CN1103009A - Preparing method for aluminium oxide carrier with double-hole - Google Patents
Preparing method for aluminium oxide carrier with double-hole Download PDFInfo
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- CN1103009A CN1103009A CN 93114901 CN93114901A CN1103009A CN 1103009 A CN1103009 A CN 1103009A CN 93114901 CN93114901 CN 93114901 CN 93114901 A CN93114901 A CN 93114901A CN 1103009 A CN1103009 A CN 1103009A
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- aluminum oxide
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- active agent
- aluminum
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- 238000000034 method Methods 0.000 title claims abstract description 31
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000006229 carbon black Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 claims abstract description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000013543 active substance Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- -1 Anions aluminium salt Chemical class 0.000 claims description 6
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 150000003138 primary alcohols Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 15
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 6
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract description 5
- 238000001125 extrusion Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000000295 fuel oil Substances 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 238000004898 kneading Methods 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 241000772415 Neovison vison Species 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical group [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 101000809257 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 4 Proteins 0.000 description 1
- 229910017318 Mo—Ni Inorganic materials 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- RUJBDQSFYCKFAA-UHFFFAOYSA-N Tofisopam Chemical compound N=1N=C(C)C(CC)C2=CC(OC)=C(OC)C=C2C=1C1=CC=C(OC)C(OC)=C1 RUJBDQSFYCKFAA-UHFFFAOYSA-N 0.000 description 1
- 102100038463 Ubiquitin carboxyl-terminal hydrolase 4 Human genes 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229960002501 tofisopam Drugs 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
A kind of method for preparing the catalyst carrier used in heavy oil hydrogenation and demetalization is adding carbon black and surfactant to two kinds of aluminium hydroxides with different properties, through kneading, column extrusion and forming process, then drying and at last the double porous aluminium oxide carrier is made up through roasting in the oxygen-bearing air-flow.
Description
The present invention relates to have the preparation method of double-hole alumina supporter, more properly say it is the preparation method of the used alumina supporter of a kind of catalyzer that is used for the heavy-oil hydrogenation treating processes.
At present, industrial used hydrogenation catalyst is that carrier and hydrogenation active metals such as Co or Ni or Mo and W are prepared from inorganic oxide such as aluminum oxide normally.This type of catalyzer has advantages such as hydrogenation activity height, physical strength is good, the life-span is long, price is low; but it is used for mink cell focus; when particularly containing the stock oil hydrogenation process of a large amount of impurity; usually can be owing to the deposition blocking catalyst duct of metallic impurity cause catalyst activity to descend rapidly, so inactivation and influence industrial application.In order to improve pore canal structure of catalyst, people have done number of research projects, thereby prolong the work-ing life of catalyzer greatly.As everyone knows, the pore structure of catalyzer is the carrier hole structures shape of catalyzer, therefore will improve the pore structure of catalyzer, at first should improve the structure of support of the catalyst.
USP4032433 has introduced a kind of hydrogenization catalyst preparation method, the method of modifying that wherein also relates to alumina supporter: with tensio-active agent and organic compound is expanding agent, change the alumina pore structure, promptly on the basis of the pore structure that former aluminum oxide had, effect by expanding agent, produce a series of macropore again, thereby make alumina supporter with double-hole structure.Though this method can be made into the double-hole aluminum oxide that contains macropore, improves the carrier hole structure effectively, intensity is low, can not adapt to industrial requirements.
JP57-123820 has introduced and has adopted a kind of aluminum oxide or its precursor aluminium hydrate powder, and by adding carbon powder and ammoniacal liquor comes modified aluminas, but the carbon powder amount that adds requires to make roasting process be difficult to controlled temperature greater than 30%, and is also unfavorable to intensity.
USP4,448,896 descriptions are raw material with a kind of aluminium hydroxide, be the preparation method of expanding agent with high poly-organism and carbon powder, but this method add HNO
3Still neutralize and reaming with ammoniacal liquor behind the peptizing agent, the result also is an intensity difference, and pore distribution too disperses.
The objective of the invention is to overcome the shortcoming of prior art, a kind of preparation method with aluminum oxide of high-intensity dual pore size distribution is provided.
The objective of the invention is to realize by following proposal: by the different aluminum oxide of two kinds of pore size distributions or its precursor and carbon powder, tensio-active agent, peptizing agent and water mixing moulding by a certain percentage, drying, roasting are made again.
