CN1047961C - Hydrogenating treatment catalyst - Google Patents
Hydrogenating treatment catalyst Download PDFInfo
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- CN1047961C CN1047961C CN94116958A CN94116958A CN1047961C CN 1047961 C CN1047961 C CN 1047961C CN 94116958 A CN94116958 A CN 94116958A CN 94116958 A CN94116958 A CN 94116958A CN 1047961 C CN1047961 C CN 1047961C
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- catalyzer
- carrier
- weight
- catalyst
- preimpregnation
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Abstract
The present invention discloses a preparation method for a hydrogenating treatment catalyst, which comprises the following steps: macroporous aluminum hydroxide prepared from sodium aluminate and aluminium sulfate at a suitable temperature and a suitable pH value is used as a raw material; gamma-Al2O3 obtained by molding, drying and roasting the raw material is used as a carrier; ammonia water solution with low concentration of 0.01 to 0.1w% is adopted to preliminarily dip the gamma-Al2O3 before VIB and VIII group active metals are supported by the carrier, and then the metals on a final catalyst can be distributed uniformly, and the activity can be improved.
Description
The present invention relates to a kind of hydrotreating catalyst.
The hydrotreating catalyst of petroleum products is generally with γ-Al
2O
3Or contain the γ-Al of a small amount of other element (Si, P, R, Ti, F etc.)
2O
3Being carrier, is the hydrogenation activity component with W, the Mo of VI family and Co, the Ni of VIII family.
High-activity hydrogenation catalyst can make the petroleum that contains high-sulfur, nitrogen organic compound under than the demulcent operational condition, makes wherein sulphur, nitrogen compound, changes into corresponding oxide compound and is excluded.Simultaneously also can under the operational condition of harshness, improve treatment capacity, or prolong the work-ing life of catalyzer, to reach the purpose of flexible operating.
Although at present the activity of heavy oil hydrogenating treatment catalyst is quite high, more highly active hydrotreating catalyst is still that we pursue.A highly active hydrotreating catalyst is except that outside the Pass having with the metal species that is supported, amount of metal, and also the character with carrier has direct relation.The distribution of main is metal component on the carrier is wanted evenly.And this distributivity is relevant with carrier surface character.The patent of the seventies has mainly been done a large amount of work aspect support modification, pore structure is reasonable in the hope of preparing, the alumina supporter on big surface.A good carrier of hydrogenating catalyst for heavy oil, its pore volume is preferably in 0.6～1.0ml/g, pore distribution accounts for 80% of total pore volume at least at the pore volume of 4.0～15.0nm, specific surface area preferably＞300M
2/ g, on such carrier, by rights with the metal component high dispersing, the catalyzer that makes just can have enough activity.
United States Patent (USP) 4,317,746 have described carrier through after preimpregnation and the vapor portion preimpregnation, soak reactive metal again, can suitably improve the distribution of metal on carrier like this, thereby can improve catalyst activity.United States Patent (USP) 4,446,248; 4,540,483 have described the carrier of three kinds of different pore distributions respectively, adopt ammonium hydroxide aqueous solution preimpregnation, the drying of concentration 20～30w%, use citric acid wetting again, soak metallic solution then, thereby make specific activity without the active high hydrotreating catalyst of ammonia preimpregnation.
The method that provides with above-mentioned patent, support of the catalyst is handled, though certain effect is arranged, but the increase rate to catalyst activity is still big inadequately, and complex process, the cost height, particularly use the method for the ammonium hydroxide aqueous solution preimpregnation carrier of 20～30w%, because ammonia concentration height, high volatility worsens and contaminate environment working conditions.
The objective of the invention is to seek a kind of more efficiently method, support of the catalyst is carried out pre-treatment, active metal component is better disperseed in catalyzer, prepare active higher hydrotreating catalyst, reduce the catalyzer cost of manufacture simultaneously, simplify technology and reduce environmental pollution.Another object of the present invention is to seek a kind of appropriate catalyst carrier.
The present invention is with macropore γ-Al
2O
3Carrier carries out preimpregnation with the lower concentration ammonium hydroxide aqueous solution, makes carrier γ-Al
2O
3Surface hydroxylation, this hydroxylated surface is useful to improving Metal Distribution.γ-Al through the ammonia preimpregnation
2O
3Carrier does not need any processing, and direct impregnation contains the dipping solution of active metal component.Drying, roasting prepare highly active hydrotreating catalyst again.
