CN1647857A - Macroporous aluminium oxide carrier and its preparing method - Google Patents
Macroporous aluminium oxide carrier and its preparing method Download PDFInfo
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- CN1647857A CN1647857A CN 200410000953 CN200410000953A CN1647857A CN 1647857 A CN1647857 A CN 1647857A CN 200410000953 CN200410000953 CN 200410000953 CN 200410000953 A CN200410000953 A CN 200410000953A CN 1647857 A CN1647857 A CN 1647857A
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- Prior art keywords
- boehmite
- pore volume
- carrier
- expanding agent
- weight
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Links
- 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 41
- 238000000034 method Methods 0.000 title claims description 58
- 239000011148 porous material Substances 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 238000002360 preparation method Methods 0.000 claims abstract description 37
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 67
- 229910001593 boehmite Inorganic materials 0.000 claims description 66
- 239000002002 slurry Substances 0.000 claims description 23
- 238000001694 spray drying Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 35
- 230000000694 effects Effects 0.000 abstract description 8
- 230000006837 decompression Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000032683 aging Effects 0.000 description 24
- 239000003292 glue Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 15
- 239000003513 alkali Substances 0.000 description 14
- 206010013786 Dry skin Diseases 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- -1 Polyethylene oxirane Polymers 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002202 Polyethylene glycol Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 229920001223 polyethylene glycol Polymers 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- 238000010009 beating Methods 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
- 239000000047 product Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 229920000609 methyl cellulose Polymers 0.000 description 5
- 239000001923 methylcellulose Substances 0.000 description 5
- 235000010981 methylcellulose Nutrition 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- 229940010552 ammonium molybdate Drugs 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 101150085553 cpb-2 gene Proteins 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000006259 organic additive Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- 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 description 2
- 241000772415 Neovison vison Species 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- 229920006243 acrylic copolymer Polymers 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
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 101150028534 cpb-1 gene Proteins 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000002156 mixing 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000640882 Condea Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-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
- 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
- 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 239000012141 concentrate Substances 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
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- GKWCCSUCDFFLBP-UHFFFAOYSA-N oxirane Chemical compound C1CO1.C1CO1 GKWCCSUCDFFLBP-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
- 238000010257 thawing Methods 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The present invention is macroporous alumina carrier and its preparation process. The carrier has pore volume of 0.9-1.3 ml/g, pore volume rate of pores smaller than 20 nm in 55-85 %, pore volume rate of 20-100 nm diameter pores in 7-25 %, and pore volume rate of pores greater than 100 nm in 7-25 %. The preparation process of the carrier includes forming and roasting pseudo-thin diasphore composition containing organic pore expanding agent. The preparation process of the present invention has relatively low organic pore expanding agent consumption and high pore expanding effect. The prepared macroporous alumina carrier is used in catalyst for hydrogenating and demetallating heavy and residual oil, especially decompression residual oil with high metal content.
Description
Technical field
The invention relates to a kind of alumina support and preparation method thereof, more specifically say so about a kind of macropore alumina supporter and preparation method thereof.
Background technology
Be used for mink cell focus,,, cause the quick decline and the inactivation of its activity easily owing to the deposition of metal impurities such as nickel, vanadium especially for the Hydrodemetalation catalyst of the higher decompression residuum of tenor.Have catalyst than large pore volume and big bore dia hold metal and hold the carbon ability strong, can slow down catalyst inactivation, prolonged the service cycle of catalyst.
The pore structure of catalyst is by the carrier decision that constitutes catalyst, and therefore, the carrier that preparation has than large pore volume and big bore dia is that preparation residual oil, especially preparation are used for the key of the higher decompression residuum Hydrodemetalation catalyst of tenor.
