CN103769136A - Preparation method of catalyst for oxidative hydrogenation of propane - Google Patents
Preparation method of catalyst for oxidative hydrogenation of propane Download PDFInfo
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- CN103769136A CN103769136A CN201210409562.2A CN201210409562A CN103769136A CN 103769136 A CN103769136 A CN 103769136A CN 201210409562 A CN201210409562 A CN 201210409562A CN 103769136 A CN103769136 A CN 103769136A
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a preparation method of a catalyst for oxidative hydrogenation of propane. The method comprises the following steps: grinding waste residual oil desulfurization catalysts into powder, adding a strong inorganic acid into the powder, filtering, adding an organic acid into the filtrate, then adding pseudo-boehmite, stirring the solution and heating at the same time until the solution is totally evaporated so as to obtain a solid substance, and then subjecting the solid substance to processes of drying, burning, and forming so as to obtain the catalyst for oxidative hydrogenation of propane. The preparation method fully utilizes the waste residual oil hydro-desulfurization catalysts, improves the resource utilization rate, and greatly reduces the cost; furthermore, the obtained catalyst has a large specific surface area, the active metal is highly dispersed on the catalyst surface, thus the utilization rate of active metal is improved, so the catalytic activity and selectivity of the catalyst are both improved.
Description
Technical field
The present invention relates to the preparation method of a kind of oxidative dehydrogenation of propane catalyst agent, particularly prepared the method for catalyst for preparing propene by oxidative dehydrogenation of propane by waste residue oil hydrotreating catalyst.
Background technology
The annual whole world all will produce a large amount of dead catalyst that cannot regenerate, and wherein hydrogenation catalyst occupies sizable proportion.Catalyst for hydrotreatment of residual oil is short service life, and cannot regenerate after inactivation due to the deposition of the impurity such as a large amount of metal Ni and V, especially in waste residue oil Hydrobon catalyst, contain the metal values oxides such as molybdenum that total amount is 20 wt%～40 wt%, cobalt, nickel, if these dead catalyst are abandoned or are used as the filler of the industries such as building, not only can cause the wasting of resources, and because the loss of metal causes certain pollution to environment, especially comparatively serious to water resource pollution.Recently, environmental regulation is more and more stricter to abandoning of dead catalyst.Useless hydrogenation catalyst is thought danger wastes by U.S. environment protection mechanism (USEPA).
The treatment technology of dead catalyst mainly comprises at present: burn (1), (2) abrasive dust, and (3) oxidizing roasting, (4) alkaline leaching reclaims molybdenum, vanadium, and (5) acidic leaching reclaims cobalt, nickel, (6) waste sludge discharge etc.The metal reclaiming in dead catalyst is a kind of selection preferably, not only can economize on resources, and can reduce environmental pollution.But existing some problems of dead catalyst metal recovery technology ubiquity: the valuable metal recoveries such as vanadium, molybdenum, cobalt, nickel are incomplete, what have only reclaims wherein one or both; The rate of recovery is lower, and the rate of recovery only has 70 %～80 % conventionally.Metal recovery processes is a kind ofly to select preferably for the catalyst really having had no value for use, but himself benefit not obvious.Especially in China, because the price of hydrogenation catalyst carried metal is relatively cheap, so from useless hydrogenation catalyst, extract reclaim metal except environmental benefit better, economic benefit is also not obvious.So from the viewpoint of environment and economy, utilizing dead catalyst is a desirable selection for raw material generates other value product.