In the Preparation of catalysts process, press carrier γ-Al
2O
3Water-intake rate and the composition of final catalyzer calculate required metal component.MoO with metering
3, basic nickel carbonate and 85% phosphoric acid and deionized water be mixed and made into steeping fluid.Under room temperature, normal pressure or decompression, flood hydroxylated γ-Al with steeping fluid
2O
3Carrier.The volume ratio of carrier and solution is 0.5～1.0, is preferably 0.7～0.9.Soak time is 0.5～4.5 hour, discharges surplus then and soaks back liquid, and 80～110 ℃ of dryings 6～10 hours, in air, in 400～600 ℃, best 400～550 ℃ of following roastings 3～6 hours made the metal that is immersed on the carrier change into metal oxide.
In the present invention, hydroxylated carrier floods preferably a kind of 10～60g/100ml MoO that contains of steeping fluid with the metal impregnation liquid that contains one or more active ingredients
3, the solution of 2～15g/100ml NiO and 1～10g/100ml P.The concentration of this solution can be decided according to the composition of the metal on the final catalyzer.
The metal constituent element of catalyzer can spray dipping, excessive impregnation method is stated from γ-Al
2O
3On the carrier.With excessive dipping is best.Can reach the high dispersing of metal by metal component and the abundant ion-exchange of surface hydroxyl, thereby improve catalyst activity.
A kind of carrier that is suitable for catalyzer of the present invention is to use CN94107259, and the disclosed macropore alumina supporter in 9 patent Shens is promptly used Al
2(SO
4)
3Or AlCl
3With ammoniacal liquor or NaAlO
2Neutralize the macropore alumina supporter that the pseudo-boehmite of generation is made through aging, washing, drying and roasting again Deng under 30～85 ℃ and PH6～10 conditions.The alumina supporter of method for preparing not only has suitable surface properties, and has positive effect to improving the hydrotreatment activity.
The composition of catalyzer of the present invention
MoO
3% (weight) 20～30 best 22～25
NiO% (weight) 1～10 best 3～5
P
2O
5% (weight) 1～10 best 5～7
The forming method of catalyzer of the present invention can be to drip ball forming, extrusion molding, compression molding, is best with extrusion molding.The shape of catalyzer is spherical, bar shaped (comprising cylindrical, trilobal, quatrefoil etc.), sheet shape or particle shape, is best with bar shaped.
Catalyzer of the present invention is the same with general hydrofining, hydrotreating catalyst, need pass through prevulcanized before use.Can in hydrogen stream, inject H
2The mode of S or other organic or inorganic sulfide is carried out.
It is that 230～550 ℃ heavy-oil hydrogenation is handled that catalyzer of the present invention can be used for boiling range.Comprising VGO, CGO, synthetic oil and shale oil, be particularly suitable for the hydrotreatment of CGO.
In another example of the present invention, use carrier of the present invention, according to U.S. Pat 4,446,248 preparation methods that announce have prepared catalyzer, under the identical operations condition, and identical raw material, result such as table 4.
Catalyzer of the present invention makes the distribution of metal on carrier very even because alumina supporter has carried out the pre-preg of lower concentration ammonium hydroxide aqueous solution.Result such as table 4.The result finds out with the catalyzer of the inventive method preparation from table, under the identical operations condition, uses identical raw material, have active high, the characteristics of good stability are compared with the catalyzer of aforesaid U.S. Patent method preparation, have both overcome the pre-wetting γ-Al of water and water vapor
2O
3The catalyst activity that carrier makes is low, has overcome the preimpregnation of high density ammoniacal liquor, drying, the citric acid also not high deficiency of wetted complex process while activity more again.
Further describe catalyst characteristics of the present invention below by several examples.
Embodiment
The present invention has prepared five kinds of different catalyzer, and the 6th catalyzer is the catalyzer of industrial application, is not have ammonia preimpregnation step with difference of the present invention, and as reference catalyst, each catalyzer all is by γ-Al
2O
3Be carrier, support molybdenum, nickel and phosphorus active constituent and auxiliary agent and make.Each catalyzer has all carried out the hydrodenitrogenationactivity activity test under use same materials oil.Detailed catalyst preparation process is described in the following example, and evaluation result is listed in table 4.
Catalyzer 1 preparation
Catalyzer 1 is the γ-Al by 100 gram CN94107259.5 method preparations
2O
3Be carrier, this carrier is bar shaped, length 3-5mm, and diameter is φ 1.3mm, is shaped as Herba Galii Bungei, pore distribution sees Table 1.
Get this carrier of 100 grams, the aqueous solution that contains 0.2 gram ammonium hydroxide with 200ml contacts, and wears out 1.0 hours under the room temperature, discharges presoak, then with isopyknic metallic solution dipping.This steeping fluid contains MoO
3123 grams, four crystal water basic nickel carbonates, 40 grams and 12.3ml concentration are 85% phosphoric acid.Left standstill 1.5 hours, and filtered, air dried overnight, 110 ℃ of dryings, under airflow, 500 ± 10 ℃ of roastings 4 hours, at last one consist of MoO
3% (weight) 24.70, NiO% (weight) 3.70, the catalyzer of P% (weight) 2.40.
