CN1088091C - Hydrogenating catalyst for heavy oil and its preparing process - Google Patents
Hydrogenating catalyst for heavy oil and its preparing process Download PDFInfo
- Publication number
- CN1088091C CN1088091C CN99113278A CN99113278A CN1088091C CN 1088091 C CN1088091 C CN 1088091C CN 99113278 A CN99113278 A CN 99113278A CN 99113278 A CN99113278 A CN 99113278A CN 1088091 C CN1088091 C CN 1088091C
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- aluminum oxide
- solution
- catalyst
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a hydrotreating catalyst and a preparing process thereof. The hydrotreating catalyst is prepared from two aluminum oxides with different forms, a solution containing element metals in the sixth group and the eighth group, etc. through mixing, extruding, forming, drying and calcining. The hydrotreating catalyst is suitable for the hydrodesulfurization and the hydrodemetalization of heavy oil.
Description
The present invention relates to a kind of preparation of hydrotreating catalyst, this catalyzer is applicable to heavy oil hydrogenation demetal and hydrodesulfurization process.
Sulfur in heavy oil, heavy metal (as V, Ni) wait foreign matter content higher, and molecular volume are bigger, so require catalyzer to have macroporous structure.In the mink cell focus hydrogenation process, catalyzer is contaminated serious, is difficult to regeneration in addition, so, require to reduce the Preparation of Catalyst cost.As select low-cost raw material and simplify preparation technology etc.
At present, it is carrier that this type of catalyzer usually adopts porous oxide compound such as aluminum oxide, is active constituent with group vib metal such as W or Mo and VIII family metal Co or Ni.Method for preparing catalyst mainly contains: coprecipitation method, kneading method and pickling process etc.
US4 adopts in 671,866 coprecipitation method to prepare catalyzer, this catalyst surface area 112m
2/ g, pore volume 1.03ml/g, mean pore size 37.6nm.Though this catalyzer has larger aperture and pore volume, specific surface area is lower.And, this method complicated operation, production cost height.
By contrast, kneading method is operated fairly simple convenience, implements easily, helps reducing the catalyzer manufacturing cost.Adopt kneading method to prepare catalyzer, maturing temperature can not be too high, otherwise reactive metal and carrier generation strong interaction reduce catalyst activity.But maturing temperature is too low, then is difficult to obtain the required macropore of heavy-oil hydrogenation (especially demetalization) catalyzer.
For addressing this problem, US4,411,824 when preparing catalyzer with kneading method, adopted steam-treated, and the catalyzer aperture is increased.This inventive method has positive effect when hanging down for active metal component, is 0.92w% as working as active ingredient CoO, MoO
3During for 2.8w%, catalyst surface area is 184m
2/ g, pore volume 1.01ml/g, mean pore size 18nm; But being increased to CoO when active ingredient is 3.1w%, MoO
3During for 9.2w%, the catalyzer mean pore size is little, is 11.5nm, uncomfortable cooperation catalyst for heavy oil hydrogenation demetal.
At the problem that exists in the present technology, the invention provides a kind of macroporous catalyst of high metal content.A kind of Preparation of catalysts method is provided simultaneously, can increases the aperture of catalyzer by this method simply and easily.
Main points of the present invention are: the alumina material that adopts two kinds of different shapes is aluminium hydroxide (being pseudo-boehmite) and baked aluminum oxide as γ-Al
2O
3, δ-Al
2O
3, η-Al
2O
3Deng, with the metal salt solution that contains requirement concentration etc., mix the moulding of pinching bar by a certain percentage, dry then, roasting, preparation catalyzer.
Preparation of catalysts process of the present invention is: the aluminum oxide that (1) takes by weighing a certain amount of two kinds of different shapes is aluminium hydroxide (being pseudo-boehmite) and baked aluminum oxide as γ-Al
2O
3, δ-Al
2O
3, η-Al
2O
3Deng; (2) salt that will contain group vib and VIII family metal is dissolved in and makes metal salt solution A in ammoniacal liquor, citric acid and the water; (3) peptizing agent is dissolved in the suitable quantity of water, gets solution B.
With material in (1) and solution A, B mixed pinch become plastic after, extruded moulding.Extruded material descended dry 2-6 hour at 80-200 ℃, at 600-800 ℃ of following roasting 0.5-4 hour, obtained catalyzer.
The catalyzer pore volume is 0.7-1.2ml/g, is preferably 0.9-1.1ml/g, and specific surface area is 120-200m
2/ g, preferably 130-190m
2/ g, mean pore size is 15-22nm, is preferably 16-20nm.Catalyzer contains group vib metal oxide 2-14w%, is preferably 5-10w%, contains group VIII metal oxide 1-5w%, 2-4w% preferably, and remainder is an aluminum oxide.