The hydrotreater of ask for something high activity and catalysts selective, after its catalysqt deactivation, the device of (or through regeneration) applicable other lower requirement uses.When hydrotreating catalyst is along with using its activity, selective constantly decline to such an extent as to the hydrotreater of other low requirement also cannot use, still can consider it on some non-hydrogenation plant, to recycle.CN1354039A has introduced a kind of method for preparing catalyst of the SCR for nitrogen oxide, prepared by the dead catalyst that this catalyst uses the hydrodesulfurization of oil plant to discharge, have excellent nitrogen oxide selective removal effect and prevent better the catalyst poisoning that sulfur oxide is produced.CN1359751A has introduced a kind of for removing the Catalysts and its preparation method of dioxin, the dead catalyst preparation that this catalyst is discharged from oil plant hydro desulfurization by regeneration, have good in dioxin performance, and because its preparation cost of dead catalyst of having regenerated is lower.USP20050075528A1 has introduced a kind of technique that uses sulphur, nitrogen, aromatic hydrocarbons in dead catalyst adsorbing and removing oil product, and this technique is used NiMo/Al
2o
3and CoMo/Al
2o
3type hydrodesulfurization dead catalyst oil purification, without specially treated, need not heat when use before using.
Useless hydrogenation catalyst is also generally used for preparing new hydrogenation catalyst, but slop cut oil hydrogenation catalysts normally.Such as US4888316 grinds useless Hydrobon catalyst, add salic material, through moulding, the processing procedure such as make charcoal, obtain continuing the Hydrobon catalyst using.CN1552521A adds a small amount of active metal component then to regenerate in useless Hydrobon catalyst powder, obtains new Hydrobon catalyst.Said method is very little to the change of useless Hydrobon catalyst part, and prepare the catalyst of new same purposes according to the purposes of dead catalyst, by increasing the mode of part carrier or active metal, the raising of catalyst combination property still depends on the performance of original catalyst to a great extent.
Waste residue oil hydrotreating catalyst is owing to wherein depositing the impurity such as a large amount of vanadium, cover catalyst surface, number of active center is reduced, or blocking catalyst aperture, the utilization of inner surface hindered, and the heavy metals such as the vanadium of deposition can make the activated centre of catalyst poisoning, if it can not be removed from catalyst, catalyst is difficult to by regeneration activity recovery, even for the preparation of new hydrogenation catalyst, also can make a big impact to catalyst performance, cause its rapid deactivation.
Propylene is a kind of very important Organic Chemicals, is widely used in generating the serial important chemical products such as polypropylene, polyacrylonitrile, phenol, oxo alcohol, expoxy propane, methacrylaldehyde and acrylic acid.At present, propylene is mainly produced by petroleum catalytic cracking, propane catalytic dehydrogenation.The production process of Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane is subject to the control of thermodynamical equilibrium, severe reaction conditions, and also existence causes the problems such as catalyst rapid deactivation because of carbon distribution.And oxidative dehydrogenation of propane is a kind of new way of preparing propylene, compared with catalytic dehydrogenation processes, can overcome at the lower temperature of being limited in of thermodynamical equilibrium and carry out, without carbon distribution, catalyst does not need frequent regeneration.Oxidative dehydrogenation of propane catalyst is mainly catalytic component based on vanadium (barium oxide of V-Mg-O, load etc.) and catalyst with base of molybdenum (Mo-Mg-O, Ni-Mo-O etc.).
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of preparation method of oxidative dehydrogenation of propane catalyst.The method has not only been utilized Mo, Co and alumina support in useless hydrotreating catalyst, and take full advantage of the V depositing on useless hydrotreating catalyst, solve the pollution problem of dead catalyst, and economize on resources, increase the benefit, easily implement technically the function admirable of the oxidative dehydrogenation of propane catalyst of gained.
The preparation method of oxidative dehydrogenation of propane catalyst of the present invention, comprising:
(1) waste residue oil Hydrobon catalyst is ground;
(2) in step (1), add strong inorganic acid, solids removed by filtration insoluble matter after reaction;
(3) in the filtrate obtaining to step (2), add organic acid;
(4) boehmite is joined in the solution that step (3) obtains, heating is stirred to solution evaporate to dryness, obtains solids;
(5) the solids that step (4) obtains obtains oxidative dehydrogenation of propane catalyst of the present invention through super-dry, roasting, moulding.