Table 1 carrier γ-Al
2O
3Physico-chemical property
| Pore volume ml/g | Specific surface m 2/g | Bulk density g/ml | Pore distribution (%) nm | Most probable bore dia nm | |||
| 2.0～4.0 | 4.0～8.0 | 8.0～15.0 | ＞15.0 | ||||
| 0.658 | 317.2 | 0.570 | 6.4 | 75.7 | 12.8 | 4.9 | 8.30 |
The preparation of catalyzer 2
The preparation of catalyzer 2 and catalyzer 1 preparation are identical, just use 200ml before impregnating metal solution, contain 0.1 gram ammonium hydroxide aqueous solution contact.Finally make to consist of and contain MoO
3% (weight) 24.30, NiO% (weight) 3.76, the catalyzer of P% (weight) 2.47.
The preparation of catalyzer 3
The preparation of catalyzer 3 is identical with catalyzer 1 preparation method, just uses 200ml before impregnating metal solution, contains 4 gram lemon aqueous acids and replaces the ammonium hydroxide aqueous solution impregnated carrier.Final that a composition contains MoO
3% (weight), 24.24, NiO% (weight), the catalyzer of 3.93P% (weight) 2.96.
The preparation of catalyzer 4
The preparation of catalyzer 4 is identical with catalyzer 2 methods, just contains MoO in the 200ml metal impregnation liquid
3100 grams, NiO35 gram, 85% phosphatase 11 9ml.Finally make consisting of of catalyzer: MoO
3% (weight) 23.99, NiO% (weight) 3.78, P% (weight) 2.50.
The preparation of catalyzer 5
Catalyzer 5 preparation methods are the alumina catalyst supports with CN94107259.5, according to U.S. Pat 4,446, and 248 first preimpregnation 13.26% (weight) ammonia soln, cryodrying, the preparation of citric acid humidity method, final catalyzer consists of MoO
3% (weight) 23.77, NiO (weight), 4.03P% (weight), 2.69.
The preparation of catalyzer 6
Catalyzer 6 is a reference catalyst, the catalyzer of industrial application, and its preparation method is identical with catalyzer 1, does not just pass through ammonium hydroxide aqueous solution preimpregnation step, and final catalyzer consists of MoO
3% (weight) 22.30, NiO% (weight) 5.30, P% (weight) 4.30.
The evaluation of catalyst activity relatively
Each catalyzer is all estimated on the 200ml small hydrogenation device, and raw materials used oil is same coke charge wax oil, and stock oil character sees Table 2, estimates used condition and sees Table 3.
Table 2 wax tailings character
| 20 ℃ of density, g/cml | 0.8836 |
| Boiling range, ℃ | 227 |
| IBP | |
| 10％ | 336 |
| 30％ | 362 |
| 50％ | 374 |
| 70％ | 394 |
| 90％ | 457 |
| EP | - |
| Sulphur, % (weight) | 0.810 |
| Total nitrogen, % (weight) | 0.42 |
| Carbon residue, % (weight) | 0.08 |
| Colloid | 4.1 |
Table 3 operational condition
| Temperature of reaction ℃ | Hydrogen dividing potential drop MPa | Air speed LHSV, hr -1 | Hydrogen/oil volume ratio |
| 380 | 6.4 | 1.0 | 1000∶1 |
As reference catalyst, under the identical operations condition, establishing its activity is 100 with the catalyzer 6 of industrial application, and the relative reactivity of other five catalyzer is listed in table 4.
From the evaluation result of table 4 as can be seen, the ammonia preimpregnation is necessary to improving activity of such catalysts.The weak ammonia preimpregnation can make Metal Distribution even, and catalyst activity is best.
