CN1015640B - Supported non-noble metal hydrocracking catalyst - Google Patents
Supported non-noble metal hydrocracking catalystInfo
- Publication number
- CN1015640B CN1015640B CN 88103069 CN88103069A CN1015640B CN 1015640 B CN1015640 B CN 1015640B CN 88103069 CN88103069 CN 88103069 CN 88103069 A CN88103069 A CN 88103069A CN 1015640 B CN1015640 B CN 1015640B
- Authority
- CN
- China
- Prior art keywords
- cross
- linked
- catalyst
- clay
- noble metal
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 24
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 11
- 239000004927 clay Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000007654 immersion Methods 0.000 claims abstract description 4
- 238000004898 kneading Methods 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 241000353097 Molva molva Species 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 6
- 239000010953 base metal Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 102000040350 B family Human genes 0.000 claims description 4
- 108091072128 B family Proteins 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 19
- 239000011707 mineral Substances 0.000 abstract description 19
- 239000002808 molecular sieve Substances 0.000 abstract description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 7
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 238000004939 coking Methods 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000011229 interlayer Substances 0.000 abstract 1
- 230000000737 periodic effect Effects 0.000 abstract 1
- 229910021647 smectite Inorganic materials 0.000 description 23
- 150000002500 ions Chemical class 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000011148 porous material Substances 0.000 description 7
- 239000011734 sodium Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910052902 vermiculite Inorganic materials 0.000 description 3
- 239000010455 vermiculite Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 101000809257 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 4 Proteins 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 102100038463 Ubiquitin carboxyl-terminal hydrolase 4 Human genes 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001919 chlorite Inorganic materials 0.000 description 2
- 229910052619 chlorite group Inorganic materials 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010335 hydrothermal treatment Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- 101100001642 Caenorhabditis elegans amt-1 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 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 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- -1 aluminium chlorohydroxide Chemical compound 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
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- Catalysts (AREA)
Abstract
A non-noble metal hydrocracking catalyst with carrier containing cross-linked clay is composed of cross-linked regular interlayer mineral clay and alumina, and its active component is non-noble metal element from VIB group and/or VII group in periodic table. The hydrocracking catalyst can be prepared by an immersion method or a kneading method, has the characteristics that the selectivity of a middle distillate product is kept unchanged when the reaction temperature is increased, the gas generation amount in the product is small, and the coking condition is similar to that of a catalyst taking a conventional molecular sieve as an acidic component, and is suitable for mild hydrocracking.
Description
The invention relates to a kind of loaded catalyst product that is used for hydro carbons processing and preparation method thereof.Exactly, be supported non-noble metal hydrocracking catalyst and preparation method thereof about containing crosslinked regular interbed mineral clay in a kind of carrier.
Cross-linked clay is as a kind of support of the catalyst, and it has the wide aperture that helps the intramolecularly diffusion, the active value volume and range of product high, crosslinked " pillar " of macromolecular cleavage is easy to advantages such as adjustment, uses in the hydrocracking catalyst field at present.For example: USP4, reported al-cross-linked bentonite-10%Al with 0.5%Pd/ in 176,090
2O
3During as hydrocracking catalyst, when hydrogen pressure 10.34 MPas (gauge pressure), air speed 1.0
-1, hydrogen/oil 880 condition under, the stock oil that boiling point can be higher than 357 ℃ transforms 16%; USP4 has reported in 579,832 with the crosslinked smectite that contains transition metal such as Mo, Cr, Ni, Co, W and as catalyzer n-dodecane has been carried out hydrocracking, under 13.79 MPas (gauge pressure), 350 ℃ condition, and C
5～C
8The yield of stable hydrocarbon reaches more than 40%; EP0180513A
1In also reported with aluminium cross-linked mica polynite-super-stable Y molecular sieves-Al
2O
3Composite carrier load base metal (as Mo, Ni) as hydrocracking catalyst in order to production middle distillate oil.