(1) adopts the aluminum oxide of different shape in, especially add baked aluminum oxide, can adjust the pore structure of catalyzer neatly.Baked aluminum oxide, since nodulizing, grain growth, the aperture increases, and helps improving the macropore ratio of catalyzer, and simultaneously, because crystal grain is assembled, associativity strengthens, and the catalyzer physical strength also increases.Two kinds of different alumina rations are 1: 25-25: 1 (w)
(2) the group vib metal described in is W or Mo, and selected salt is preferably ammonium salt; VIII family metal is Co or Ni, and selected salt is preferably carbonate or acetate.In the drying and roasting process, the decomposition of all cpds also can be played certain reaming effect in the solution.
(3) peptizing agent described in is formic acid, acetate etc., and peptizing agent content is 0.3-4.0w% (is benchmark with alumina content in the material).
In kneading process, also can add an amount of extrusion aid such as polyvinyl alcohol, methylcellulose gum, sesbania powder and carbon black etc.These materials can play lubricated when extrusion and help the effect of squeezing, and in roasting process, owing to be oxidized to volatilizable material, have certain reaming effect simultaneously.Extrusion aid content is 1.5-5.5w% (being as the criterion with alumina content in the material).
Compared with prior art, process of the present invention is simple, and is easy to operate, and the production handiness is strong, and cost is low.The present invention adopts the aluminum oxide of two kinds of different shapes, without steam-treated, need not improve the pore structure that maturing temperature can be adjusted catalyzer easily and flexibly.By the catalyzer of the inventive method preparation, aperture and pore volume are bigger, and specific surface area is moderate, catalyst activity change of component a wider range.Catalyzer of the present invention is applicable to heavy oil hydrogenation demetal and hydrodesulfurization process.
Further describe the present invention below in conjunction with embodiment.
Embodiment 1
(1) takes by weighing aluminum hydroxide solid elastomer powder (water content 30%) and baked aluminum oxide powder of 500g and the 21g carbon black that 500g is produced by first fertilizer plant of Chinese Qilu Petrochemical company.
(2) get the 102g ammonium molybdate, the 48g nickelous carbonate, the 68g citric acid, adding 540ml concentration is the ammoniacal liquor of 14w%, stirring and dissolving.Be that the volume that 58% ammoniacal liquor and water purification are adjusted solution is 600ml with concentration then, solution A.
(3) be that the acetate of 99w% is dissolved in the 300g water with 17g concentration, solution B.
(4) solid materials in (1) is mixed with solution A and B, become plastic after, extruded moulding on banded extruder.
(5) with the extruded moulding material under 120 ℃, dry 6 hours.
(6) with material after the drying under 650 ℃, roasting 3 hours obtains catalyzer C1.
Embodiment 2
(1) take by weighing with embodiment 1 in identical aluminum hydroxide solid elastomer powder 500g and baked aluminum oxide powder 50g
With 12g sesbania powder.
(2) get the 31g ammonium molybdate, the 13g cobaltous carbonate, the 17g citric acid, adding 250ml concentration is the ammoniacal liquor of 14w%,
Stirring and dissolving.Then with concentration be 58% ammoniacal liquor and water purification to adjust liquor capacity be 300ml, solution A 1.
(3) be that the formic acid of 99w% is dissolved in the 120g water with 8g concentration, solution B 1.
(4) solid materials in (1) is mixed with solution A 1 and B1, become plastic after,
Extruded moulding on banded extruder.
(5) with the extruded moulding material under 120 ℃, dry 6 hours.
(6) with material after the drying under 650 ℃, roasting 3 hours obtains catalyzer C2.
Embodiment 3
(1) takes by weighing aluminum hydroxide solid elastomer powder (water content 30%) and baked aluminum oxide powder of 500g and the 13g carbon black that 50g is produced by first fertilizer plant of Chinese Qilu Petrochemical company.
(2) get the 64g ammonium molybdate, the 30g cobaltous carbonate, the 40g citric acid, adding 340ml concentration is the ammoniacal liquor of 14w%, stirring and dissolving.Be that the volume that 58% ammoniacal liquor and water purification are adjusted solution is 400ml with concentration then, solution A 2.
(3) be that the acetate of 99w% is dissolved in the 170g water with 11g concentration, solution B 2.
(4) solid materials in (1) is mixed with solution A 2 and B2, become plastic after, extruded moulding on banded extruder.
(5) with the extruded moulding material under 120 ℃, dry 6 hours.
(6) with material after the drying under 650 ℃, roasting 3 hours obtains catalyzer C3.
Comparative example 1
Catalyzer is according to patent US4 in this example, the preparation of 411,824 methods.