Principal feature of the present invention is its preparation method: two kinds of different aluminum oxide of pore size distribution are mixed, alumina mixture and carbon powder, tensio-active agent, peptizing agent are 1: 0.05～0.1: 0.05～0.1: 0.02～0.05 and suitable quantity of water mixes, moulding by weight, again through 100～130 ℃ of dryings, 550～650 ℃ of roastings are 1～4 hour in air, the hole of promptly making diameter 100～200A account for total pore volume greater than 50%, diameter accounts for the alumina supporter of total pore volume 5～30% greater than the hole of 1000A.
The weight ratio of described alumina mixture and carbon powder, tensio-active agent, peptizing agent preferably 1: 0.06～0.08: 0.05～0.06: 0.03～0.04, the weight ratio of water and aluminium hydrate powder preferably 0.06～0.09: 1.
Described aluminum oxide precursor is often referred to hydrated aluminum oxide or aluminium hydroxide such as pseudo-boehmite, boehmite etc., and the pore size distribution range of two kinds of aluminum oxide precursor and their blending ratio can be adjusted flexibly according to the different requirement of product.Two kinds of used aluminum oxide of the present invention can make aluminum oxide (I) and aluminum oxide (II) respectively by alkyl aluminum hydrolysis method and Tai-Ace S 150 method, its pore radius distributes: aluminum oxide (I) is for＜50A accounts for 95～96%, 50～100A accounts for 2～3%, 100～250A accounts for 0.5～1.0%, 250～500A accounts for 0.2～0.5%, and aluminum oxide (II) is for＜50A accounts for 35～60%, 50～100A accounts for 21～25%, 100～250A accounts for 13～15%, 250～500A accounts for 5～6%.Aluminum oxide (I) and aluminum oxide (II) mix by weight 0.7～1.2:1.
Described carbon powder has the secondary chain usually, but adhesive aggregation becomes flourishing reticulated structure, and development degree is generally represented with oil-absorption(number) DBP.The used carbon powder of the present invention is the commercially available prod, can be industrial ethene carbon powder commonly used, thermally oxidized black powder, high wear-resistant carbon black powder etc., and preferably granularity is the high wear-resistant carbon black powder of 20～50 μ m, DBP 0.9～1.30ml/g.
The carbon powder consumption is 5～10 heavy %, and preferably 6～8 heavy %(are benchmark with the weight of aluminum oxide).The carbon powder consumption very little, and is not obvious to the reaming effect; Consumption is too many, and the reaming effect is outstanding, but aluminum oxide intensity can reduce greatly, thereby influence the catalyzer use.In order to solve this contradiction, except that the consumption with carbon powder is controlled at suitable scope, also selected tensio-active agent as second kind of expanding agent.
Described tensio-active agent is nonionic surface active agent normally, preferably unazotized linear primary alcohol polyethers or polyester.
Described peptizing agent is a Soluble Anions aluminium salt, or organic acid such as formic acid, acetate etc., particularly Soluble Anions aluminium salt, wherein is preferably aluminum nitrate, aluminum chloride, Tai-Ace S 150, preferably aluminum nitrate.Because negatively charged ion aluminium salt also contains al composition except that having proper acidic, it not only can play good adhesive action in moulding process, and helps formation-O-Al-O-bridge between particle, improves the intensity of carrier.
Prepare aluminum oxide with method of the present invention, also can in aluminium hydroxide, carbon powder, tensio-active agent and peptizing agent mixture, add proper amount of lubricating agent and/or extrusion aid such as starch, polyvinyl alcohol, methylcellulose gum, sesbania powder, so that extruded moulding successfully.
Alumina preparation method of the present invention also can require to make different shape such as spherical, sheet and various special-shaped strip particle such as trilobal cross, four blade profiles, butterfly type etc. according to difference.
In addition, also can in carrier, add other inorganic oxide material such as silicon oxide, magnesium oxide and/or zeolite etc., to obtain the different support of the catalyst of physico-chemical property.