Described waste residue oil Hydrobon catalyst is take aluminium oxide as carrier, and active metal component is containing Mo and Co.
In the present invention, described dead catalyst is not reached former reaction requirement, or due to grating is former thus there is no the fixed bed of complete deactivation or ebullated bed on the residuum hydrodesulfurization catalyst that uses.In step (1), also can add the useless Hydrodemetalation catalyst of part.Wherein in useless Hydrobon catalyst, conventionally contain active metal Mo and Co in oxide more than 13 wt%.In described dead catalyst, also can contain other active metal component such as Ni, can also contain adjuvant component, such as one or more in titanium, boron etc.Described dead catalyst is owing to being hydrotreating catalyst used in hydrogenation process, so in hydrogenation process, generally have part metals Ni and V deposition.
In described oxidative dehydrogenation of propane catalyst, take the weight of catalyst as benchmark, MoO
3content be 2.7 % ~ 9.6 %, the content of CoO is 0.2% ~ 1.9 %, V
2o
5content be 0.9 % ~ 3.7 %, Al
2o
3content be 85.0 % ~ 96.0 %.In the inventive method, also can suitably supplement according to the content of Mo, Co, V in dead catalyst as required, in step (3), add one or more in the precursor of Mo, Co, V, wherein the precursor of Mo is one or more in ammonium heptamolybdate, ammonium tetramolybdate, the precursor of Co is one or more in cobalt nitrate, cobalt carbonate, and the precursor of V is one or more in ammonium metavanadate, vanadic sulfate.
In step (1), dead catalyst is preferably first removed the oil on catalyst surface through extracting before pulverizing, after being dried, carries out high-temperature roasting processing, to remove the materials such as carbon elimination and sulphur.Wherein, sintering temperature is 300 ℃ ~ 600 ℃, and roasting time is 2.0 h～6.0 h.
In step (1), useless hydrotreating catalyst grinds to more than 120 orders, preferably more than 200 orders.
Strong inorganic acid described in step (2) is one or more mixed acid in red fuming nitric acid (RFNA), the concentrated sulfuric acid, concentrated hydrochloric acid, is preferably the concentrated sulfuric acid or red fuming nitric acid (RFNA) and concentrated hydrochloric acid mixed acid or red fuming nitric acid (RFNA) and concentrated sulfuric acid mixed acid.The concentration of strong inorganic acid is generally 30 wt%～100 wt%, and wherein the concentration of concentrated hydrochloric acid is more than 30 wt%, and the concentration of red fuming nitric acid (RFNA) is more than 50 wt%, and the concentration of the concentrated sulfuric acid is more than 50 wt%.The addition of strong inorganic acid, making the volume ratio of strong inorganic acid and dead catalyst is 1:1 ~ 1:10, and the boehmite adding in step (4) is not exclusively dissolved.
Described in step (2), in dead catalyst course of dissolution, need heating, temperature, at 40 ℃ ~ 80 ℃, needs strong stirring in course of dissolution.
Organic acid described in step (3) is one or more in citric acid, tartaric acid, malic acid, with the mol ratio of Mo in oxidative dehydrogenation of propane catalyst be 0.2 ~ 0.8.
Boehmite described in step (4) joins in the solution that step (3) obtains, and at temperature 50 C ~ 80 ℃, is stirred to the whole evaporates to dryness of solution.The addition of described boehmite adds according to the requirement of dead catalyst and final catalyst.
The described drying condition of step (5) is dry 4 h ~ 12 h at 60 ℃ ~ 120 ℃, and roasting condition is roasting 2 h ~ 6 h at 400 ℃ ~ 700 ℃.
Method of the present invention compared with prior art, has the following advantages and feature:
1, physical property (specific surface, pore volume and aperture) and the mechanical performance of the inventive method to dead catalyst requires lower, be specially adapted to recycle and do not reached former reaction requirement, or due to grating is former thus there is no the fixed bed of complete deactivation or ebullated bed on the catalyst for hydrotreatment of residual oil that uses as residuum hydrodesulfurization catalyst.