According to reports, at present the cross-linked clay of the hydrocracking catalyst that is useful on all is to be the crosslinked smectite class clay that raw material is made with smectite class clay.Smectite class clay is a single-storeyed mineral structure, and its unit layer is only by 2: 1 a layers of formation, its basal spacing (d
001) be 0.90～1.50nm(natural wind dry sample), the chemical general formula of its single cell is { Ca, Na }
x(Al, Mg)
VI 4[Si, Al, Fe]
VI 8O
20(OH)
4, promptly its component part is: hexa-coordinate ion, four-coordination ion and electrobalance positively charged ion (or it is for the set positively charged ion, or is exchangeable cation).Such clay comprises that mainly polynite, wilkinite, the Hunk of natural or synthetic take off stone, beidellite, vermiculite etc.By crosslinking reaction organic amine or inorganic metal hydroxy polymer are inserted in adjacent 2: 1 layers of two of smectite class clay, and 2: the 1 layers of support that will therefore expand, fix, this has just obtained crosslinked smectite.The greatest drawback of crosslinked smectite is that its thermostability and hydrothermal stability are poor, under the condition of high temperature or hydrothermal treatment consists, upholder can leave 2: 1 layers and go up original point of suppon and come off, and the laminate structure of smectite class clay itself also can Yin Gaowen or hydrothermal treatment consists and destroyed.According to reports, be difficult to stand 250～500 ℃ thermal treatment (USP4,367,163) with organic amine and the crosslinked cross-linked montmorillonite of making of polynite; Also only can stand 550 ℃ thermal treatment (USP4,216,188, USP4,238,364) with inorganic metal hydroxy polymer and the crosslinked crosslinked smectite of making of smectite class clay; Promptly use the comparatively stable crosslinked smectite of preparing of improving one's methods also can stand 676 ℃, 5 pounds steam-treated 8 hours (USP4,176,090, USP4,248,739).If through 730 ℃ of steam-treated 4 hours, then specific surface will lose 90% with this type of cross-linked clay, pore volume will lose 80%, and little anti-lytic activity will be reduced to 30%(Occelli, M.L., I﹠amp by original 80%; EC, Prod.Res﹠amp; Dev., 22,553,1983).
For overcoming the above-mentioned deficiency of crosslinked smectite class clay, at EP197012A
2In reported a class of developing with another kind of clay catalytic material and had macropore and the good novel cross-linked clay of high-temperature hydrothermal stability, promptly crosslinked regular interbed mineral clay.Such cross-linked clay is to be its unit layer with the not expandable layer in the regular interbed mineral clay structure, is that pillar constitutes to insert inorganic oxide between the expandable layer in this rule interbed mineral clay structure, that formed through roasting by the inorganic metal hydroxy polymer.The clay of rule interbed mineral structure is meant a class crystalline mineral clay that is formed according to mode interleaved, the ordered arrangement of public adjacent 2: 1 clay seams by expandable and nondistensible two kinds of individual layer mineral clays, its unit layer is by two 2: 1 layers and these two 2: 1 layers intermediary set positively charged ions formations, its basal spacing (d
001) being not less than 1.70nm, the component part of its single cell is: hexa-coordinate ion, four-coordination ion, set positively charged ion and exchangeable cation.The structure expression (dehydration back) that for example belongs to the rectorite leng of such clay is:
｛（Na
0.72K
0.02Ca
0.05）（Ca
0.24Na
0.07）｝
（Al
4.00Mg
0.02）
Ⅵ[Si
6.58Al
1.62]
ⅣO
22
Set positively charged ion exchangeable cation
Such clay mainly comprises mica-smectite (as: rectorite leng, Yun Mengshi, mica-polynite), illite-smectite, glaukonine-smectite, chlorite-smectite (as: hydroxyl cimita, Ke's chlorite), mica-vermiculite, kaolinite-smectite of natural and synthetic etc.Crosslinked regular interbed mineral structure clay has overcome the disadvantage of crosslinked in the past smectite class slime fever and hydrothermal stability difference, for example after 17 hours, structure does not collapse cross-linked rectorite substantially, interlamellar spacing remains unchanged substantially through 800 ℃, normal pressure, 100% steam-treated, specific surface keeps 70%, the little anti-lytic activity of solar oil keeps 90%.
