CN1611300A - Quasi-thin empholite composition containing organic reaming agent - Google Patents
Quasi-thin empholite composition containing organic reaming agent Download PDFInfo
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- CN1611300A CN1611300A CN 200310103035 CN200310103035A CN1611300A CN 1611300 A CN1611300 A CN 1611300A CN 200310103035 CN200310103035 CN 200310103035 CN 200310103035 A CN200310103035 A CN 200310103035A CN 1611300 A CN1611300 A CN 1611300A
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- Prior art keywords
- pseudo
- boehmite
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- composition
- expanding agent
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Links
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- 229910001648 diaspore Inorganic materials 0.000 title abstract 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 43
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 81
- 238000000034 method Methods 0.000 claims description 53
- 239000002002 slurry Substances 0.000 claims description 41
- 238000002360 preparation method Methods 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 32
- -1 polyoxyethylene Polymers 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 26
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 16
- 238000005507 spraying Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229920002678 cellulose Polymers 0.000 claims description 7
- 239000001913 cellulose Substances 0.000 claims description 7
- 229920000609 methyl cellulose Polymers 0.000 claims description 7
- 239000001923 methylcellulose Substances 0.000 claims description 7
- 239000013543 active substance Substances 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229920006243 acrylic copolymer Polymers 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 50
- 239000003054 catalyst Substances 0.000 abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003921 oil Substances 0.000 abstract description 3
- 239000012876 carrier material Substances 0.000 abstract 1
- 239000000295 fuel oil Substances 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 239000003292 glue Substances 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 230000029087 digestion Effects 0.000 description 23
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 16
- 229910052753 mercury Inorganic materials 0.000 description 16
- 239000002253 acid Substances 0.000 description 14
- 239000003513 alkali Substances 0.000 description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 14
- 230000032683 aging Effects 0.000 description 13
- 238000010009 beating Methods 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 206010013786 Dry skin Diseases 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000006259 organic additive Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 101150028534 cpb-1 gene Proteins 0.000 description 3
- 101150085553 cpb-2 gene Proteins 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 241000772415 Neovison vison Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 159000000013 aluminium salts Chemical class 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 241000640882 Condea Species 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical class [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CUWODFFVMXJOKD-UVLQAERKSA-N buserelin Chemical compound CCNC(=O)[C@@H]1CCCN1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@H](CC(C)C)NC(=O)[C@@H](COC(C)(C)C)NC(=O)[C@@H](NC(=O)[C@H](CO)NC(=O)[C@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CC=1NC=NC=1)NC(=O)[C@H]1NC(=O)CC1)CC1=CC=C(O)C=C1 CUWODFFVMXJOKD-UVLQAERKSA-N 0.000 description 1
- 229960002719 buserelin Drugs 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to a pseudothin diaspore composition containing organic pore-expanding agent. Said composition contains 92-99.5 wt% of pseudothin diaspore and 0.5-8 wt% of organic pore-expanding agent, in which the crystallinity of pseudothin diaspore is 10-70%. In the pseudothin diaspore composition provided by said invention the organic pore-expanding agent content is low, after high-temperature calcination the alumina with large pore capacity and large pore diameter can be obtained. Said alumina can be used as carrier material for preparing hydrodemetalization catalyst for heavy oil, residual oil and short residuum specially.
Description
Technical field
The invention relates to a kind of pseudo-boehmite composition and method of making the same that contains organic expanding agent.
Background technology
Be used for the particularly Hydrodemetalation catalyst of the higher vacuum residuum of metal content of mink cell focus, because the deposition of metallic impurity such as nickel, vanadium, cause the quick decline and the inactivation of catalyst activity easily.Employing has the catalyzer than large pore volume and big bore dia, can slow down catalyzer deactivation rate, prolonged the running period of catalyzer.The pore structure of catalyzer is by the carrier decision that constitutes catalyzer, therefore, in certain sense, preparing the carrier that has than large pore volume and big bore dia is that preparation residual oil, especially preparation are used for the key of the higher vacuum residuum Hydrodemetalation catalyst of metal content.