The present invention is owing to adopt two kinds of different aluminium hydrate powders of pore size distribution to make the precursor of preparation aluminum oxide, adopt carbon powder and tensio-active agent to prepare aluminum oxide as compound expanding agent simultaneously with double-hole, make it compared with prior art not only have advantages such as the production handiness is strong, easy to operate, also can make the more suitable alumina product of pore structure simultaneously according to different needs; Owing to make peptizing agent with Soluble Anions aluminium salt, and the carbon powder consumption be controlled in the optimum range, therefore compared with prior art not only have better adhesiveproperties, but also improved the physical strength of alumina supporter greatly.
The alumina supporter that adopts method of the present invention to make can be used as catalyst carrier for hydrgenating, is specially adapted to higher stock oil of foreign matter content or mink cell focus catalyst carrier for hydrgenating.
The technical characterstic that the invention is further illustrated by the following examples, but invention should not be deemed limited to this.
It is mercury penetration method that the present invention tests aluminum oxide aperture distribution experimental technique, with Carlo Erba Porosimto Seriel mercury injection apparatus, in 1500 kilograms per centimeter
2Condition under record.The data that the present invention tests the aluminum oxide physical strength are to adopt the QCY-60 type electrodynamictype intensity meter of Dalian system alkali institute production, are that 5 millimeters oxidation aluminum strip is measured its radially arithmetical av of crushing strength to 20 grain length degree.
Used carbon powder is Tianjin Carbon Black Factory's product in the example, and character sees Table 1.
Table 1 example carbon black character
| Title | Average diameter of particles μ m | Oil-absorption(number) ml/g | The BET surface-area, m 2/g |
| High wear-resistant carbon black | 26～45 | 1.0～1.2 | 70～100 |
| Second hydrocarbon carbon black | 35～45 | 2.5～3.5 | 55～70 |
Example 1
With 34.1 gram aluminum hydroxide solid elastomer powder (I) (salic 75% alkyl aluminum hydrolysis products, as follows) and aluminium hydrate powder (II) 39.3 grams (salic 70%) that make of the employing Tai-Ace S 150 method of long refining oil-refining chemical factory catalyst plant production mix, and the back adds high wear-resistant carbon black powder 4.7 grams and tensio-active agent SA-20(Tianjin tensio-active agent factory produces) 3.5 grams and 2.1 restrain aluminum nitrates, it is mixed that 66 ml waters fully grind, on the screw rod banded extruder, be extruded into 1.8 millimeters cloverleaf pattern extrusions of diameter then, in 120 ℃ of oven dry 8 hours, blowing air roasting in tube furnace again, 600 ℃ of maturing temperatures, 4 hours, obtain carrier A, its physical properties is listed in table 2.Adopt Mo-Ni to soak the method carrying metal altogether, after drying in 480 ℃ of roastings 4 hours, catalyst A ', activity sees Table 4.
Example 2
To mix back adding high wear-resistant carbon black powder 2.8 grams, SA-20 2 grams, aluminum nitrate 1.2 grams and 30 ml water thorough mixing with example 1 identical two kinds of aluminium hydrate powders (weight is respectively 16.7 grams and 27.6 grams) and roll the back in above-mentioned banded extruder extrusion, obtain 1.8 millimeters cloverleaf pattern bars of diameter, press after the method drying, roasting of example 1 carrier B, its character sees Table 2.By example 1 method obtain catalyst B ', its activity sees Table 4.
Example 3
(adopt the Tai-Ace S 150 method to produce 20 gram aluminium hydrate powders (I) and 20 gram aluminium hydrate powders (II), trade mark TAG-201, salic 68%) mixes, adding carbon powder 2.5 grams, SA-20 2.5 grams, aluminum nitrate 1.4 grams and 20 ml waters mixes, method by example 1 obtains support C and catalyzer C ' then, and their character sees Table 2 and table 4 respectively.
Example 4
This example is three Comparative Examples of the present invention.
Comparative Examples 1
USP4 presses in this Comparative Examples system, the alumina supporter of 448, the 896 method preparations of describing.
The aluminium hydroxide of example 1 (I) 125 grams add 135 milliliters and contain 3.8 gram polyvinyl alcohol (molecular-weight average 6 * 10
4) the aqueous solution, mix and to pinch the back and add 37.5 gram high wear-resistant carbon black powder and 20 gram water, mix and pinched 0.5 hour, in 5 minutes, add the HNO of concentration 4.3%
3Solution 122 gram mixes and pinched 25 minutes, on the screw rod banded extruder, squeeze then 1.8 millimeters cloverleaf pattern bars of diameter, the step of pressing example 1 obtains carrier D and catalyzer D ', sees Table 2 and table 4.
