contains 2.0% dimethyl disulphide under 320 ℃ of hydrogen carried out prevulcanized 8 hours, advanced stock oil then and reacted.Reaction conditions: hydrogen dividing potential drop 4.0MPa, volume space velocity are 3.0 hours
-1, hydrogen to oil volume ratio 280～320: 1, temperature of reaction 250.Generate oil and mainly carry out the analysis of bromine valency and diene number, analytical results sees Table 1.Table 1 central hole structure data, be to adopt cryogenic nitrogen absorption BET method to measure: the ZQJ intelligence granule strength trier that the physical strength of catalyzer adopts Dalian Device Diagnostic device factory to produce is measured.
The data of table 1 show, the shape difference of catalyzer, and pore volume, specific surface area change little, but the physical strength of catalyzer is obviously different, and cloverleaf pattern is better than the intensity of cylinder shape catalyst, and the intensity of tooth spherical catalyst is much better than other two kinds of shapes.In addition, from analytical results also as can be seen, the tooth spherical catalyst has active preferably, especially in the industrial reactor of packing into, have filling evenly, do not have short circuit, channeling, fall thereby reduce bed layer pressure, overcome the shortcoming that increase falls in cylindrical and cloverleaf pattern catalyst bed stressor layer.
Table 2 and table 3 have provided the technique effect of catalyzer of the properties-correcting agent of different content.
Table 1
The rerum natura of different shapes catalyzer and evaluation result
| Numbering | 1 | 2 | 3 | |
| Catalyst shape | Cylindrical | Cloverleaf pattern | The tooth sphere | |
| The catalyzer rerum natura | Specific surface area, rice 2/ gram | 327 | 320 | 328 |
| Pore volume, milliliter/gram | 0.38 | 0.39 | 0.38 | |
| Physical strength, newton/grain | 14.5 | 15.7 | 49 newton/grains | |
| Size, millimeter | Diameter 1.6 | External diameter 1.6 | Diameter 2.5 | |
| Stock oil | The bromine valency, gram bromine/100 gram oil | 22.1 | ||
| Diene number, gram iodine/100 gram oil | 1.79 | |||
| Generate oil | The bromine valency, gram bromine/100 gram oil | 0.39 | 0.23 | 0.19 |
| Diene number, gram iodine/100 gram oil | 1.0 | 1.0 | 1.0 | |
Table 2
Catalyzer rerum natura and evaluation result
| Numbering | A | B | C | D | E | |
| The properties-correcting agent add-on | 0 | 6.0 | 13 | 17 | ||
| The catalyzer rerum natura | Specific surface area, rice 2/ gram | 235 | 229 | 219 | 210 | 150 |
| Pore volume, milliliter/gram | 0.40 | 0.45 | 0.48 | 0.51 | ||
| Physical strength, newton/grain | 61.0 | 53.2 | 48.5 | 34.0 | ||
| Stock oil | The bromine valency, gram bromine/100 gram oil | 22.1 | ||||
| Diene number, gram iodine/100 gram oil | 1.79 | |||||
| Generate oil | The bromine valency, gram bromine/100 gram oil | 1.60 | 0.90 | 0.18 | 0.65 | 0.61 |
| Diene number, gram iodine/100 gram oil | 0.10 | 0.00 | 0.00 | 0.01 | 0.03 | |
Table 3
Catalyzer is formed and evaluation result
| Numbering | F | G | H | I | J | K | L | M | N | |
| Molybdenum oxide, weight % | 9 | 17 | 22 | 10～23 | 10～23 | |||||
| Cobalt oxide, weight % | 2～5 | 1.2 | 2.5 | 4.5 | 2～5 | |||||
| Nickel oxide, weight % | 1.5～3.5 | 1.5～3.5 | 1.0 | 1.9 | 2.9 | |||||
| Tungsten oxide 99.999, weight % | 0.8 | 0.8 | 0.8 | |||||||
| Stock oil | The bromine valency, gram bromine/100 gram oil | 22.1 | ||||||||
| Diene number, gram iodine/100 gram oil | 1.79 | |||||||||
| Generate oil | The bromine valency, gram bromine/100 gram oil | 1.90 | 0.17 | 1.12 | 1.62 | 0.17 | 1.02 | 1.55 | 0.20 | 1.07 |
| Diene number, gram iodine/100 gram oil | 0.12 | 0.00 | 0.05 | 0.16 | 0.00 | 0.10 | 0.15 | 0.00 | 0.09 | |
Embodiment:
Below in conjunction with embodiment the present invention is further described.