The aluminum oxide that is directly obtained by market generally needs could use through reaming, at the one-tenth glue, washing process of preparation pseudo-boehmite or in the pseudo-boehmite moulding process, introduce organic expanding agent, be that prior art for preparing has than large pore volume with than the normal method that adopts of macropore diameter carrier.People such as D.L.Trimm " THECONTROL OF PORE SIZE IN ALUMINA CATALYST SUPPORTS:A REVIEW[AppliedCatalysis 21 (1986) 215-238] in this is summarized.Some organic expanding agents in effect and the amount ranges aspect the preparation carrier are:
| Additive | Consumption | Influence to the alumina pore radius |
| Polyethylene oxyethane polyoxyethylene glycol | 40 weight % | Low-molecular weight polymer disappears pore radius 20-100 nanoporous, and the 2-20 nanoporous is increased; High-molecular weight polymer causes hole pore distribution broadening in the 5-1000 nanometer. |
| The poly-buserelin (2-4 monomer) of the poly-propyl alcohol of polyoxyethylene glycol | Polymkeric substance: aluminum oxide=0.5-4 | Hole in the 5-50 nanometer increases |
| Oxyethane | Oxyethane/aluminum halide=1.5-2.0 | The hole mainly concentrates in 5-14 nanometer or the 5-10 nanometer range |
| Poly-propyl amides polyvinyl alcohol | About 10% | 5-1000 nanometer endoporus increases, and pore volume has big increase |
| Methylcellulose gum polyoxyethylene glycol and methylcellulose gum mixture | ＜40 weight %-50% | Pore radius＞8000 nanoporouss significantly increase the 2-100 nanometer and 8000 nanoporouss all increase, and effect adds identical with separately |
Adopt the composition of existing pseudo-boehmite and organic expanding agent can prepare macropore alumina supporter, but that shortcoming is the content of organic expanding agent is big, reaming weak effect when the content of organic expanding agent is low.
Summary of the invention
The objective of the invention is provides the pseudo-boehmite composition and method of making the same that a kind of organic expanding agent content newly is low and have better reaming effect at having organic expanding agent content shortcoming big, reaming weak effect when the content of organic expanding agent hangs down in the pseudo-boehmite composition that contains organic expanding agent now.
The present inventor finds that the degree of crystallinity of the pseudo-boehmite in the pseudo-boehmite composition that contains organic expanding agent that prior art provides is higher, is the important factor of reaming weak effect when causing the content of organic expanding agent low.
The pseudo-boehmite composition that contains the machine expanding agent provided by the invention contains pseudo-boehmite and organic expanding agent, it is characterized in that, described composition contains the pseudo-boehmite of 92-99.5 weight %, organic expanding agent of 0.5-8 weight %, and the degree of crystallinity of pseudo-boehmite wherein is 10-70%.
The pseudo-boehmite preparation of compositions method that contains organic expanding agent provided by the invention comprises and will contain the slurries spraying drying of pseudo-boehmite, organic expanding agent, it is characterized in that, the consumption of each component in the described slurries makes the pseudo-boehmite that contains 92-99.5 weight % in the final composition, organic expanding agent of 0.5-8 weight %, and the degree of crystallinity of pseudo-boehmite wherein is 10-70%.
Compare with the existing pseudo-boehmite composition that contains organic expanding agent, pseudo-boehmite degree of crystallinity in the composition provided by the invention is low, even when organic expanding agent content is reduced to 1 weight %, after high-temperature roasting, still can obtain large pore volume, wide-aperture aluminum oxide.
For example, the composition of a kind of pseudo-boehmite provided by the invention and polyoxyethylene glycol, the content of polyoxyethylene glycol is 1 weight %, wherein the degree of crystallinity of pseudo-boehmite is 58%, said composition adopts mercury penetration method to measure its pore volume in 600 ℃ of following roastings after 2 hours be 1.49 milliliters/gram, and bore dia accounts for 26.2% of total pore volume greater than 100 nanometer pore volumes; And the content of polyoxyethylene glycol is all 1 weight %, just the degree of crystallinity of pseudo-boehmite is 95% composition, adopting mercury penetration method to measure its pore volume after 2 hours in 600 ℃ of following roastings only is 0.54 milliliter/gram, and bore dia is 0 greater than the percentage ratio that 100 nanometer pore volumes account for total pore volume.
Embodiment
The pseudo-boehmite composition that contains the machine expanding agent provided by the invention preferably contains the pseudo-boehmite of 94-99 weight %, organic expanding agent of 1-6 weight %, and the degree of crystallinity of pseudo-boehmite is preferably 25-60%.
The pseudo-boehmite (the industrial trade mark is SB) that the German Condea of described degree of crystallinity system's employing company produces is a standard specimen, measures on SIMENS D5005 type X-ray diffractometer.The X-ray diffraction conditions are: CuK α radiation, and 44KV, 40mA, sweep velocity is 2 °/minute.Concrete method of calculation are:
Described organic expanding agent can be one or more in starch, synthetic cellulose, polymeric alcohol and the tensio-active agent, and synthetic cellulose wherein is preferably one or more in carboxymethyl cellulose, methylcellulose gum, ethyl cellulose, the hydroxyl fiber fat alcohol polyethylene ether; Polymeric alcohol is preferably one or more in polyoxyethylene glycol, poly-propyl alcohol, the polyvinyl alcohol; It is the acrylic copolymer of 200-10000 and in the maleic acid copolymer one or more that tensio-active agent is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight.