(1) the 48g Cobaltous diacetate is added in the 350ml water; (2) with 15ml, concentration is that 88% formic acid joins in the 200ml distilled water; (3) solution in (1) is joined solution in (2), get solution a1; (4) 83gMoO
3Be dissolved in 400ml, concentration and be 14% NH
4In the OH solution, get solution b1.
When temperature was 50 ℃, solution a1 mixed peptization with 850g aluminium hydroxide (with example 1).After solution a1 all adds, continue to mix 20 minutes.Then, the speed adding solution b1 with per minute 50ml after all adding, continues to mix 20 minutes, and the final mixture temperature is 65 ℃.Extrusion then, and 120 ℃ dry 2 hours down, 200 ℃ dry 2 hours down, there are roasting down 1 hour in 680 ℃, water vapor, roasting is 0.5 hour in 680 ℃, air.Get catalyzer C4, its character sees Table 1.
Embodiment 4
Present embodiment has been listed the main character and the evaluation result of catalyzer, referring to table 1.
Table 1 catalyzer salient features
| Catalyzer | C1 | C2 | C3 | C4 |
| Surface-area, m 2/ g pore volume, ml/g mean pore size, nm Al (OH) 3/γ-Al 2O 3MoO 3，m％ NiO，m％ CoO，m％ | 175 1.02 17.4 1∶1 8.58 2.95 - | 184 1.01 18.1 10∶1 6.23 - 2.02 | 155 1.04 18.3 1∶10 8.94 - 3.32 | 252 0.97 11.5 - 9.11 - 3.09 |
| Impurity removes activity relatively, and m% takes off the S activity and takes off the Ni+V activity | 1 1 | 1.00 1.02 | 1.01 1.03 | 1.02 0.87 |
Catalyst impurities removes active in following two formula calculating in the table 1:
S in the formula (1)
p, S
fBe respectively the content of sulphur in stock oil and the generation oil: S
Pr, S
FrBe respectively stock oil and the content that generates sulphur in the oil when adopting reference catalyst.
M in the formula (2)
p, M
fBe respectively stock oil and generate metals content impurity in the oil; M
Pr, M
FrMetals content impurity in stock oil and the generation oil when being respectively the employing reference catalyst.
As can be seen from Table 1: reference catalyst (C4) specific surface area is bigger, has desulphurizing activated preferably; But its aperture is little, thereby, the demetalization poor-performing.Catalyzer pore volume of the present invention and aperture are bigger, and specific surface area is moderate; Has good demetalization and desulphurizing activated.
Claims (9)
1. hydrotreating catalyst, with W and/or Mo, Ni and/or Co is active ingredient, it consists of the metal oxide 2-14w% of W and/or Mo, the metal oxide 1-5w% of Ni and/or Co, all the other are aluminum oxide, it is characterized in that adopting the aluminum oxide of two kinds of different shapes in catalyst preparation process is that aluminium hydroxide and baked aluminum oxide are carrier.
2. according to the described catalyzer of claim 1, its pore volume is 0.7-1.2ml/g, and specific surface area is 120-200m
2/ g, mean pore size is 15-22nm.
3. according to the described catalyzer of claim 2, it is characterized in that the catalyzer pore volume is 0.9-1.1ml/g, specific surface area is 130-190m
2/ g, mean pore size is 16-20nm.
4. according to the described catalyzer of claim 1, it consists of the metal oxide 5-10w% of W and/or Mo, the metal oxide 2-4w% of Ni and/or Co, and all the other are aluminum oxide.
5. according to the described catalyzer of claim 1, wherein the ratio of two kinds of aluminum oxide is 1: 25-25: 1.
6. a preparation method of hydrotreatment catalyst the steps include:
(1) aluminum oxide that takes by weighing two kinds of different shapes is hydrogen aluminium hydroxide and baked oxygen
Change aluminium, its ratio is 1: 25-25: 1;
(2) salt that will contain W/Mo and/or Ni/Co is dissolved in ammoniacal liquor, citric acid and the water and makes
Get metal salt solution A;
(3) peptizing agent is soluble in water, get solution B;
Mixed the pinching of material in (1) and solution A, B become extruded moulding behind the plastic, extrudate drying, roasting are obtained catalyzer.
7. according to the described preparation method of claim 6, wherein said baked aluminum oxide is γ-Al
2O
3, δ-Al
2O
3And/or η-Al
2O
3
8. according to the described preparation method of claim 6, wherein the peptizing agent in the step (3) is formic acid or acetate, and peptizing agent content is that benchmark is 0.3-4.0w% with alumina content in the material.