At the one-tenth glue, washing process of preparation boehmite or in the boehmite forming 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 " THE CONTROL OF PORE SIZE IN ALUMINA CATALYST SUPPORTS:A REVIEW[Applied Catalysis 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 oxirane polyethylene glycol | 40 weight % | Low-molecular weight polymer disappears pore radius 20-100 nano-pore, and the 2-20 nano-pore is increased; Heavy polymer causes hole pore size distribution broadening in the 5-1000 nanometer. |
| The poly-buserelin (2-4 monomer) of the poly-propyl alcohol of polyethylene glycol | Polymer: aluminium oxide=0.5-4 | Hole in the 5-50 nanometer increases |
| Oxirane | Oxirane/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 polyethylene glycol and methylcellulose mixture | ＜40 weight %-50% | Pore radius＞8000 nano-pores significantly increase the 2-100 nanometer and 8000 nano-pores all increase, and effect adds identical with separately |
Adopt the composition of existing boehmite and organic expanding agent can prepare macropore alumina supporter, but that shortcoming is the consumption of organic expanding agent is big, reaming weak effect when the consumption of organic expanding agent is low.
Summary of the invention
The objective of the invention is provides a kind of new method for preparing macropore alumina supporter that organic expanding agent consumption is low, reaming is effective and the macropore alumina supporter that is prepared by this method at having organic expanding agent consumption shortcoming big, reaming weak effect when the consumption of organic expanding agent hangs down in the method for preparing macropore alumina supporter now.
The preparation method of macropore alumina supporter provided by the invention comprises boehmite composition molding and the roasting that contains organic expanding agent with a kind of, it is characterized in that, described composition contains the boehmite of 92-99.5 weight %, organic expanding agent of 0.5-8 weight %, and boehmite wherein is a kind of degree of crystallinity less than 70% boehmite.
The pore volume of macropore alumina supporter provided by the invention is 0.9-1.3 milliliter/gram, it is characterized in that the method preparation that described carrier is provided by the invention described above.
Compare with existing method, method provided by the invention has adopted a kind of new boehmite composition that contains organic expanding agent, and the organic expanding agent content in the said composition is low, but the reaming effect is remarkable.The hole that said composition can be obtained large pore volume, big bore dia after according to conventional method moulding and roasting accounts for the high carrier of ratio of total pore volume.
For example, is 1 weight % according to method provided by the invention with a kind of content of the spray-dried polyethylene glycol that obtains, wherein the degree of crystallinity of boehmite is that 58% composition made carrier in 3 hours through moulding and in 750 ℃ of following roastings, adopting mercury injection method to measure its pore volume is 1.17 milliliters/gram, and it is that the hole of 20-100 nanometer accounts for total pore volume 18.9%, bore dia accounts for total pore volume 16.1% for the hole greater than 100 nanometers that bore dia accounts for total pore volume 65.0%, bore dia less than the hole of 20 nanometers; And in the Comparative Examples method, the content of polyethylene glycol is all 1 weight %, just wherein the degree of crystallinity of boehmite is 95%, made carrier in 3 hours through moulding and in 750 ℃ of following roastings, adopting mercury injection method to measure its pore volume only is 0.37 milliliter/gram, and it is that the hole of 20-100 nanometer accounts for total pore volume 1.9%, bore dia is 0 greater than the hole of 100 nanometers that bore dia accounts for total pore volume 98.1%, bore dia less than the hole of 20 nanometers.
The specific embodiment
According to method provided by the invention, the wherein said boehmite composition that contains organic expanding agent preferably contains the boehmite of 94-99 weight %, organic expanding agent of 1-6 weight %.Described degree of crystallinity is the incomplete boehmite of a kind of crystallization less than 70% boehmite, can be amorphous hydroted alumina, and preferred degree of crystallinity is 10-68%, more preferably the boehmite of 25-60%.
The 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 speed is 2 °/minute.Concrete computational methods are:
Described organic expanding agent can be one or more in starch, synthetic cellulose, polymeric alcohol and the surfactant, and synthetic cellulose wherein is preferably one or more in carboxymethyl cellulose, methylcellulose, ethyl cellulose, the hydroxyl fiber fat alcohol polyethylene ether; Polymeric alcohol is preferably one or more in polyethylene 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 surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight.