According to method provided by the invention, the consumption of each component preferably makes the pseudo-boehmite that contains 94-99 weight % in the final composition, organic expanding agent of 1-6 weight % in the described slurries, and pseudo-boehmite degree of crystallinity wherein is preferably 25-60%.
Described spray-dired method adopts ordinary method well known in the art, and spray-dired condition comprises that temperature in is 350-600 ℃, is preferably 400-550 ℃, and temperature out is 95-180 ℃, is preferably 110-150 ℃.
Described pseudo-boehmite can be by any one existing method preparation.For example, can be with a kind of solution that contains aluminium salt with a kind of alkali or acid-respons, become glue and the preparation of aged method; It can be method preparation with the aluminum alkoxide hydrolysis; Also can be directly to adopt commodity pseudo-boehmite to prepare through the method for part peptization with high-crystallinity; Can also be one or more pseudo-boehmites by above-mentioned different methods preparation to be mixed obtain.
When adopting existing method through one-tenth glue, when crystallization prepares described pseudo-boehmite, can finally make the boehmite degree of crystallinity of intending in the pseudo-boehmite composition by the conciliation to preparation condition such as strength of solution, one-tenth glue temperature, aging temperature and digestion time etc. is 10-70%, is preferably 25-60%.
When direct commodity in use pseudo-boehmite and its degree of crystallinity greater than 70% the time, can adopt ordinary method, as using solution and its reaction that contains acid or alkali, temperature of reaction is room temperature-120 ℃, time 0.2-10 hour, it is 10-70% that the consumption of described acid or alkali makes the degree of crystallinity of the pseudo-boehmite in the final pseudo-boehmite composition, is preferably 25-60%.Wherein, described acid or alkali are selected from the acid or the alkali that can decompose or burn and remove through high-temperature roasting, for example, described acid can be selected from one or more acid in nitric acid, acetic acid, oxalic acid, the citric acid, and it is 0.005-0.1 that the consumption of preferred acid makes the acid and the weight ratio of pseudo-boehmite; Described alkali can be selected from one or more alkali in ammoniacal liquor, the organic amine, and it is 0.005-0.1 that the consumption of preferred bases makes the weight ratio of alkali and pseudo-boehmite.
According to the method described in the present invention, wherein said organic expanding agent can be a starch, synthetic cellulose, in polymeric alcohol and the tensio-active agent one or more, synthetic cellulose wherein is preferably carboxymethyl cellulose, methylcellulose gum, ethyl cellulose, in the hydroxyl fiber fat alcohol polyethylene ether one or more, polymeric alcohol is preferably polyoxyethylene glycol, poly-propyl alcohol, in the polyvinyl alcohol one or more, tensio-active agent is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight is the acrylic copolymer of 200-10000 and in the maleic acid copolymer one or more.
In preferred embodiments, the described pseudo-boehmite preparation of compositions method that contains organic expanding agent is:
(1) pseudo-boehmite preparation:
Method 1: with a kind of solution that contains aluminium salt with a kind of solution reaction that contains alkali or acid, becomes glue and aging obtaining, for example at 5-80 ℃, preferred 20-60 ℃, preferably 35-50 ℃ with agitation condition under with NaAlO
2Solution and carbonic acid gas, Al
2(SO
4)
3Solution or Al (NO
3)
3Solution reaction, one-tenth glue, the pH value is controlled to be 5-11, is preferably 6-8.5, wears out down at 30-60 ℃ afterwards, and digestion time is 0.2-3 hour, is preferably 0.5-1.5 hour;
Method 2: aluminum alkoxide is hydrolyzed into glue and aging obtaining, for example with the C1-C4 low-carbon alkoxy aluminium, preferably tri-propyl aluminum and water content are less than 20 weight %, preferably the low-carbon alcohol (as aqueous isopropanol) of 4-15 weight the control water yield near but be not more than under the condition of the required stoichiometry water of low-carbon alkoxy aluminium hydrolysis reaction, 50-120 ℃ of reaction 1-96 hour, be preferably 1-16 hour, steam the low-carbon alcohol of water content less than 0.2 weight %, in solid product, add deionized water, aging down at 30-60 ℃ afterwards, digestion time is 0.2-3 hour, is preferably 0.5-1.5 hour;
Method 3: the pseudo-boehmite part peptization of high-crystallinity is obtained, for example ℃ reacted 0.2-10 hour in room temperature-120 with the pseudo-boehmite of the solution that contains acid or alkali and high-crystallinity, the weight ratio of acid or alkali and pseudo-boehmite is 0.005-0.1, described acid or alkali are for decomposing or the acid or the alkali of burn off through high-temperature roasting, as be selected from one or more acid in nitric acid, acetic acid, oxalic acid, the citric acid, or be selected from one or more alkali in ammoniacal liquor, the organic amine.