Comparative Examples 2
The alumina supporter of the method preparation of JP57-123821 introduction is pressed by this Comparative Examples system.
The aluminium hydrate powder of example 1 (II) 225 grams add high wear-resistant carbon black powder 67.5 grams, mix the HNO that adds concentration 4.3% after 60 minutes
3Solution 220 grams, mix and to pinch that to add concentration after 25 minutes again be 2.1% ammoniacal liquor, 128 grams, mix pinch on the screw rod banded extruder, squeeze after 25 minutes 1.8 millimeters cloverleaf pattern bars of diameter, obtain carrier E and catalyzer E ' by the method for example 1, their character and activity see Table 2 and table 4.
Comparative Examples 3
The aluminum oxide of the method preparation of USP4032433 introduction is pressed by this Comparative Examples system.
The aluminium hydrate powder of example 1 (II) 100 grams add 2 gram methylcellulose gum mixings, add the aqueous solution that contains 10 gram SA-20, grind after 30 minutes and obtain 1.8 millimeters cloverleaf pattern extrusions of diameter in banded extruder, 120 ℃ of dryings after 4 hours in 650 ℃ in tube furnace the blowing air roasting get carrier F, method by example 1 gets catalyzer F ', and its performance sees Table 2 and table 4 respectively.
Example 5
This example is the intensity and the hydrodemetallation (HDM) activity of A ', B ', C ', D ', E ', F ' catalyzer relatively.
The 0.5 liter of autoclave evaluate catalysts metal removal activity that stirs with oscillatory type up and down.
Reaction raw materials character sees Table 3.In autoclave, put into 10 gram 40～60 order oxidized catalyst and 200 gram stock oils, use H
2Be pressurized to 4.0MPa after the displacement, pressure rises to 8.0MPa when being warming up to 380 ℃, and stirring velocity 60 times/minute was reacted 2 hours, and reaction is used H after finishing
2Stripping 1 hour.Oil, agent are separated, analyze and generate metal content in the oil, evaluation result is listed in table 4.
From table 2 and table 4 as can be known, not only intensity is apparently higher than correlated catalyzer for catalyzer of the present invention, and it takes off the Ni activity and also is higher than correlated catalyzer.
Table 4 catalyzer is formed and is taken off the Ni activity
| Catalyzer | A′ | B′ | C′ | D′ | E′ | F′ |
| Carrier | A | B | C | D | E | F |
| MoO 3,wt% | 5.5 | 6.2 | 6.0 | 6.3 | 6.2 | 6.4 |
| NiO,wt% | 1.3 | 1.4 | 1.5 | 1.4 | 1.4 | 1.5 |
| Take off Ni and lead, % | 38 | 35 | 35 | 22 | 22 | 26.8 |
Claims (7)
1, a kind of alumina preparation method with double-hole structure is characterized in that it is that drying, roasting are made, concrete steps by two kinds of aluminum oxide or its precursor and carbon powder, tensio-active agent, peptizing agent and water mixing mouldings that pore size distribution is different:
Two kinds of aluminum oxide that pore size distribution is different mix, with itself and carbon powder, tensio-active agent and peptizing agent is 1: 0.05～0.1: 0.05～0.1: 0.02～0.05 and suitable quantity of water mixing aftershaping by weight, forming composition is through 100～130 ℃ of dryings, 550～650 ℃ of roastings are after 1～4 hour in air, the hole that obtains bore dia and be 100～200A account for total pore volume greater than 50%, to account for total pore volume greater than the hole of 1000A be 5～30% alumina product to bore dia.
2, according to the described preparation method of claim 1, it is characterized in that two kinds of aluminum oxide can get aluminum oxide (I) and the Tai-Ace S 150 legal system gets aluminum oxide (II) by the alkyl aluminum hydrolysis legal system, its pore radius distributes: aluminum oxide (I) accounts for 95～96% for＜50A, 50～100A accounts for 2～3%, 100～250A accounts for 0.5～1.0%, 250～500A accounts for 0.2～0.5%, aluminum oxide (II) accounts for 35～60% for＜50A, 50～100A accounts for 21～25%, 100～250A accounts for 13～15%, 250～500A accounts for 5～6%, and aluminum oxide (I)/aluminum oxide (II) is that 0.7～1.2:1(is heavy).