The described boehmite preparation of compositions method that contains organic expanding agent comprises and will contain the slurries spray-drying of boehmite, organic expanding agent, the consumption of each component makes the boehmite that contains 92-99.5 weight % in the final composition, is preferably 94-99 weight % in the described slurries, 0.5-8 weight %, be preferably organic expanding agent of 1-6 weight %, boehmite wherein is degree of crystallinity less than 70%, be preferably 10-68%, the boehmite of 25-60% more preferably.
Described spray-dired method adopts conventional method well known in the art, and spray-dired condition comprises that inlet temperature is 350-600 ℃, is preferably 400-550 ℃, and outlet temperature is 95-180 ℃, is preferably 110-150 ℃.
Described 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 reaction, become glue and aging method preparation; It can be method preparation with the aluminum alkoxide hydrolysis; Also can be directly to adopt commodity boehmite to prepare through the method for part peptization with high-crystallinity; Can also be one or more boehmites by above-mentioned distinct methods preparation to be mixed obtain.
When adopt existing method through become glue, when crystallization prepares the incomplete boehmite of described crystallization, can by to preparation condition such as solution concentration, to become the conciliation of glue temperature, aging temperature and ageing time etc. make boehmite in the final boehmite composition be degree of crystallinity less than 70%, be preferably 10-68%, the boehmite of 25-60% more preferably.
When direct commodity in use boehmite and its degree of crystallinity greater than 70% the time, can adopt conventional method, as using solution and its reaction that contains acid or alkali, reaction temperature is room temperature-120 ℃, time 0.2-10 hour, and it is degree of crystallinity less than 70% that the consumption of described acid or alkali should make boehmite in the final boehmite composition, be preferably 10-68%, the boehmite of 25-60% more preferably.Wherein, acid or alkali that described acid or alkali preferably can decompose or burn and remove through high-temperature roasting, for example, described acid can be selected from one or more in nitric acid, acetic acid, oxalic acid, the citric acid, and the consumption of preferred acid to make the acid and the weight ratio of boehmite be 0.005-0.1; Described alkali can be selected from one or more alkali in ammoniacal liquor, the organic amine, and the consumption of preferred bases to make the weight ratio of alkali and boehmite be 0.005-0.1.
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 surfactant one or more, synthetic cellulose wherein is preferably carboxymethyl cellulose, methylcellulose, ethyl cellulose, in the hydroxyl fiber fat alcohol polyethylene ether one or more, polymeric alcohol is preferably polyethylene glycol, poly-propyl alcohol, in the polyvinyl alcohol one or more, surfactant 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 boehmite preparation of compositions method that contains organic expanding agent is:
(1) boehmite preparation:
Method 1: with a kind of solution that contains aluminium salt and a kind of solution reaction that contains alkali or acid, becomes glue and wear out.For example at 5-80 ℃, preferred 20-60 ℃, preferably under 35-50 ℃ and the stirring condition with NaAlO
2Solution and carbon dioxide, 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 ageing time is 0.2-3 hour, is preferably 0.5-1.5 hour;
Method 2: aluminum alkoxide is hydrolyzed into glue and aging.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 alcohols (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, 50-120 ℃ of reaction 1-96 hour, be preferably 1-16 hour, steam the low-carbon alcohols of water content less than 0.2 weight %, in solid product, add deionized water, aging down at 30-60 ℃ afterwards, ageing time is 0.2-3 hour, is preferably 0.5-1.5 hour;
Method 3: with the boehmite part peptization of high-crystallinity.For example ℃ reacted 0.2-10 hour in room temperature-120 with the boehmite of the solution that contains acid or alkali and high-crystallinity, the weight ratio of acid or alkali and 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 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 boehmite that contains 92-99.5 weight % in the final composition in the described slurries, is preferably 94-99 weight %, and organic expanding agent of 0.5-8 weight % is preferably 1-6 weight %;
(3) spray-drying:
With the slurries spray-drying that step (2) obtains, the control inlet temperature is 350-600 ℃, is preferably 400-550 ℃, and outlet temperature is 95-180 ℃, is preferably 110-150 ℃.