(2) contain the preparation of pseudo-boehmite, organic additive slurries:
The product that is obtained by step (1) obtains filter cake after filtration, and this filter cake, organic additive and water are mixed, and makes slurries through stirring.The consumption of each component makes the pseudo-boehmite that contains 92-99 weight % in the final composition in the described slurries, is preferably 94-99.5 weight %, and organic expanding agent of 0.5-8 weight % is preferably 1-6 weight %;
(3) spraying drying:
With the slurries spraying drying that step (2) obtains, the control temperature in is 350-600 ℃, is preferably 400-550 ℃, and temperature out is 95-180 ℃, is preferably 110-150 ℃.
When adopting described method 1 to prepare pseudo-boehmite, preferably include a water-washing step.Method for washing is conventional method, and finally makes the sodium oxide content in the pseudo-boehmite be lower than 1 weight %.
The pseudo-boehmite composition that contains organic expanding agent provided by the invention can obtain large pore volume, wide-aperture carrier according to ordinary method after moulding and roasting.Zhi Bei carrier is suitable for preparing the especially carrier of the Hydrodemetalation catalyst of the higher vacuum residuum of metal content of mink cell focus, residual oil thus.Compare with the similar carrier of existing method preparation, this preparing carriers technology is simple, maturing temperature is controlled easily, makes it in industrial easier enforcement.
Below by example explanation the present invention.
Agents useful for same in the example except that specifying, is chemically pure reagent.
Example 1-10 explanation is applicable to pseudo-boehmite in the composition provided by the invention and preparation method thereof.
Example 1
Adopt aluminium hydroxide (Shandong Aluminum Plant's product) and sodium hydroxide (Beijing Chemical Plant's product) prepared in reaction concentration be 200 gram aluminum oxide/liter NaAlO
2Solution, with this solution and concentration be 90 gram aluminum oxide/liter Al
2(SO
4)
3Solution (Chang Ling refinery catalyst plant product) with and the mode of stream join simultaneously in one 2 liters the one-tenth glue jar, put into 1.5 premium on currency in advance, NaAlO in jar
2The flow of solution is 1.1 liters/hour, regulates Al
2(SO
4)
3The flow of solution, making into glue pH value is 8, and becoming the temperature of glue process is 50 ℃, and the slurries that become glue to generate are collected in a digestion tank, collect after 20 minutes, slurries are switched in another digestion tank collect.Collected and added yellow soda ash adjusting pH value to 10 in the digestion tank that finishes, aging 50 minutes then, filter, with 30 times of 50 ℃ of deionized water wash 4 times, prepare 14 kilograms of pseudo-boehmite wet cakes thus, get this wet cake 50 and restrain in 120 ℃ of dryings 4 hours, it is 68% that the X-ray diffraction is measured its relative crystallinity.
Example 2
With concentration be 240 the gram aluminum oxide/liter NaAlO
2Solution (preparation method is with example 1) and concentration be 50 the gram aluminum oxide/liter Al (NO
3)
3(Beijing Chemical Plant's product) solution with and the mode of stream join simultaneously in one 2 liters the one-tenth glue jar, put into 1.5 premium on currency in advance, NaAlO in jar
2The flow of solution is 1.1 liters/hour, regulates Al (NO
3)
3The flow of solution, making into glue pH value is 7.5, and becoming the temperature of glue process is 35 ℃, and the slurries that become glue to generate are collected in a digestion tank, collect after 20 minutes, slurries are switched in another digestion tank collect.Collected in the digestion tank that finishes slurries aging 150 minutes, and filtered, with 30 times of 55 ℃ of deionized water wash 2 times, prepared 8 kilograms of pseudo-boehmite wet cakes thus, got this wet cake 50 and restrain in 110 ℃ of dryings 8 hours, it is 47% that the X-ray diffraction is measured its relative crystallinity.
Example 3
Get 20 liters of concentration and be 20 gram aluminum oxide/liter sodium aluminate solution (preparation method is with example 1), place one 25 liters one-tenth glue jar, 15 ℃ of initial temperatures, feed carbonic acid gas and the Air mixing gas of carbon dioxide content 30 volume % from the bottom that becomes the glue jar, the flow of gas mixture be 35 meters 3/ hour, reacted 5 minutes, the pH value drops to 6.8 (endpoint pH), this moment, temperature of reaction was 28 ℃, become the glue reaction to finish, filter,, filter and obtain the pseudo-boehmite wet cake at last with 20 times of 45 ℃ of deionized waters making beating washings 5 times, by becoming glue again with quadrat method, wash 2 times, altogether about 8 kilograms of pseudo-boehmite wet cakes, get this wet cake 50 and restrain in 130 ℃ of dryings 3 hours, it is 58% that the X-ray diffraction is measured its relative crystallinity.