3, in accordance with the method for claim 1, the weight ratio that it is characterized in that alumina mixture, carbon powder, tensio-active agent and peptizing agent is 1:0.06～0.08:0.05～0.07:0.03～0.05.
4, in accordance with the method for claim 1, it is characterized in that preferably 0.6～0.9:1 of water and aluminium hydrate powder weight ratio.
5, in accordance with the method for claim 1, it is characterized in that used carbon powder comprises ethene carbon powder, thermally oxidized black powder, high wear-resistant carbon black powder, preferably granularity is the high wear-resistant carbon black powder of 20～50 μ m, DBP 0.9～1.3ml/g.
6, in accordance with the method for claim 1, it is characterized in that tensio-active agent is a nonionic surface active agent, preferably unazotized linear primary alcohol polyethers or polyester.
7, in accordance with the method for claim 1, it is characterized in that peptizing agent is Soluble Anions aluminium salt or organic acid, particularly Soluble Anions aluminium salt is preferably aluminum nitrate, aluminum chloride, Tai-Ace S 150, preferably aluminum nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93114901A CN1044337C (en) | 1993-11-23 | 1993-11-23 | Preparing method for aluminium oxide carrier with double-hole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93114901A CN1044337C (en) | 1993-11-23 | 1993-11-23 | Preparing method for aluminium oxide carrier with double-hole |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1103009A true CN1103009A (en) | 1995-05-31 |
| CN1044337C CN1044337C (en) | 1999-07-28 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93114901A Expired - Lifetime CN1044337C (en) | 1993-11-23 | 1993-11-23 | Preparing method for aluminium oxide carrier with double-hole |
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| CN1058982C (en) * | 1997-12-24 | 2000-11-29 | 中国石化齐鲁石油化工公司 | Catalyst for heavy oil hydrogenation demetal and preparation method |
| CN1089039C (en) * | 1998-09-28 | 2002-08-14 | 中国石油化工集团公司 | Macroporous alumina carrier and preparing process thereof |
| CN1101452C (en) * | 2000-01-04 | 2003-02-12 | 中国石油化工集团公司 | Hydroactivity protector and its preparing process |
| CN100340334C (en) * | 2004-10-29 | 2007-10-03 | 中国石油化工股份有限公司 | Hydrogenation demetalation catalyst preparation method |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4032433A (en) * | 1976-04-30 | 1977-06-28 | Uop Inc. | Hydrorefining asphaltenic petroleum charge stocks |
| JPS57123820A (en) * | 1981-01-19 | 1982-08-02 | Mitsubishi Chem Ind Ltd | Production of formed body of porous activated alumina |
| GB2101005B (en) * | 1981-06-02 | 1984-09-05 | Asia Oil Co Ltd | Hydrogenation catalyst |
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1993
- 1993-11-23 CN CN93114901A patent/CN1044337C/en not_active Expired - Lifetime
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| CN1058982C (en) * | 1997-12-24 | 2000-11-29 | 中国石化齐鲁石油化工公司 | Catalyst for heavy oil hydrogenation demetal and preparation method |
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| CN1101452C (en) * | 2000-01-04 | 2003-02-12 | 中国石油化工集团公司 | Hydroactivity protector and its preparing process |
| CN100340334C (en) * | 2004-10-29 | 2007-10-03 | 中国石油化工股份有限公司 | Hydrogenation demetalation catalyst preparation method |
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| CN104560138A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Fluidized bed heavy oil hydrotreating method |
| CN105582951A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Preparation method of hydrodemetallization catalyst containing alkaline earth metals |
| CN105582952B (en) * | 2014-10-22 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of preparation method of the Hydrodemetalation catalyst containing rare earth |
| CN105582952A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Preparation method of rare-earth-containing hydrodemetallization catalyst |
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| CN104607197A (en) * | 2015-01-12 | 2015-05-13 | 北京三聚环保新材料股份有限公司 | Organic sulphur hydrogenation catalyst and preparation method thereof |
| CN104607197B (en) * | 2015-01-12 | 2017-07-25 | 北京三聚环保新材料股份有限公司 | A kind of Organic sulphur hydrogenation catalyst and preparation method thereof |
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