When adopting described method 1 to prepare boehmite, preferably include a water-washing step.Method for washing is conventional method, and finally makes the sodium oxide content in the boehmite be lower than 1 weight %.
According to method provided by the invention, described moulding can be carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.For example when extrusion, described mixture can be mixed and add an amount of peptizing agent, extrusion molding then with an amount of water.The kind of described peptizing agent and consumption all can be this area routines.
Described sintering temperature is the sintering temperature of conventional preparation macropore alumina supporter, is preferably 600-1100 ℃, more preferably 700-1000 ℃, more be preferably 800-950 ℃, and roasting time is preferably 0.5-4 hour, more is preferably 1-3 hour.
Carrier according to method preparation provided by the invention, its pore volume is 0.9-1.3 milliliter/gram, and it is that the hole of 20-100 nanometer accounts for total pore volume 7-25%, bore dia accounts for total pore volume 7-25% for the hole greater than 100 nanometers that preferred bore dia accounts for total pore volume 55-85%, bore dia less than the hole of 20 nanometers.
Macropore alumina supporter provided by the invention is suitable for preparing the especially Hydrodemetalation catalyst of the higher decompression residuum of tenor of mink cell focus, residual oil.In addition, compare with the similar carrier of existing method preparation, this preparing carriers technology is simple, makes it easier of industrial enforcement.
Below by example explanation the present invention.
Agents useful for same in the example except that specifying, is chemically pure reagent.
Example 1-6 illustrates macropore alumina supporter provided by the invention and preparation method thereof.
Example 1
Adopt aluminium hydroxide (Shandong Aluminum Plant's product) and NaOH (Beijing Chemical Plant's product) prepared in reaction concentration be 200 gram aluminium oxide/liter NaAlO
2Solution, with this solution and concentration be 90 gram aluminium oxide/liter Al
2(SO
4)
3Solution (Chang Ling oil plant 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 an ageing can, collect after 20 minutes, slurries are switched in another ageing can collect.Collected and added sodium carbonate adjusting pH value to 10 in the ageing can that finishes, aging 50 minutes then, filter, with 30 times of 50 ℃ of deionized waters washings 4 times, prepare 14 kilograms of 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.
Get 6.5 kilograms of (Al of this wet cake
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 inlet temperatures, spray-drying under 145 ℃ of conditions of outlet temperature obtains 930 gram composition PB-1, and the content of organic expanding agent is 2.1 weight % among the PB-1.
PB-1 is extruded into circumscribed circle diameter on banded extruder be 1.4 millimeters three leaf bars, and 120 ℃ of dryings in 800 ℃ of roastings 3.5 hours, obtained carrier Z1 after 4 hours, and the pore volume of Z1 and pore size distribution (mercury injection method is measured, down with) are listed in the table 1.
Comparative Examples 1
This Comparative Examples illustrates 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, inlet temperature is 600 ℃ afterwards, and spray-drying under 145 ℃ of conditions of outlet temperature obtains 890 gram boehmite CPB-1.
CPB-1 is extruded into circumscribed circle diameter on banded extruder be 1.4 millimeters three leaf bars, carries out roasting according to example Z1 condition after 120 ℃ of oven dry, makes carrier R1, and the pore volume and the pore size distribution of carrier are listed in the table 1.