Example 4
With concentration be 30 the gram aluminum oxide/liter Al (NO
3)
3Solution (preparation method is with example 1) and concentration be 8 weight % ammonia soln with and the mode of stream join one 3 liters becoming in the glue jar simultaneously, put into 1.5 premium on currency in advance, Al (NO in jar
3)
3The flow of solution is 3.5 liters/hour, regulates the flow of ammonia soln, and making into glue pH value is 8.5, and becoming the temperature of glue process is 42 ℃, and the slurries that become glue to generate are collected in a digestion tank, collect after 70 minutes, slurries are switched in another digestion tank collect.Collected in the digestion tank that finishes slurries aging 60 minutes, and filtered, with 30 times of 40 ℃ of deionized water wash 4 times, prepared 8 kilograms of pseudo-boehmite wet cakes thus, got this wet cake 50 and restrain in 120 ℃ of dryings 4 hours, it is 51% that the X-ray diffraction is measured its relative crystallinity.
Example 5
With concentration be 50 the gram aluminum oxide/liter Al
2(SO
4)
3Solution (preparation method is with example 1) and concentration be 15 weight % ammonia soln with and the mode of stream join one 3 liters becoming in the glue jar simultaneously, put into 1.5 premium on currency in advance, Al in jar
2(SO
4)
3The flow of solution is 2.5 liters/hour, regulates the flow of ammonia soln, and making into glue pH value is 7.5, and becoming the temperature of glue process is 40 ℃, and the slurries that become glue to generate are collected in a digestion tank, collect after 60 minutes, slurries are switched in another digestion tank collect.Collected in the digestion tank that finishes slurries aging 90 minutes, and filtered, with 30 times of 58 ℃ of deionized water wash 4 times, prepared 7 kilograms of pseudo-boehmite wet cakes thus, got this wet cake 50 and restrain in 120 ℃ of dryings 4 hours, it is 39% that the X-ray diffraction is measured its relative crystallinity.
Example 6
With concentration be 15 the gram aluminum oxide/liter Al
2(SO
4)
3(Beijing Chemical Plant's product) solution and concentration are the NH of 17 grams per liters
4HCO
3(Beijing Chemical Plant's product) solution with and the mode of stream join simultaneously in one 3 liters the one-tenth glue jar, put into 1.5 premium on currency in advance, Al in jar
2(SO
4)
3The flow of solution is 2.5 liters/hour, regulates NH
4HCO
3The flow of solution, making into glue pH value is 6.0, and becoming the temperature of glue process is 30 ℃, and the slurries that become glue to generate are collected in a digestion tank, collect after 60 minutes, slurries are switched in another digestion tank collect.Collected the interior slurries of the digestion tank that finishes aging 30 minutes, filter,, prepare 7.5 kilograms of pseudo-boehmite wet cakes thus with 30 times of 55 ℃ of deionized water wash 4 times, get this wet cake 50 and restrain in 130 ℃ of dryings 3 hours, it is 28% that the X-ray diffraction is measured its relative crystallinity.
Example 7
With concentration be 12 the gram aluminum oxide/liter Al (NO
3)
3(preparation method is with example 1) solution and concentration are the NH of 10 grams per liters
4HCO
3Solution with and the mode of stream join simultaneously in one 3 liters the one-tenth glue jar, put into 1.5 premium on currency in advance, Al (NO in jar
3)
3The flow of solution is 2.0 liters/hour, regulates NH
4HCO
3The flow of solution, making into glue pH value is 6.0, and becoming the temperature of glue process is 30 ℃, and the slurries that become glue to generate are collected in a digestion tank, collect after 60 minutes, slurries are switched in another digestion tank collect.Collected in the digestion tank that finishes slurries aging 30 minutes, and filtered, with 30 times of 30 ℃ of deionized water wash 3 times, prepared 6 kilograms of pseudo-boehmite wet cakes thus, got this wet cake 50 and restrain in 110 ℃ of dryings 8 hours, it is 35% that the X-ray diffraction is measured its relative crystallinity.
Example 8
With concentration be 150 the gram aluminum oxide/liter NaAlO
2Solution (preparation method is with example 1) and concentration be 50 the gram aluminum oxide/liter Al
2(SO
4)
3Solution with and the mode of stream join simultaneously in one 2 liters the one-tenth glue jar (once becoming the glue jar), put into 1.5 premium on currency in advance, NaAlO in jar
2The flow of solution is 1.4 liters/hour, regulates Al
2(SO
4)
3The flow of solution, making into glue pH value is 7.0, and becoming the temperature of glue process is 40 ℃, and the slurries that become glue to generate become in the glue jar to collect at a secondary, collect after 30 minutes, slurries are switched to another secondary become in the glue jar to collect.Having collected the secondary that finishes becomes to add NH in the glue jar
4HCO
3Regulate pH value to 7.5, aging 40 minutes then, filtration with 30 times of 50 ℃ of deionized water wash 4 times, prepared 7.5 kilograms of pseudo-boehmite wet cakes thus, got this wet cake 50 and restrained in 100 ℃ of dryings 10 hours, and it is 43% that the X-ray diffraction is measured its relative crystallinity.