Table 4 is catalyst activity relatively
| Catalyzer | Catalyzer is formed % (weight) | The preimpregnation mode | Relative denitrification activity | ||
| MoO 3 | NiO | P | |||
| 1 | 24.70 | 3.70 | 2.40 | The preimpregnation of concentration 0.1% (weight) weak ammonia | 120 |
| 2 | 24.30 | 3.76 | 2.47 | The preimpregnation of concentration 0.05% (weight) weak ammonia | 128 |
| 3 | 24.24 | 3.93 | 2.96 | The preimpregnation of concentration 2% (weight) aqueous citric acid solution | 110 |
| 4 | 23.99 | 3.78 | 2.50 | Condition is with 2, steeping fluid metal concentration difference | 125 |
| 5 | 23.77 | 4.03 | 2.69 | The preimpregnation of concentration 13.26% (weight) ammonia soln, | 115 |
| 6 | 22.30 | 5.30 | 4.30 | Drying, the wetting no ammonia preimpregnation of citric acid | 100 |
Claims (6)
1, a kind of hydrotreating catalyst is with γ-Al
2O
3Be carrier, support group vib and VIII family metallic element and phosphate builder, it is characterized in that Al
2O
3Carrier carries out preimpregnation with the ammonium hydroxide aqueous solution of 0.01～0.2w%, floods pre-impregnated Al with dipping solution
2O
3Carrier supports group vib, VIII family metallic element and phosphate builder, catalyzer pore volume 0.32～0.37ml/g, specific surface 160～190m
2/ g, average pore diameter 7.5～8.3nm contains group vib metal oxide 22.5～25.5w%, VIII family metal oxide 3.6～4.4w% and P
2O
55.5～70w%.
2,, it is characterized in that described Al according to the catalyzer of claim 1
2O
3Carrier has average pore diameter 7～12nm, pore volume 0.7～1.2ml/g, specific surface 250～500m
2/ g.
3,, it is characterized in that described Al according to the catalyzer of claim 2
2O
3Carrier is by Al
2(SO
4)
3Or Al (NO
3)
3With NaAlO
2Or KAlO
2Or NH
4OH or NaOH neutralisation make.
4, according to the catalyzer of claim 1, it is characterized in that Al
2O
3Carrier carries out preimpregnation with 0.04～0.06w% ammonium hydroxide aqueous solution.
5, according to the catalyzer of claim 1, it is characterized in that described group vib metallic element is a molybdenum, VIII family metallic element is a nickel.
6,, it is characterized in that described steeping fluid made by molybdic oxide, basic nickel carbonate, 85% phosphoric acid and deionized water according to the catalyzer of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94116958A CN1047961C (en) | 1994-10-19 | 1994-10-19 | Hydrogenating treatment catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94116958A CN1047961C (en) | 1994-10-19 | 1994-10-19 | Hydrogenating treatment catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1121048A CN1121048A (en) | 1996-04-24 |
| CN1047961C true CN1047961C (en) | 2000-01-05 |
Family
ID=5038181
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94116958A Expired - Lifetime CN1047961C (en) | 1994-10-19 | 1994-10-19 | Hydrogenating treatment catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1047961C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376106B (en) * | 2007-08-31 | 2010-12-22 | 中国石油化工股份有限公司 | Heavy oil hydrogenating treatment catalyst and its preparing method |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103785404B (en) * | 2012-11-01 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
| CN104588016B (en) * | 2013-11-03 | 2017-01-25 | 中国石油化工股份有限公司 | Preparation method for hydrogenation catalyst |
| CN104588015B (en) * | 2013-11-03 | 2017-02-01 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method thereof |
| CN106466601A (en) * | 2015-08-14 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocatalyst for saturating arylhydrocarbon and the application of the catalyst prepared by the method and this catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4446248A (en) * | 1982-08-16 | 1984-05-01 | Union Oil Company Of California | Hydrotreating catalyst |
| US4540483A (en) * | 1982-08-16 | 1985-09-10 | Union Oil Company Of California | Hydrotreating process |
-
1994
- 1994-10-19 CN CN94116958A patent/CN1047961C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4446248A (en) * | 1982-08-16 | 1984-05-01 | Union Oil Company Of California | Hydrotreating catalyst |
| US4540483A (en) * | 1982-08-16 | 1985-09-10 | Union Oil Company Of California | Hydrotreating process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101376106B (en) * | 2007-08-31 | 2010-12-22 | 中国石油化工股份有限公司 | Heavy oil hydrogenating treatment catalyst and its preparing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1121048A (en) | 1996-04-24 |
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Owner name: CHINA PETROCHEMICAL CORPORATION; CHINA PETROLEUM & Free format text: FORMER NAME OR ADDRESS: CHINA PETRO-CHEMICAL CORP.; FUSHUN PETROCHEMICAL INSTITUTE., CHINA PETROCHEMICAL CORP. |
|
| CP01 | Change in the name or title of a patent holder |
Patentee after: China Petrochemical Group Corp. Patentee after: Sinopec Group Fushun Research Institute of Petroleum and Petrochemicals Patentee before: China Petrochemical Corporation Patentee before: Fushun Research Inst. of Petroleum Processing, China Petro-chem. Corp. |
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Expiration termination date: 20141019 Granted publication date: 20000105 |