Example 2
Get 20 liters of concentration and be 20 gram aluminium oxide/liter sodium aluminate solution (preparation method is with example 1), place one 25 liters one-tenth glue jar, 15 ℃ of initial temperatures feed carbon dioxide and the Air mixing gas of carbon dioxide content 30 volume % from the bottom that becomes the glue jar, the flow of gaseous mixture is 35 meters
3/ hour, reacted 5 minutes, the pH value drops to 6.8 (endpoint pH), and this moment, reaction temperature was 28 ℃, become the glue reaction to finish, filter,, filter and obtain the boehmite wet cake at last with 20 times of 45 ℃ of deionized waters making beating washings 5 times, by become glue, washing 2 times again with quadrat method, altogether about 8 kilograms of 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.
Get 5.5 kilograms of (Al of this wet cake
2O
3Content 14 weight %) be that 2000 polyethylene glycol, 7.7 grams mix with molecular weight, add water and pull an oar, finally obtain 10 liters in slurries, afterwards in 580 ℃ of inlet temperatures, spray-drying under 120 ℃ of conditions of outlet temperature obtains 700 gram composition PB-2, and the content of organic expanding agent is 1 weight % among the PB-2.
PB-2 is extruded into circumscribed circle diameter on banded extruder be 1.4 millimeters three leaf bars, and 120 ℃ of dryings in 750 ℃ of roastings 3 hours, obtained carrier Z2 after 4 hours, and pore volume and the pore size distribution of Z2 are listed in the table 1.
Comparative Examples 2
This illustrates the same the present invention of preparation method, contains organic expanding agent example, but the boehmite composition and method of making the same that boehmite degree of crystallinity can not meet the demands.
Change initial one-tenth glue temperature in the example 2 into 40 ℃, endpoint pH is controlled at 10.5, and aging temperature is 95 ℃, and ageing time is 240 minutes, and other condition is constant, makes 8 kilograms of 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 polyethylene glycol, 7.7 grams mix with molecular weight, add water and pull an oar, finally obtain 10 liters in slurries, afterwards in 580 ℃ of inlet temperatures, spray-drying under 120 ℃ of conditions of outlet temperature obtains 700 gram composition CPB-2, and the content of organic expanding agent is 1 weight % among the CPB-2.
CPB-2 is extruded into circumscribed circle diameter on banded extruder be 1.4 millimeters three leaf bars, carries out roasting according to example Z2 condition after 120 ℃ of oven dry, makes carrier R2, and the pore volume and the pore size distribution of carrier are listed in the table 1.
Example 3
With concentration be 15 the gram aluminium 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 an ageing can, collect after 60 minutes, slurries are switched in another ageing can collect.Collected the interior slurries of the ageing can that finishes aging 30 minutes, filter,, prepare 7.5 kilograms of boehmite wet cakes thus with 30 times of 55 ℃ of deionized waters washings 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.
Get 5 kilograms of (Al of this wet cake
2O
3Content 18 weight %) with peregal (SA-20, a kind of AEO) 18 grams mix, add the water making beating, finally obtain 9 liters in slurries, afterwards in 550 ℃ of inlet temperatures, spray-drying under 125 ℃ of conditions of outlet temperature obtains 890 gram composition PB-3, and the content of organic expanding agent is 2 weight % among the PB-3.
PB-3 is extruded into circumscribed circle diameter on banded extruder be 1.4 millimeters three leaf bars, and 120 ℃ of dryings in 900 ℃ of roastings 3 hours, obtained carrier Z3 after 4 hours, and pore volume and the pore size distribution of Z3 are listed in the table 1.
Example 4
With concentration be 12 the gram aluminium 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 an ageing can, collect after 60 minutes, slurries are switched in another ageing can collect.Collected in the ageing can that finishes slurries aging 30 minutes, and filtered, washed 3 times with 30 times of 30 ℃ of deionized waters, prepared 6 kilograms of 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.