Example 9
Method by Chinese patent CN 85 1 00218A examples 1 prepares pseudo-boehmite, promptly in 2 liters of there-necked flasks of band stirring and backflow, the azeotrope (water content is about 1.5%) that adds 1100 gram Virahol-water, after being heated to boiling the about 500 thawing aluminium isopropoxides that restrain are added dropwise in the flask by separating funnel, reflux time is 5 hours, steam about 700 grams of dehydration Virahol, water content about 0.2%, gradation adds about 1.5 liters of deionized waters and wears out then, aging temperature is controlled at 60 ℃, digestion time is 55 minutes, and weathering process steams about 1200 grams of aqueous isopropanol, filters afterwards and obtains about 850g pseudo-boehmite wet cake, revision test 10 times, obtain about 8.5 kilograms of pseudo-boehmite wet cake, get this wet cake 50 and restrain in 110 ℃ of dryings 5 hours, it is 57% that the X-ray diffraction is measured its relative crystallinity.
Example 10
In 30 liters the reactor that a band stirs, add 20 liters in water, start whipping appts, stirring velocity is 180 rev/mins, adds 30 milliliters of concentrated nitric acids (concentration 65-68 weight %), add 1 kilogram of SB powder (relative crystallinity is 100%) then gradually, and temperature risen to 55 ℃, and kept 4 hours, stop to stir, with dope filtration, obtain about 5 kilograms of pseudo-boehmite wet cakes, get this wet cake 50 and restrain in 110 ℃ of dryings 5 hours, it is 65% that the X-ray diffraction is measured its relative crystallinity.
Example 11-20 illustrates the pseudo-boehmite composition and method of making the same that contains organic expanding agent provided by the invention.
Example 11
Get 6.5 kilograms of (Al of wet cake of example 1 preparation
2O
3Content 15 weight %) mix with sesbania powder 20.5 grams, add the water making beating, finally obtain 8 liters in slurries, afterwards in 600 ℃ of temperature ins, spraying drying under 145 ℃ of conditions of temperature out obtains 930 gram composition PB-1, and its composition sees Table 1.PB-1 in 600 ℃ of following roastings 2 hours, is cooled to adopt after the room temperature and presses the mercury method to measure its aperture and pore volume, the results are shown in Table 1.
Comparative Examples 1
This Comparative Examples illustrates pseudo-boehmite that does not contain organic expanding agent of spray drying process preparation routinely and preparation method thereof.
Get 6.5 kilograms of (Al of wet cake of example 1 preparation
2O
3Content 15 weight %), add the water making beating, finally obtain 8 liters in slurries, temperature in is 600 ℃ afterwards, and spraying drying under 145 ℃ of conditions of temperature out obtains 890 gram pseudo-boehmite CPB-1.CPB-1 in 600 ℃ of following roastings 2 hours, is cooled to adopt after the room temperature and presses the mercury method to measure its aperture and pore volume, the results are shown in Table 1.
Example 12
Get 5 kilograms of (Al of wet cake of example 2 preparations
2O
3Content 18 weight %) mix with methylcellulose gum 45 grams, add the water making beating, finally obtain 9 liters in slurries, afterwards in 550 ℃ of temperature ins, spraying drying under 125 ℃ of conditions of temperature out obtains 850 gram composition PB-2, and its composition sees Table 1.PB-2 in 600 ℃ of following roastings 2 hours, is cooled to adopt after the room temperature and presses the mercury method to measure its aperture and pore volume, the results are shown in Table 1.
Example 13
Get 5.5 kilograms of (Al of wet cake of example 3 preparations
2O
3Content 14 weight %) be that 2000 polyoxyethylene glycol, 7.7 grams mix with molecular weight, add the water making beating, finally obtain 10 liters in slurries, afterwards in 580 ℃ of temperature ins, spraying drying under 120 ℃ of conditions of temperature out obtains 700 and restrains composition PB-3, and its composition sees Table 1.PB-3 in 600 ℃ of following roastings 2 hours, is cooled to adopt after the room temperature and presses the mercury method to measure its aperture and pore volume, the results are shown in Table 1.
Comparative Examples 2
This illustrates the same the present invention of preparation method, contains organic expanding agent example, but the pseudo-boehmite composition and method of making the same that pseudo-boehmite degree of crystallinity can not meet the demands.