Up to now, do not see that useful crosslinked regular interbed mineral clay is as the report of hydrocracking catalyst on the document, purpose of the present invention just is to provide supported non-noble metal hydrocracking catalyst that contains crosslinked regular interbed mineral clay in a kind of carrier and preparation method thereof.
The carrier of hydrocracking catalyst provided by the invention is by accounting for vehicle weight 5～30%, the crosslinked regular interbed mineral clay of best 10～15% aluminum oxide and surplus is formed, active ingredient can be and accounts for catalyst weight 10～45%(in oxide compound) VI B family or VIII family base metal element, also can be and account for catalyst weight 8～30%(in oxide compound) VI B family element with account for catalyst weight 2～15%(in oxide compound) the composition of VIII B family base metal element.
Hydrocracking catalyst provided by the invention can load on the mixture of aluminum oxide precursor and crosslinked regular interbed mineral clay by pickling process or the kneading method precursor with active ingredient, then through moulding, drying, 450～650 ℃ of roastings 2～4 hours and make.Forming step also can carry out before dipping.
The precursor of said aluminum oxide can be aluminium hydroxide, pseudo-boehmite, aluminium colloidal sol etc. among the present invention.Crosslinked regular interbed mineral clay is to carry out crosslinking reaction by clay with regular interbed mineral structure and inorganic metal hydroxy polymer to make, (for example according to EP197012A
2Described in method).Clay with regular interbed mineral structure is meant mica-smectite (as: rectorite leng, Yun Mengshi, mica-polynite) of comprising natural and synthetic, illite-smectite, glaukonine-smectite, chlorite-smectite (as: hydroxyl cimita, Ke's chlorite), mica-vermiculite, kaolinite-smectite etc., form according to mode interleaved, the ordered arrangement of public adjacent 2: 1 clay seams by expandable and nondistensible two kinds of individual layer mineral clays, basal spacing (d
001) be not less than the crystalline mineral clay of 1.70nm.The precursor of active ingredient can be to contain these non-noble metal various salts, as nitrate, carbonate, hydrochloride, acetate etc., and contains these non-noble metal various ammonium salts, as ammonium paramolybdate, ammonium metawolframate etc.The immersion condition that adopts can be: admittedly liquid/be 2～5: 1, best 4: 1; Normal temperature; Flooded best 4 hours 2～6 hours; Steeping fluid pH1～4.5, best 3～4.5.
The middle distillate selectivity of product remained unchanged when hydrocracking catalyst provided by the invention had temperature of reaction and raises, gas generating amount is few in the product, the coking situation is similar to conventional molecular sieve is the characteristics of acidic components catalyzer, is applicable to the mild hydrocracking of hydro carbons.
Following example will be to Catalysts and its preparation method provided by the invention in advance with further instruction.
Example 1
With the rectorite leng is raw material, according to EP197012A
2Described in method prepare aluminum cross-linked rectorite.
