CN1098731C - Catalyst carrier for heavy oil hydrogenation treatment and preparation thereof - Google Patents
Catalyst carrier for heavy oil hydrogenation treatment and preparation thereof Download PDFInfo
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- CN1098731C CN1098731C CN98121083A CN98121083A CN1098731C CN 1098731 C CN1098731 C CN 1098731C CN 98121083 A CN98121083 A CN 98121083A CN 98121083 A CN98121083 A CN 98121083A CN 1098731 C CN1098731 C CN 1098731C
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- Prior art keywords
- pore
- preparation
- carrier
- acid
- alumina
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- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000295 fuel oil Substances 0.000 title claims abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229920003023 plastic Polymers 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000006229 carbon black Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 150000007524 organic acids Chemical group 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 241000237509 Patinopecten sp. Species 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims 1
- 125000005619 boric acid group Chemical group 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 235000010981 methylcellulose Nutrition 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 1
- 235000020637 scallop Nutrition 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 4
- 229910001648 diaspore Inorganic materials 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 241000219782 Sesbania Species 0.000 description 6
- 229910001593 boehmite Inorganic materials 0.000 description 6
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 238000000746 purification Methods 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- 241001101998 Galium Species 0.000 description 2
- 235000014820 Galium aparine Nutrition 0.000 description 2
- 241000772415 Neovison vison Species 0.000 description 2
- 241000612118 Samolus valerandi Species 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- -1 nitric acid etc. Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 1
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- Catalysts (AREA)
Abstract
The present invention relates to a heavy oil hydrogenation treatment catalyst carrier and preparation thereof. In the process of the carrier preparation, after being mixed according to a certain proportion, pseudo thin diaspore and alumina are mixed and kneaded with a compound pore-expanding agent, etc. into a plastic body, and then, the required carrier is prepared by extruded moulding on an extruding machine, drying and high temperature calcination.
Description
Technical field
The present invention relates to a kind of carrier of hydrogenating catalyst for heavy oil and preparation method thereof, particularly residuum hydrogenating and metal-eliminating and hydrodesulfurization catalyst support and preparation method thereof.
Background technology
At present, industrial hydrotreating catalyst is a carrier with aluminium oxide or the aluminium oxide that contains a little auxiliary normally, is active component with VIII family and group vib metallic element.As everyone knows, the pore structure of catalyst is to the serviceability important influence of catalyst.For catalyst for hydroprocessing of heavy oil, especially residual hydrocracking catalyst system therefor, generally need have bigger aperture and pore volume, be beneficial to the interior diffusion of macromolecular reaction thing in the mink cell focus, avoid or slow down because the deposition of metal impurities and blocking catalyst duct, cause catalyst activity to descend fast, shorten the service cycle of device.Because the pore structure of catalyst depends primarily on the pore structure of carrier, so, at first to prepare the carrier that has than large pore volume and aperture.
The method for preparing large-pore alumina carrier is a lot, and wherein, adding expanding agent in forming process is one of method comparatively commonly used.This method is fairly simple, easily operation.But the adding of expanding agent although the porosity of carrier increases, makes the caking property variation between the alumina particle also, thereby, causing the pore size distribution disperse of carrier easily, bulk density descends, the mechanical strength variation.
USP4,448,896 and JP57-123820 in the catalyst introduced adopt physics expanding agent carbon black to carry out reaming, the carbon black use amount is big, causes prepared catalyst aperture distribution disperse, bad mechanical strength, the catalyst aperture is also less.
CN1 in 160,602, adopts physics and chemical enlargement agent simultaneously, prepared carrier and above-mentioned three kinds of patents relatively, its pore size distribution and mechanical strength all improve significantly, bulk density is moderate.But the mechanical strength of this catalyst is still lower, and pore size distribution is also not too concentrated.
Summary of the invention
It is good to the purpose of this invention is to provide a kind of mechanical strength, alumina support of pore distribution concentration and preparation method thereof.This bright carrier has sends out aperture and pore volume more greatly, moderate specific surface, suitable bulk density.
Carrier involved in the present invention, pore volume is 0.80-1.30ml/g, is preferably 0.9-1.2ml/g; Specific surface is 100-200m
2/ g is preferably 150-180m
2/ g; Can several apertures be 15-20nm, be preferably 16-19nm; The aperture accounts for more than 70% of total pore volume, mechanical strength 〉=10.0N/mm, bulk density 〉=0.52g/ml at the pore volume between the 10-20nm.