Change initial one-tenth glue temperature in the example 3 into 40 ℃, endpoint pH is controlled at 10.5, and aging temperature is 95 ℃, and digestion time is 240 minutes, and other condition is constant, makes 8 kilograms of pseudo-boehmite wet cakes thus, and its dry back relative crystallinity of XRD determining is 95%; Get 5.5 kilograms of (Al of wet cake
2O
3Content 14 weight %) be that 2000 polyoxyethylene glycol, 7.7 grams mix with molecular weight, add the water making beating, finally obtain 10 liters in slurries, afterwards in 580 ℃ of temperature ins, spraying drying under 120 ℃ of conditions of temperature out obtains 700 and restrains composition CPB-2, and its composition sees Table 1.CPB-2 in 600 ℃ of following roastings 2 hours, is cooled to adopt after the room temperature and presses the mercury method to measure its aperture and pore volume, the results are shown in Table 1.
Example 14
Get 4 kilograms of (Al of wet cake of example 4 preparations
2O
3Content 18 weight %) be that 800 polyoxyethylene glycol, 12 grams mix with molecular weight, add the water making beating, finally obtain 8 liters in slurries, afterwards in 450 ℃ of temperature ins, spraying drying under 110 ℃ of conditions of temperature out obtains 680 and restrains composition PB-4, and its composition sees Table 1.PB-4 in 600 ℃ of following roastings 2 hours, is cooled to adopt after the room temperature and presses the mercury method to measure its aperture and pore volume, the results are shown in Table 1.
Example 15
Get 6.5 kilograms of (Al of wet cake of example 5 preparations
2O
3Content 15 weight %) mix with ethyl cellulose 30 grams, add the water making beating, finally obtain 10 liters in slurries, afterwards in 580 ℃ of temperature ins, spraying drying under 140 ℃ of conditions of temperature out obtains 950 gram composition PB-5, and its composition sees Table 1.PB-5 in 600 ℃ of following roastings 2 hours, is cooled to adopt after the room temperature and presses the mercury method to measure its aperture and pore volume, the results are shown in Table 1.
Example 16
Get 5 kilograms of (Al of wet cake of example 6 preparations
2O
3Content 18 weight %) mix with peregal (SA-20, a kind of fatty alcohol-polyoxyethylene ether) 18 grams, add the water making beating, finally obtain 9 liters in slurries, afterwards in 550 ℃ of temperature ins, spraying drying under 125 ℃ of conditions of temperature out, obtain 890 gram composition PB-6, its composition sees Table 1.PB-6 in 600 ℃ of following roastings 2 hours, is cooled to adopt after the room temperature and presses the mercury method to measure its aperture and pore volume, the results are shown in Table 1.
Example 17
Get 5.5 kilograms of (Al of wet cake of example 7 preparations
2O
3Content 16 weight %) be that 6000 polyoxyethylene glycol, 15 grams mix with molecular weight, add the water making beating, finally obtain 9 liters in slurries, afterwards in 580 ℃ of temperature ins, spraying drying under 120 ℃ of conditions of temperature out obtains 790 and restrains composition PB-7, and its composition sees Table 1.PB-7 in 600 ℃ of following roastings 2 hours, is cooled to adopt after the room temperature and presses the mercury method to measure its aperture and pore volume, the results are shown in Table 1.
Example 18
Get 4 kilograms of (Al of wet cake of example 8 preparations
2O
3Content 18 weight %) mix with carboxymethyl cellulose 12 grams, add the water making beating, finally obtain 8 liters in slurries, afterwards in 450 ℃ of temperature ins, spraying drying under 110 ℃ of conditions of temperature out obtains 680 gram composition PB-8, and its composition sees Table 1.PB-8 in 600 ℃ of following roastings 2 hours, is cooled to adopt after the room temperature and presses the mercury method to measure its aperture and pore volume, the results are shown in Table 1.
Example 19
Get 8 kilograms of (Al of wet cake of example 9 preparations
2O
3Content 16 weight %) mix with carboxymethyl cellulose 75 grams, add the water making beating, finally obtain 15 liters in slurries, afterwards in 450 ℃ of temperature ins, spraying drying under 110 ℃ of conditions of temperature out obtains 1700 gram composition PB-9, and its composition sees Table 1.PB-9 in 600 ℃ of following roastings 2 hours, is cooled to adopt after the room temperature and presses the mercury method to measure its aperture and pore volume, the results are shown in Table 1.
Example 20
Get 4.5 kilograms of (Al of wet cake of example 10 preparations
2O
3Content 17 weight %) mix with methylcellulose gum 12 grams, add the water making beating, finally obtain 10 liters in slurries, afterwards in 450 ℃ of temperature ins, spraying drying under 110 ℃ of conditions of temperature out obtains 950 gram composition PB-10, and its composition sees Table 1.PB-10 in 600 ℃ of following roastings 2 hours, is cooled to adopt after the room temperature and presses the mercury method to measure its aperture and pore volume, the results are shown in Table 1.