Example 1
(1) when preparation aluminum oxide precursor, introduces superpolymer, IV subgroup metal and IIIB family metal, and add extrusion aid therein;
(2) material that (1) is obtained places kneading machine, do and mix, add the aqueous solution that contains materials such as peptizing agent, expanding agent then, carry out wet mixing, mixed material is put into the forcing machine hopper, can obtain containing of different shape of wet carrier by special orifice plate;
(3), obtain containing the carrier of IV subgroup metal and IIIB family metal with dry 2～14 hours, 400～700 ℃ following roastings 2～8 hours in air atmosphere of the carrier that is shaped;
(4) (3) are obtained containing the carrier of IV subgroup metal and IIIB family metal, through containing the ammonia co-impregnated solution dipping of molybdenum, cobalt, nickel and tungsten active constituent, at room temperature carry out health, 100～120 ℃ of dryings, 400～700 ℃ of air activate 2.5～8.5 hours down, obtain the tooth spherical catalyst.
Example 2
Special-shaped Hydrobon catalyst, be the carrier of properties-correcting agent and be active ingredient with IV subgroup metal and IIIB family metal with molybdenum, cobalt, nickel, tungsten, each component content weight percent is: molybdenum oxide 9%, cobalt oxide 5%, nickel oxide 2%, Tungsten oxide 99.999 1%, the IV subgroup metal 10%, HIB family metal 2%, all the other are alumina supporters.
Example 3
Special-shaped Hydrobon catalyst, be the carrier of properties-correcting agent and be active ingredient with IV subgroup metal and IIIB family metal with molybdenum, cobalt, nickel, tungsten, each component content weight percent is: molybdenum oxide 15%, oxidation bores 2%, nickel oxide 4.5%, Tungsten oxide 99.999 2.5%, the IV subgroup metal 14%, IIIB family metal 4.5%, all the other are alumina supporters.
Example 4
Special-shaped Hydrobon catalyst, be the carrier of properties-correcting agent and be active ingredient with IV subgroup metal and IIIB family metal with molybdenum, cobalt, nickel, tungsten, each component content weight percent is: molybdenum oxide 24%, oxidation bores 8%, nickel oxide 2%, Tungsten oxide 99.999 1%, the IV subgroup metal 20%, IIIB family metal 2.5%, all the other are alumina supporters.
Claims (10)
1. special-shaped Hydrobon catalyst, it is characterized in that: it is made up of the carrier that contains IV subgroup metal and IIIB family metal and molybdenum, cobalt, nickel, tungsten active constituent, each component content weight percent is: molybdenum oxide 8～25%, oxidation bores 1～9%, nickel oxide 1～5%, Tungsten oxide 99.999 0.5～3%, IV subgroup metal 7～22%, IIIB family metal 0.1～5.0%, all the other are alumina supporters.
2. special-shaped Hydrobon catalyst as claimed in claim 1, it is characterized in that: the consisting of of the carrier of described IV subgroup metal and IIIB family metal and molybdenum, cobalt, nickel, tungsten active constituent: molybdenum oxide 10～23%, cobalt oxide 2～5%, nickel oxide 1.5～3.5%, Tungsten oxide 99.999 0.5～3%, IV subgroup metal 10～17%, the IIIB family metal 0.2～3.0%, all the other are aluminum oxide.