Get 5.5 kilograms of (Al of this wet cake
2O
3Content 16 weight %) be that 6000 polyethylene glycol, 15 grams mix with molecular weight, add water and pull an oar, finally obtain 9 liters in slurries, afterwards in 580 ℃ of inlet temperatures, spray-drying under 120 ℃ of conditions of outlet temperature obtains 790 gram composition PB-4, and the content of organic expanding agent is 1.7 weight % among the PB-4.
PB-4 is extruded into circumscribed circle diameter on banded extruder be 1.4 millimeters three leaf bars, and 120 ℃ of dryings in 900 ℃ of roastings 3.5 hours, obtained carrier Z4 after 4 hours, and pore volume and the pore size distribution of Z4 are listed in the table 1.
Example 5
Method by Chinese patent CN 85 1 00218A examples 1 prepares boehmite, promptly in 2 liters of there-necked flasks of band stirring and backflow, the azeotropic mixture (water content is about 1.5%) that adds 1100 gram isopropyl alcohol-water, after being heated to boiling the about 500 thawing aluminium isopropoxides that restrain are added dropwise in the flask by separatory funnel, reflux time is 5 hours, steam about 700 grams of dehydration isopropyl alcohol, water content about 0.2%, gradation adds about 1.5 liters of deionized waters and wears out then, aging temperature is controlled at 60 ℃, ageing time is 55 minutes, and ageing process steams about 1200 grams of aqueous isopropanol, filters afterwards and obtains about 850g boehmite wet cake, repeated test 10 times, obtain about 8.5 kilograms of 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.
Get 8 kilograms of (Al of this wet cake
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 inlet temperatures, spray-drying under 110 ℃ of conditions of outlet temperature obtains 1700 gram composition PB-5, and the content of organic expanding agent is 5.9 weight % among the PB-5.
PB-4 is extruded into circumscribed circle diameter on banded extruder be 1.4 millimeters three leaf bars, and 120 ℃ of dryings in 900 ℃ of roastings 3 hours, obtained carrier Z5 after 4 hours, and pore volume and the pore size distribution of Z5 are listed in the table 1.
Example 6
In 30 liters the reactor that a band stirs, add 20 liters in water, start agitating device, mixing speed is 180 rev/mins, adds 30 milliliters of red fuming nitric acid (RFNA)s (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 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.
Get 4.5 kilograms of (Al of this wet cake
2O
3Content 17 weight %) mix with methylcellulose 12 grams, add the water making beating, finally obtain 10 liters in slurries, afterwards in 450 ℃ of inlet temperatures, spray-drying under 110 ℃ of conditions of outlet temperature obtains 950 gram composition PB-10, and the content of organic expanding agent is 1.6 weight % among the PB-5.
PB-4 is extruded into circumscribed circle diameter on banded extruder be 1.4 millimeters three leaf bars, and 120 ℃ of dryings in 900 ℃ of roastings 3 hours, obtained carrier Z6 after 4 hours, and pore volume and the pore size distribution of Z6 are listed in the table 1.
Table 1
| Example | Carrier | Press mercury character | |||
| Pore volume ml.g -1 | Pore size distribution (diameter)/% | ||||
| ????＜20nm | ???20-100nm | ??＞100nm | |||
| ????1 | ????Z1 | ????1.00 | ????76.4 | ????11.7 | ????11.9 |
| Comparative Examples 1 | ????R1 | ????0.79 | ????92.6 | ????4.1 | ????3.3 |
| ????2 | ????Z2 | ????1.17 | ????65.0 | ????18.9 | ????16.1 |
| Comparative Examples 2 | ????R2 | ????0.37 | ????98.1 | ????1.9 | ????0 |
| ????3 | ????Z3 | ????1.23 | ????58.5 | ????21.0 | ????20.5 |
| ????4 | ????Z4 | ????1.24 | ????58.1 | ????19.8 | ????22.1 |
| ????5 | ????Z5 | ????1.10 | ????70.9 | ????13.2 | ????15.9 |
| ????6 | ????Z6 | ????1.07 | ????78.9 | ????10.9 | ????10.2 |
The result of table 1 can show, compare with Comparative Examples, the inventive method adopts organic additive to contain the carrier that low boehmite composition obtains after moulding, roasting, and its pore volume median pore diameter obviously improves between the percentage that the pore volume of 20-100 nanometer and＞100 nanometers accounts for total pore volume.