Technical essential of the present invention is: boehmite and alumina powder and compound expanding agent, extrusion aid, peptizing agent, water mix pinching by a certain percentage and go out moulding, and drying and high-temperature roasting obtain carrier of the present invention.Among the present invention, use physics and chemically composited expanding agent, the two synergy can reach tangible reaming effect, also can reduce its consumption separately.Simultaneously, add appropriate amount of alumina and peptizing agent among the present invention, aluminium oxide structure is relatively stable, plays skeleton function, can increase the intensity of carrier; The intervention of peptizing agent makes cohesiveness enhancing between the alumina powder surface particles, thereby helps adjusting the pore-size distribution of catalyst, improves its mechanical strength.
Principal character of the present invention is that the preparation process of carrier of the present invention is:
(1), boehmite dry glue powder and alumina powder and physics expanding agent, chemical enlargement agent, extrusion aid, peptizing agent, water mixes according to a certain percentage and pinches, and becomes plastic.
(2), by (1) gained material extruded moulding on banded extruder.
(3), by (2) gained material under 90-200 ℃, dry 2-8 hour or air dry.
(4), by (3) gained material at 800-1100 ℃ of following roasting 1-5 hour.
Wherein the described alumina powder of step (1) is that aluminum hydroxide solid elastomer forms 300-600 ℃ of following roasting, and this aluminum hydroxide solid elastomer can be identical or different with the used boehmite of preparation process.The consumption of aluminium oxide is 5-30m% (being benchmark with aluminium oxide total content in the material, as follows).
Described physics expanding agent is the Flammable Solid Class 4.1 particle, is preferably carbon black, and its consumption is 3-10m%; The chemical enlargement agent is the compound of phosphorous, silicon or boron, is preferably boric acid, phosphoric acid or borate, phosphate, and addition is 0.1-1.5m%.
Described extrusion aid is sesbania powder, methylcellulose, starch, polyvinyl alcohol, is preferably the sesbania powder, and addition is 4.0-6.0m%.
Described peptizing agent can be organic acid such as formic acid, acetate etc., or inorganic acid such as nitric acid etc., and addition is 1.0-3.0m%.
Not only mechanical strength is good, pore distribution concentration for the carrier of the inventive method preparation, and has bigger aperture and pore volume, moderate specific surface, suitable bulk density.Be applicable to the preparation hydrogenation catalyst, particularly be applicable to especially catalyst for hydrotreatment of residual oil of preparation mink cell focus.
The specific embodiment
Further set forth feature of the present invention below by embodiment.
Embodiment 1
230g boehmite (butt 70%) and 15g alumina powder and 12.1g carbon black, 1.55g phosphoric acid, 3.6g acetate, 7.2g sesbania powder, 211g water purification are mixed and pinch, become plastic, on banded extruder, be extruded into 1.2mm bunge bedstraw herb bar then, in 120 ℃ of dryings 4 hours, 850 ℃ of roastings 2 hours, get carrier A, its character is listed in table 1.
Embodiment 2
230g boehmite dry glue powder and 28.4g alumina powder and 10.1g carbon black, 1.82g phosphoric acid, 4.0g formic acid, 7.6g starch, 220g water purification are mixed and pinch, become plastic, on banded extruder, be extruded into 1.2mm bunge bedstraw herb bar then, in 120 ℃ of dryings 4 hours, 950 ℃ of roastings 2 hours, get carrier B, its character is listed in table 1.
Embodiment 3
In embodiment 1, phosphoric acid changes boric acid into, and acetate changes nitric acid into, and it is the cost example that the sesbania powder changes 11.8g into by 7.2g, gets support C, and its character is referring to table 1.
Embodiment 4
In embodiment 1, alumina powder changes 54g into by 15g, and the sesbania powder changes 11.8g into by 7.2g, and water purification changes 270g acetate into by 211g, and to change nitric acid into be the cost example, carrier D, its character sees Table 1.
Embodiment 5
In embodiment 1, alumina powder changes 10g into by 15g, and carbon black changes 16.2g into by 12.1g, and it is the cost example that while phosphoric acid changes aluminum phosphate into, gets carrier E, and its character sees Table 1.
Embodiment 6
In embodiment 1, changing ammonium borate 2.28g into by adding phosphatase 11 .55g is the cost example, gets carrier F, and its character sees Table 1.
Comparative example 1 (CN1,160,602)
230g boehmite dry glue powder and mixed the pinching of 11.1g carbon black, 1.45g phosphoric acid, 6.5g sesbania powder and 207g water are become plastic, press embodiment 1 same procedure extruded moulding and drying and roasting then, get carrier G, its character is referring to table 1.
Embodiment 7
This example provides the Main physical character of carrier in above-mentioned each example, sees Table 1.