9. according to the described preparation method of claim 6, add extrusion aid polyvinyl alcohol, methylcellulose gum, sesbania powder or carbon black in kneading process, extrusion aid content is that benchmark is 1.5-5.5w% with alumina content in the material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113278A CN1088091C (en) | 1999-09-29 | 1999-09-29 | Hydrogenating catalyst for heavy oil and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113278A CN1088091C (en) | 1999-09-29 | 1999-09-29 | Hydrogenating catalyst for heavy oil and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1289824A CN1289824A (en) | 2001-04-04 |
| CN1088091C true CN1088091C (en) | 2002-07-24 |
Family
ID=5276485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99113278A Expired - Lifetime CN1088091C (en) | 1999-09-29 | 1999-09-29 | Hydrogenating catalyst for heavy oil and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1088091C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102247895B (en) * | 2010-05-20 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation methods for catalyst carrier and Fischer-Tropsch synthesis catalyst |
| CN103285934A (en) * | 2012-03-01 | 2013-09-11 | 中国石油天然气股份有限公司 | Distillate oil hydrogenation deacidification catalyst carrier containing molecular sieve and preparation method thereof |
| CN103480422B (en) * | 2012-06-12 | 2016-01-13 | 中国石油化工股份有限公司 | There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and hydrotreating method |
| CN108607618B (en) * | 2016-12-09 | 2020-12-18 | 中国石油化工股份有限公司 | Alumina carrier, silver catalyst prepared from carrier and application of silver catalyst |
| CN109722333B (en) * | 2017-10-27 | 2021-10-08 | 中国石油化工股份有限公司 | Method for improving running period of waste lubricating oil regenerating device |
| 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 |
| CN113562751B (en) * | 2020-04-28 | 2023-05-09 | 中国石油化工股份有限公司 | Modified pseudo-boehmite, preparation method thereof, modified alumina and hydrogenation catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4411824A (en) * | 1981-05-12 | 1983-10-25 | Chevron Research Company | Method of making a catalyst suitable for hydrometalation of hydrocarbonaceous feedstocks |
| US4671866A (en) * | 1986-02-26 | 1987-06-09 | Phillips Petroleum Company | Hydrodemetallization of oils |
-
1999
- 1999-09-29 CN CN99113278A patent/CN1088091C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4411824A (en) * | 1981-05-12 | 1983-10-25 | Chevron Research Company | Method of making a catalyst suitable for hydrometalation of hydrocarbonaceous feedstocks |
| US4671866A (en) * | 1986-02-26 | 1987-06-09 | Phillips Petroleum Company | Hydrodemetallization of oils |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1289824A (en) | 2001-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1782031A (en) | Slag oil hydro-demetallization catalyst and its preparing method | |
| CN1796500A (en) | Alumina supporter possessing duplicate orifice, catalyst and preparation method | |
| CN1088091C (en) | Hydrogenating catalyst for heavy oil and its preparing process | |
| CN1853777A (en) | Hydrogenation catalyst and production thereof | |
| CN1243081C (en) | Hydrotreating catalyst and preparing method thereof | |
| CN1219600C (en) | Aluminia carrier and hydrogenating catalyst with the carrier | |
| JPH05192573A (en) | Boron containing catalyst | |
| CN1107102C (en) | Demetalating and desulfurizing hydrocatalyst and its preparing process | |
| CN1123628C (en) | Heavy oil hydrogenating treatment catalyst and its preparing method | |
| JPS61138537A (en) | Production of hydrogenated desulfurizing catalyst | |
| CN110227481A (en) | A kind of catalyst for hydroprocessing of heavy oil and preparation method thereof | |
| CN1272409C (en) | Refined catalyst for fraction oil hydrogenation and its preparing method | |
| CN1120972A (en) | Hydrodesulfurizing catalyst | |
| CN1211157C (en) | Hydrocracking after-treatment catalyst and preparing method thereof | |
| CN108452849B (en) | Diesel oil hydrofining catalyst and preparation method and application thereof | |
| CN1097484C (en) | Liquid phase hydrogenating catalyst, its preparation process and application | |
| CN1714937A (en) | Great pore volume formed aluminium oxide carrier and its preparing method | |
| CN1105053A (en) | Fine catalyst produced by fraction oil hydrogenation | |
| CN1147569C (en) | Process for preparing hydrocatalyst | |
| CN1088093C (en) | Process for preparing hydrorefining catalyst | |
| CN1053458C (en) | Catalyzer for hydrotreating residuum and its prepn. method | |
| CN1590511A (en) | Fraction oil hydrogenation and acid removing eatalyst | |
| CN1210378C (en) | Hydrofining catalyst and its prepn | |
| CN1448477A (en) | Heavy raw oil hydrogenating treatment catalyst and its preparing method | |
| CN1251797C (en) | Prepn process of hydroprocessing catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20020724 |
|
| CX01 | Expiry of patent term |