With 20 kilograms of 1 kilogram of natural calcium type rectorite lengs, deionized water and exchange capacity is that the strongly acidic styrene of 4 milligramequivalent/grams is that sodium type Zeo-karb mixes for 3 kilograms, stirs standing over night 8 hours.Take out soil particle diameter that the upper strata suspends less than 2 microns clay slurry, recording its solid content is 2.29 heavy %.With 0.2 moles of NaOH and 0.2 mole of AlCl
3Reaction is after aged at room temperature 6 days and dilute one times of polymerization aluminium chlorohydroxide that makes (its concentration be 33.3 mmole aluminium/liter) and be linking agent, with the feed ratio of every gram soil clay slurry is added in the linking agent by 3.29 mmole aluminum crosslinkers, crosslinking reaction is 30 minutes under stirring at normal temperature, uses 3%NH during reaction
4The pH value of OH control solution makes it to remain on 4～6, continues to keep pH value of solution 4～6 at room temperature to leave standstill then aging 24 hours, more after filtration, wash to there not being Cl
-, roasting promptly got aluminum cross-linked rectorite in 2 hours in the 110 ℃ of dryings, 650 ℃ of air.
It is as follows to record its scantlings of the structure with conventional x-ray diffraction method: bed thickness is 2.00～2.10nm, basal spacing (d
001) not being all 2.70～3.10nm with water content, interlamellar spacing is 0.60～1.00nm.Record its main chemical constitution with standard chemical process and see Table 1,2.Record its specific surface, pore volume and pore distribution data with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature and see Table 2.
Example 2～4
Contain the preparation of the hydrocracking catalyst of aluminum cross-linked rectorite in the carrier.
Get cross-linked rectorite 14 grams of preparing in the example 1, the mixed solution that adds 4.4 gram pseudo-boehmites (refinery, Chang Ling Industrial products), 0.6 gram sesbania powder (refinery, Chang Ling Industrial products) and 0.24 milliliter of nitric acid (chemical pure) and 11.2 ml distilled waters, mix the moulding of pinching bar, through 120 ℃ of dryings after 1 hour, get the carrier of 15 grams after the moulding, admittedly restrain Ni(NO with containing 48 with 4: 1 ratio of liquid/be
3)
26H
2O(Beijing 57601 chemical plant products, chemical pure, content is no less than 98.0%) and 24.3 milliliters of ammonium metatungstate solutions (wherein contain WO
31.002 grams per milliliter) and use 10%NH
4The steeping fluid that OH transfers to pH4.2 flooded 4 hours at normal temperatures, through 1 hour, 500 ℃ roastings of 120 ℃ of dryings 3 hours, promptly got 8.9%Ni0-23%WO then
3Cross-linked rectorite-15%Al
2O
3Catalyzer, the called after catalyst A.
Get cross-linked rectorite 12.8 grams of preparing in the example 1, add 4 gram pseudo-boehmites (refinery, Chang Ling Industrial products), 7.8 gram Ni(Ac)
24H
2O(Beijing Chemical Plant product, analytical pure, content is more than 98.0%), 5.9 gram ammonium metawolframate (Zigong Hard Alloy Foundry product, AMT-1 level, WO
3Content is more than 99.5%), the mixing solutions of 0.6 gram sesbania powder (refinery, Chang Ling Industrial products) and 0.2 milliliter of nitric acid (chemical pure) and 8 ml distilled waters, kneading and compacting through 1 hour, 500 ℃ roastings of 120 ℃ of dryings 3 hours, promptly gets 10%NiO-24%Wo
3/ cross-linked rectorite-15%Al
2O
3Catalyzer, the called after catalyst B.
By the preparation method of catalyst B,, make 10%NiO-24%MoO with the ammonium metawolframate in 6.7 gram ammonium paramolybdates (content is more than 99.0% for Changsha reagent chemical plant product, analytical pure) the replacement catalyst B
3/ cross-linked rectorite-15%Al
2O
3Catalyzer, called after catalyzer C.
Record the basal spacing (d of catalyst A, B, C with conventional x-ray diffraction method and B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature
001), the data of specific surface and pore volume see Table 3.