The Main physical character of table 1 carrier
| Carrier | A | B | C | D | E | F | G |
| Bulk density g/ml mechanical strength N/mm specific surface m 2/ g pore volume (mercury injection method) ml/g can a few aperture nm pore-size distribution %＜10nm 10-20nm | 0.53 11.9 161 1.15 17.3 12 72 | 0.54 12.1 157 1.05 17.8 10 74 | 0.53 12.6 158 1.10 18.0 12 71 | 0.55 14.0 172 0.90 16.8 9 75 | 0.55 11.3 135 1.00 17.1 12 71 | 0.53 11.4 147 1.20 18.1 10 72 | 0.52 7.6 162 1.20 17.1 13 60 |
As can be seen from Table 1, carrier A of the present invention, B, C, D, E, F all have bigger aperture and concentrated pore size distribution, and intensity is good, and bulk density is suitable.
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98121083A CN1098731C (en) | 1998-12-16 | 1998-12-16 | Catalyst carrier for heavy oil hydrogenation treatment and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98121083A CN1098731C (en) | 1998-12-16 | 1998-12-16 | Catalyst carrier for heavy oil hydrogenation treatment and preparation thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1256969A CN1256969A (en) | 2000-06-21 |
| CN1098731C true CN1098731C (en) | 2003-01-15 |
Family
ID=5226995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98121083A Expired - Lifetime CN1098731C (en) | 1998-12-16 | 1998-12-16 | Catalyst carrier for heavy oil hydrogenation treatment and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1098731C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101632934B (en) * | 2009-08-19 | 2012-03-28 | 中国海洋石油总公司 | Preparation method and application of a catalyst for hydrogenation of carbon five fractions |
| CN102389786B (en) * | 2011-09-16 | 2014-04-09 | 南京农业大学 | High-performance composite photocatalyst and preparation method thereof |
| CN103418349B (en) * | 2012-05-17 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of containing alcohol hydrated alumina forming matter and preparation method thereof |
| CN103418352B (en) * | 2012-05-25 | 2016-01-20 | 中国石油化工股份有限公司 | Phosphorous hydrated alumina forming matter and preparation method and prepare the method for phosphorus-containing alumina article shaped |
| CN104226286A (en) * | 2013-06-24 | 2014-12-24 | 丁章云 | Catalyst carrier and preparation method thereof |
| CN104549537B (en) * | 2013-10-23 | 2017-01-18 | 中国石油化工股份有限公司 | Preparation method for heavy oil hydrogenation catalyst carrier |
| CN104588125B (en) * | 2013-11-03 | 2016-11-16 | 中国石油化工股份有限公司 | A kind of preparation method of alumina carrier |
| CN106669649B (en) * | 2015-11-11 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of preparation method of flue gas reduction and desulfurization catalyst |
| CN106669707B (en) * | 2015-11-11 | 2019-04-12 | 中国石油化工股份有限公司 | The preparation method of Hydrodemetalation catalyst |
| CN106914280A (en) * | 2015-12-28 | 2017-07-04 | 中国石油天然气股份有限公司 | Preparation method of catalyst carrier for residual oil hydrotreating |
| CN107774278B (en) * | 2016-08-31 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of preparation method of flue gas reduction and desulfurization catalyst |
| CN107774240B (en) * | 2016-08-31 | 2019-10-15 | 中国石油化工股份有限公司 | The preparation method of flue gas reduction and desulfurization catalyst |
| CN108187709B (en) * | 2017-12-22 | 2020-06-19 | 洛阳金达石化有限责任公司 | Preparation method of deep hydrodesulfurization catalyst and application of catalyst |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57123820A (en) * | 1981-01-19 | 1982-08-02 | Mitsubishi Chem Ind Ltd | Production of formed body of porous activated alumina |
| DE3841114A1 (en) * | 1987-12-12 | 1989-06-22 | Kansai Coke & Chemicals | METHOD FOR PRODUCING AN ADSORPTION AGENT FOR SEPARATING AND DETERMINING CO |
| US5157007A (en) * | 1989-12-09 | 1992-10-20 | Degussa Ag | Catalyst for purification of exhaust gases of diesel engines and method of use |
| CN1160602A (en) * | 1996-03-26 | 1997-10-01 | 中国石油化工总公司抚顺石油化工研究院 | Large-pore alumina carrier and its preparation process |
-
1998
- 1998-12-16 CN CN98121083A patent/CN1098731C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57123820A (en) * | 1981-01-19 | 1982-08-02 | Mitsubishi Chem Ind Ltd | Production of formed body of porous activated alumina |
| DE3841114A1 (en) * | 1987-12-12 | 1989-06-22 | Kansai Coke & Chemicals | METHOD FOR PRODUCING AN ADSORPTION AGENT FOR SEPARATING AND DETERMINING CO |
| US5157007A (en) * | 1989-12-09 | 1992-10-20 | Degussa Ag | Catalyst for purification of exhaust gases of diesel engines and method of use |
| CN1160602A (en) * | 1996-03-26 | 1997-10-01 | 中国石油化工总公司抚顺石油化工研究院 | Large-pore alumina carrier and its preparation process |
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| CN1256969A (en) | 2000-06-21 |
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