3. special-shaped Hydrobon catalyst as claimed in claim 1 or 2, described IV subgroup metal can be a kind of or certain two kinds the mixture among Ti, Zr, the Hf.
4. special-shaped Hydrobon catalyst as claimed in claim 1 or 2, described IIIB family metal can be a kind of or certain two kinds the mixtures among Sc, Y, the La.
5. special-shaped Hydrobon catalyst as claimed in claim 1 or 2 is characterized in that: described special-shaped Hydrobon catalyst be shaped as the tooth sphere.
6. the preparation method of a special-shaped Hydrobon catalyst is characterized in that its adopts to be prepared as follows step:
(1) when preparation aluminum oxide precursor, introduces superpolymer, IV subgroup metal and IIIB family metal, and add extrusion aid therein;
(2) material that (1) is obtained places kneading machine, do and mix, add the aqueous solution that contains materials such as peptizing agent, expanding agent then, carry out wet mixing, mixed material is put into the forcing machine hopper, can obtain containing of different shape of wet carrier by special orifice plate;
(3), obtain containing the carrier of IV subgroup metal and IIIB family metal with dry 2～14 hours, 400～700 ℃ following roastings 2～8 hours in air atmosphere of the carrier that is shaped;
(4) (3) are obtained containing the carrier of IV subgroup metal and IIIB family metal, through containing the ammonia co-impregnated solution dipping of molybdenum, cobalt, nickel and tungsten active constituent, at room temperature carry out health, 100～120 ℃ of dryings, 400～700 ℃ of air activate 2.5～8.5 hours down, obtain catalyzer.
7. the preparation method of special-shaped Hydrobon catalyst as claimed in claim 6, the hole that it is characterized in that described special orifice plate is the tooth sphere.
8. the preparation method of special-shaped Hydrobon catalyst as claimed in claim 6, it is characterized in that described aluminum oxide precursor, be meant boehmite, pseudo-boehmite, promise diaspore, unformed aluminium hydroxide or gibbsite with sodium metaaluminate-carbonic acid gas or the preparation of aluminum alkoxide hydrolysis method.
9. the preparation method of special-shaped Hydrobon catalyst as claimed in claim 6 is characterized in that: described in air atmosphere, and 500～600 ℃ of dry 4～12 hours, roasting.
10. the preparation method of special-shaped Hydrobon catalyst as claimed in claim 6, it is characterized in that: described co-impregnated solution, being meant the inorganic aqueous solution that contains molybdenum, cobalt, nickel, tungsten, is to be made by molybdenum oxide, ammonium molybdate and Xiao Suangu, cobaltous acetate, cobaltous dihydroxycarbonate and nickelous nitrate, nickelous acetate, basic nickel carbonate and wolframic acid and ammoniacal liquor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03149862 CN1204230C (en) | 2003-07-30 | 2003-07-30 | Irregular hydrofining catalyst and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03149862 CN1204230C (en) | 2003-07-30 | 2003-07-30 | Irregular hydrofining catalyst and its prepn |
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| Publication Number | Publication Date |
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| CN1468940A CN1468940A (en) | 2004-01-21 |
| CN1204230C true CN1204230C (en) | 2005-06-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 03149862 Expired - Lifetime CN1204230C (en) | 2003-07-30 | 2003-07-30 | Irregular hydrofining catalyst and its prepn |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101724447B (en) * | 2008-10-29 | 2013-03-20 | 中国石油化工股份有限公司 | Method for producing gasoline blend component with high octane value by using cracking gasoline heavy fractions |
| CN101497044B (en) * | 2009-03-10 | 2011-05-11 | 北京高新利华催化材料制造有限公司 | Teeth spherical heavy oil hydrotreating catalyst and preparation method thereof |
| CN103160312A (en) * | 2011-12-15 | 2013-06-19 | 中国石油天然气股份有限公司 | Application of tooth-spherical distillate oil hydrogenation catalyst |
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