Comparative Examples
By the preparation method of catalyst B, with 14 gram γ-Al
2O
3, 6 grams two hand over two roasting REY molecular sieve (Zhou village catalyst plant Industrial products, SiO
2/ Al
2O
3=5.1, RE
2O
319.7%, Na
2O1.5%), 8.3 gram Ni(Ac)
24H
2The mixing solutions of O, 7.3 gram ammonium metawolframates, 0.4 gram sesbania powder and 0.24 milliliter of nitric acid and 11.2 ml distilled waters is prepared 10%NiO-24%Wo
3/ γ-Al
2O
3-30%REY catalyzer, called after catalyzer D.
Example 5
The non-precious metal catalyst that contains cross-linked rectorite in the carrier provided by the invention is applicable to mild hydrocracking, has the advantages that the product gas growing amount is few, the middle distillate selectivity of product remained unchanged when temperature of reaction raise.
On 100 milliliters of small hydrogenation devices, VGO is raw material (performance sees Table 4) with triumph, and catalyst A, comparative sample D and the U.S. are united the base metal commercial catalysts that the oily hydrocracking catalyst HC-22(of company contains molecular sieve) activity in mild hydrocracking process under the differential responses temperature estimates.60 milliliters of hydrodenitrogenation catalysts are equipped with on reactor top, and 40 milliliters of catalyzer to be evaluated (A or B or D or HC-22) are adorned in the bottom.The evaluation response condition is: hydrogen pressure 7.06 MPas, air speed 0.8(is refining)/the 1.2(cracking), hydrogen to oil volume ratio is 800: 1.Evaluation result sees Table 5 and table 6.The relation of middle bottoms product selectivity and temperature of reaction is seen Fig. 1, curve among the figure (1) is for containing the catalyst A or the B of cross-linked rectorite in the carrier provided by the invention, curve (2) is comparative catalyst D, curve (3) the non-noble metal hydrocracking catalyst HC-22 that contains molecular sieve that oily company produces for the U.S. unites.
Example 6
The coking situation that contains the non-precious metal catalyst of cross-linked rectorite in the carrier provided by the invention is similar to the catalyzer that conventional molecular sieve is acidic components.
Catalyst A, D, the HC-22(U.S. are united oily company hydrocracking catalyst) turned round respectively 300 hours from 355 ℃ to 395 ℃ by the reaction conditions in the example 5 after, carry out the carbon deposit analysis with sulphur carbon analyzer (U.S. Leco company product), the results are shown in Table 7.
Table 1
Main chemical constitution Na
2O Fe
2O
3Al
2O
3SiO
2
Content, heavy % 1.3～2.0 0.29 45.5 47.6
Table 2
The project specific surface, pore volume, pore distribution, %
＜5.0 5.0～ 10.0～ 15.0～
Sample m
2/ g ml/g nm 10.0nm 15.0nm 20.0nm
Fresh sample 174 0.17 66.9 22.8 9.7 0.6
800 ℃ of normal pressure 100% water
Steam treatment is after 17 hours 129 0.20 43.8 21.5 15.9 18.8
Table 3
Example 234
The preparation method is flooded Hun Pinch Hun Pinch
Loaded metal, NiO 8.9 10.0 10.0
Heavy % WO
323.0 24.0/
MoO
3/ / 24.0
Vehicle group becomes cross-linked rectorite-15%Al
2O
3The same
Basal spacing is after 120 ℃ 2.78 2.82 2.88
Behind 500 ℃ of the nm 2.75 2.79 2.81
Specific surface, m
2/ g 141 138 112
Pore volume, ml/g 0.11 0.12 0.11
Catalyzer numbering A B C
Table 4
d
0.9024
Full nitrogen, ppm 1300
Alkali nitrogen, ppm 576
Sulphur, heavy % 0.64
The bromine valency, gram bromine/100 grams 4.4
Aniline point, ℃ 90.6
Zero pour, ℃+39
Viscosity (100 ℃), centistoke 7.74
BMCI value 40.40
Boiling range, ℃
Initial boiling point 285
10% 372
30% 422
50% 448
70% 470
90% 507
Do 564
Table 7
Catalyzer coke content, heavy %
A:Ni-W/ cross-linked rectorite-15%Al
2O
36.4
D：Ni-W/γ-Al
2O
3-30%REY 9.8
HC-22: contain molecular sieve, load base metal 5.3
Claims (9)
1, the loaded catalyst that contains cross-linked clay in a kind of carrier, it is characterized in that its carrier is made up of the cross-linked rectorite of aluminum oxide that accounts for vehicle weight 5～30% and surplus, active ingredient is VI B family element that accounts for catalyst weight 8～30% (in oxide compound) and the composition that accounts for the VIII family base metal element of catalyst weight 2～15% (in oxide compound).