Example 7-11 explanation is by the catalyst of macropore alumina supporter preparation provided by the invention.
Example 7
Get Z1 carrier 200 grams, contain MoO with 550 milliliters
365 grams per liters, the ammonium molybdate of NiO 11.8 grams per liters and nickel nitrate mixed solution dipping 2 hours filters the back in 120 ℃ of oven dry 2 hours, and 500 ℃ of roastings 4 hours obtain catalyst C1.Molybdenum oxide among the catalyst C31, the content of nickel oxide are listed in the table 2.
Comparative Examples 4
Get carrier R1 200 grams, be prepared into catalyst CD1 by example 7 methods.Molybdenum oxide among the catalyst CD1, the content of nickel oxide are listed in the table 2.
Example 8
Get Z2 carrier 200 grams, contain MoO with 250 milliliters
360 grams per liters, the ammonium molybdate of NiO 12 grams per liters and nickel nitrate mixed solution dipping 2 hours, in 120 ℃ of oven dry 2 hours, 550 ℃ of roastings 2 hours obtained catalyst C2.Molybdenum oxide among the catalyst C2, the content of nickel oxide are listed in the table 2.
Example 9
Get Z3 carrier 200 grams, contain MoO with 600 milliliters
3110 grams per liters, the ammonium molybdate of NiO 19 grams per liters and nickel nitrate mixed solution dipping 1.5 hours filters the back in 120 ℃ of oven dry 2 hours, and 470 ℃ of roastings 4 hours obtain catalyst C3.Molybdenum oxide among the catalyst C3, the content of nickel oxide are listed in the table 2.
Example 10
Get Z4 carrier 200 grams, contain WO with 500 milliliters
368 grams per liters, the ammonium metatungstate of NiO 31 grams per liters and nickel nitrate mixed solution dipping 1 hour filters the back in 120 ℃ of oven dry 2 hours, and 450 ℃ of roastings 4 hours obtain catalyst C4.Tungsten oxide among the catalyst C4, the content of nickel oxide are listed in the table 2.
Example 11
Get Z5 carrier 200 grams, contain MoO with 500 milliliters
352 grams per liters, the molybdic acid of CoO 14.5 grams per liters acid ammonium and cobalt nitrate mixed solution dipping 1 hour filter the back in 120 ℃ of oven dry 2 hours, and 480 ℃ of roastings 2.5 hours obtain catalyst C5.Molybdenum oxide among the catalyst C5, the content of cobalt oxide are listed in the table 2.
Table 2
| Example number | Used carrier | The catalyst numbering | Metal oxide content, heavy % | |||
| ??MoO 3 | ????WO 3 | ????NiO | ????CoO | |||
| ????7 | ????Z1 | ????C1 | ??6.2 | ????/ | ????1.2 | ????/ |
| Comparative Examples 4 | ????R2 | ????CD1 | ??6.4 | ????/ | ????1.3 | ????/ |
| ????8 | ????Z2 | ????C2 | ??7.9 | ????/ | ????1.8 | ????/ |
| ????9 | ????Z3 | ????C3 | ??12.3 | ????/ | ????2.1 | ????/ |
| ????10 | ????Z4 | ????C4 | ??/ | ????6.7 | ????2.8 | ????/ |
| ????11 | ????Z5 | ????C5 | ??4.6 | ????/ | ????/ | ????1.7 |
Example 12-16
Example 12-16 explanation is by the HDM performance of the catalyst of preparing carriers provided by the invention.