Table 1
| Example | ??11 | Comparative Examples 1 | ????12 | ??13 | Comparative Examples 2 |
| The PB numbering | ??PB-1 | ????CPB-1 | ????PB-2 | ??PB-3 | ??CPB-2 |
| Organic additive content, weight % | ??2.1 | ????0 | ????5 | ??1 | ??1 |
| Pore volume, the milliliter gram -1 | ??1.46 | ????1.12 | ????1.57 | ??1.49 | ??0.54 |
| The pore volume of bore dia＞100 nanometers and the ratio of total pore volume, % | ??16.7 | ????5.5 | ????29.9 | ??26.2 | ??0 |
Continuous table 1
| Example | ????14 | ????15 | ????16 | ????17 | ????18 |
| The PB numbering | ????PB-4 | ????PB-5 | ????PB-6 | ????PB-7 | ????PB-8 |
| Organic additive content, weight % | ????1.7 | ????3.1 | ????2 | ????1.7 | ????1.7 |
| Pore volume, the milliliter gram -1 | ????1.52 | ????1.56 | ????1.70 | ????1.74 | ????1.62 |
| The pore volume of bore dia＞100 nanometers and the ratio of total pore volume, % | ????27.6 | ????29.5 | ????35.3 | ????36.8 | ????32.1 |
Continuous table 1
| Example | ????19 | ????20 |
| The PB numbering | ????PB-9 | ????PB-10 |
| Organic additive content, weight % | ????5.9 | ????1.6 |
| Pore volume, the milliliter gram -1 | ????1.48 | ????1.41 |
| The pore volume of bore dia＞100 nanometers and the ratio of total pore volume, % | ????33.7 | ????20.5 |
The result of table 1 can show, compares with Comparative Examples, and the low-crystallinity pseudo-boehmite composition that contains organic additive provided by the invention is after roasting, and the per-cent that the pore volume of its pore volume and bore dia＞100 nanometers accounts for total pore volume obviously improves.For example, a kind of pseudo-boehmite that provides according to example 13 of the present invention and the composition of polyoxyethylene glycol, wherein the degree of crystallinity of pseudo-boehmite is 58%, the content of polyoxyethylene glycol is 1 weight %, said composition was in 600 ℃ of following roastings 2 hours, adopting mercury penetration method to measure its pore volume is 1.49 milliliters/gram, and bore dia accounts for 26.2% of total pore volume greater than 100 nanometer pore volumes; And in the Comparative Examples 2, the content of polyoxyethylene glycol is all 1 weight %, just the degree of crystallinity of pseudo-boehmite is 95% composition, and adopting mercury penetration method to measure its pore volume after 2 hours through 600 ℃ of following roastings only is 0.54 milliliter/gram, and bore dia accounts for 0 of total pore volume greater than 100 nanometer pore volumes.
Claims (8)
1, a kind of pseudo-boehmite composition that contains organic expanding agent is characterized in that, said composition contains the pseudo-boehmite of 92-99.5 weight %, organic expanding agent of 0.5-8 weight %, and the degree of crystallinity of pseudo-boehmite wherein is 10-70%.
2, composition according to claim 1 is characterized in that, described composition contains the pseudo-boehmite of 94-99 weight %, organic expanding agent of 1-6 weight %, and the degree of crystallinity of pseudo-boehmite wherein is 25-60%.
3, composition according to claim 1 and 2 is characterized in that, described organic expanding agent is selected from one or more in starch, synthetic cellulose, polymeric alcohol, the tensio-active agent.
4, composition according to claim 3 is characterized in that, described synthetic cellulose is selected from one or more in carboxymethyl cellulose, methylcellulose gum, ethyl cellulose, the hydroxylated cellulose.
5, composition according to claim 3 is characterized in that, described polymeric alcohol is selected from one or more in polyoxyethylene glycol, poly-propyl alcohol, the polyvinyl alcohol
6, composition according to claim 3 is characterized in that, it is the acrylic copolymer of 200-10000 that described tensio-active agent is selected from fatty alcohol-polyoxyethylene ether, fatty alkanol amide, molecular weight, in the maleic acid copolymer one or more.
7, the described preparation of compositions method of claim 1, this method comprises and will contain the slurries spraying drying of pseudo-boehmite, organic expanding agent, it is characterized in that, each components contents makes the pseudo-boehmite that contains 92-99.5 weight % in the final composition in the composition, organic expanding agent of 0.5-8 weight % in the described slurries, and pseudo-boehmite degree of crystallinity wherein is 10-70%.
8, method according to claim 7, it is characterized in that, each components contents makes the pseudo-boehmite that contains 94-99 weight % in the final composition, organic expanding agent of 1-6 weight % in the described slurries, and the degree of crystallinity of pseudo-boehmite wherein is 25-60%.
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| CN1123628C (en) * | 2000-11-08 | 2003-10-08 | 中国石油化工股份有限公司 | Heavy oil hydrogenating treatment catalyst and its preparing method |
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