2,, it is characterized in that the aluminum oxide in its carrier preferably accounts for 10～15% of vehicle weight according to the described catalyzer of claim 1.
3, a kind of method for preparing claim 1 or 2 described catalyzer, it is characterized in that this catalyzer can load on the mixture of aluminum oxide precursor and cross-linked rectorite by pickling process or the kneading method precursor with active ingredient, make through moulding, drying, 450～650 ℃ of roastings 2～4 hours then, forming step also can carry out before dipping.
4, according to the described preparation method of claim 3, the precursor that it is characterized in that said aluminum oxide can be aluminium hydroxide, pseudo-boehmite, aluminium colloidal sol.
5,, it is characterized in that said cross-linked rectorite is by rectorite leng and inorganic metal hydroxy polymer crosslinking reaction and make according to the described preparation method of claim 3.
6, according to the described preparation method of claim 3, the precursor that it is characterized in that said active ingredient can be to contain these non-noble metal various salts, as nitrate, carbonate, hydrochloride, acetate etc., and contain these non-noble metal various ammonium salts, as ammonium paramolybdate, ammonium metawolframate etc.
7,, it is characterized in that said immersion condition is: Gu liquid/2～5 according to the described preparation method of claim 3: 1, normal temperature flooded steeping fluid pH1～4.5 2～6 hours.
8,, it is characterized in that said immersion condition is according to claim 3 or 7 described preparation methods: Gu liquid/4: 1, normal temperature flooded steeping fluid pH3～4.5 4 hours.
9, the loaded catalyst that contains cross-linked clay described in the claim 1 in the carrier is used for the mild hydrocracking of hydro carbons.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88103069 CN1015640B (en) | 1988-05-28 | 1988-05-28 | Supported non-noble metal hydrocracking catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88103069 CN1015640B (en) | 1988-05-28 | 1988-05-28 | Supported non-noble metal hydrocracking catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1038119A CN1038119A (en) | 1989-12-20 |
| CN1015640B true CN1015640B (en) | 1992-02-26 |
Family
ID=4832430
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88103069 Expired CN1015640B (en) | 1988-05-28 | 1988-05-28 | Supported non-noble metal hydrocracking catalyst |
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| CN (1) | CN1015640B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072708C (en) * | 1998-12-16 | 2001-10-10 | 中国石油化工集团公司 | Mild hydrocracking method |
| DE102008064648A1 (en) * | 2008-01-23 | 2010-05-20 | Tradium Gmbh | Reaction vessel for the production of metal powders |
| WO2013054282A1 (en) * | 2011-10-11 | 2013-04-18 | The South African Nuclear Energy Corporation Limited | Treatment of chemical feedstocks |
| CN103952574B (en) * | 2014-04-30 | 2015-08-19 | 中国科学院过程工程研究所 | A kind of method utilizing magnesium metal reduction anhyd chromic chloride to produce high-purity metal chromium |
| CN111135819A (en) * | 2020-01-17 | 2020-05-12 | 福州大学 | Hydrocracking supported catalyst for inferior residual oil suspension bed and preparation method thereof |
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1988
- 1988-05-28 CN CN 88103069 patent/CN1015640B/en not_active Expired
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| Publication number | Publication date |
|---|---|
| CN1038119A (en) | 1989-12-20 |
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