With nickel content is that 24.4ppm, content of vanadium are that the reduced crude of 77.8ppm is a raw material, evaluate catalysts on 100 milliliters of small stationary bed bioreactors.
Catalyst C1, C2, C3, C4, C5 are broken into the particle of diameter 2-3 millimeter, and the catalyst loading amount is 100 milliliters.Reaction condition is: 385 ℃ of reaction temperatures, hydrogen dividing potential drop 14 MPas, liquid hourly space velocity (LHSV) are 0.8 hour
-1, hydrogen to oil volume ratio is 1000, reacts sampling after 200 hours.
Adopt plasma emission spectrum (AES/ICP) method to measure the content that generates nickel, vanadium in the oil, calculate demetallization per, the results are shown in table 3.
Comparative Examples 4
HDM performance according to the method evaluate catalysts CD1 of example 12 the results are shown in Table 3.
Table 3
| Example number | The catalyst numbering | Demetallization per/% |
| ????12 | ????C1 | ????67.3 |
| Comparative Examples 4 | ????CD1 | ????58.1 |
| ????13 | ????C2 | ????71.8 |
| ????14 | ????C3 | ????72.4 |
| ????15 | ????C4 | ????69.8 |
| ????16 | ????C5 | ????67.0 |
Can be seen that by table 3 catalyst C1 and the contained active metal component of catalyst CD1 and content are basic identical, different is that the carrier that C1 adopts is carrier Z1 provided by the invention, and the carrier that CD1 adopts is the carrier R2 of Comparative Examples 2 preparations.But the demetallization per of C1 exceeds 9.2 percentage points than CD1.And the HDM activity of catalyst C3 that the invention provides preparing carriers shows and adopts the Hydrodemetalation catalyst that the invention provides preparing carriers to have superior demetalization function more up to 72.4%.
Claims (13)
1, a kind of preparation method of macropore alumina supporter, this method comprises boehmite composition molding and the roasting that contains organic expanding agent with a kind of, it is characterized in that, total amount with composition is a benchmark, described composition contains the boehmite of 92-99.5 weight %, organic expanding agent of 0.5-8 weight %, and boehmite wherein is a kind of degree of crystallinity less than 70% boehmite.
2, method according to claim 1 is characterized in that, is benchmark with the total amount of composition, and described composition contains the boehmite of 94-99 weight %, organic expanding agent of 1-6 weight %.
3, method according to claim 1 is characterized in that, described boehmite is that a kind of degree of crystallinity is the boehmite of 10-68%.
4, method according to claim 3 is characterized in that, described boehmite is that a kind of degree of crystallinity is the boehmite of 25-60%.
5, method according to claim 1 and 2 is characterized in that, described preparation of compositions method is drawn together and will be contained the slurries spray-drying of boehmite, organic expanding agent.
6, method according to claim 5 is characterized in that, described spray-dired inlet temperature is 350-600 ℃, and outlet temperature is 95-180 ℃.
7, method according to claim 6 is characterized in that, described inlet temperature is 400-550 ℃, and outlet temperature is 110-150 ℃.
8, method 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 surfactant.
9, method according to claim 1 is characterized in that, described sintering temperature is 600-1100 ℃, and roasting time is 0.5-4 hour,
10, method according to claim 9 is characterized in that, described sintering temperature is 700-1000 ℃.
11, method according to claim 10 is characterized in that, described sintering temperature is 800-950 ℃.
12, a kind of macropore alumina supporter, this carrier pore volume is 0.9-1.3 milliliter/gram, it is characterized in that, described carrier is by any described method preparation among the claim 1-11.
13, carrier according to claim 12, it is characterized in that it is that the hole of 20-100 nanometer accounts for total pore volume 7-25%, bore dia accounts for total pore volume 7-25% for the hole greater than 100 nanometers that described carrier hole diameter accounts for total pore volume 55-85%, bore dia less than the hole of 20 nanometers.
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