2, the inventive method takes full advantage of active metal Mo and the Co in dead catalyst, and be deposited on the V on catalyst, as the active metal of catalyst for preparing propene by oxidative dehydrogenation of propane, also take full advantage of the alumina catalyst support of dead catalyst simultaneously, thereby realize the comprehensive utilization of metal and carrier, improve resource utilization, saved great amount of cost.
3, the present invention by adding strong inorganic acid solution in dead catalyst, dissolving metal in catalyst is entered in solution, and add boehmite under acid condition, boehmite disperses at acid condition, make boehmite particle from large to small, and the accumulation mode of granule interior particle has destruction to a certain degree, and first deposit as carrier precursor using part boehmite solid particle, in follow-up heating whipping process, aluminium in solution can be in advance deposited on not only the surface of boehmite particle soon but also uniformly, make the pore structure of the aluminium oxide obtaining tightr, increase the specific area of catalyst, active metal is deposited on the surface of alumina support afterwards, avoid like this active metal to enter in a large number caltalyst inner mutually, so not only improve the utilization rate of active metal, and due to organic acid and active metal interaction, further promote active metal better to disperse on carrier, improve the decentralization of active metal, the acidity of catalyst dehydrogenating propane reaction preferably simultaneously, improve the catalytic activity of catalyst with selective.
4, technology novelty of the present invention, reasonable flowsheet structure, method is simple, operation easy to implement, energy consumption is low.
The specific embodiment
Further illustrate the solution of the present invention and effect below by specific embodiment.In the present invention, wt% is mass fraction.
Embodiment 1
(1) preparation of catalyst, step is as follows:
Select the useless hydrodesulfurization HDS catalyst (MoCo/Al of fixed bed residual hydrogenation commercial plant
2o
3), remove the oil on catalyst surface through extracting, and useless HDS catalyst after obtaining processing after dry, roasting (containing Mo:12.7 wt%, Co:2.2 wt%, V:2.4 wt%, Ni:1.7 wt%, Al
2o
3: 71.6 wt%), catalyst is ground to 200 orders (referring to by 200 mesh sieves), take 100 grams of powder weight, add the 98 wt% concentrated sulfuric acid 250 mL, at 50 ℃, constant temperature stirs, and makes dissolution of solid, filters and collects filtrate, in filtrate, adds 2.1 g NH
4vO
3, after stirring and dissolving, add citric acid 12.5 g, after all dissolving, add boehmite 135 g, at 70 ℃, be stirred to solution evaporate to dryness, by gained solid, at 100 ℃ of dry 8 h, roasting 4 h at 600 ℃, obtain final catalyst MoCoV/Al after compression molding
2o
3.Take the weight of catalyst as benchmark, MoO
3content be 9.6 %, the content of CoO is 1.4 %, V
2o
5content be 3.0 %, Al
2o
3content be 86 %.The physico-chemical property of catalyst is listed in table 1.
(2) evaluating catalyst:
Catalyst performance evaluation is carried out on atmospheric fixed bed micro-reaction equipment, catalyst loading amount 0.5 g, reaction gas composition C
3h
8: Air=1.0:4.0, flow velocity: 30 mL/min, air speed: 3600 mLh
-1gcat.
-1, 540 ℃ of reaction temperatures, the gas chromatograph on-line analysis of unstripped gas and product.The preparing propene by oxidative dehydrogenation of propane reaction result of catalyst is in table 2.
Embodiment 2
In embodiment 1, the concentrated sulfuric acid is changed into mixed solution 300 mL of the 98 wt% concentrated sulfuric acids and 65 wt% nitric acid, volume ratio is 2:1, and citric acid changes 7.5 g into, and boehmite changes 370 g into, and all the other are with embodiment 1, and gained catalyst is MoCoV/Al
2o
3.Take the weight of catalyst as benchmark, MoO
3content be 5.6 %, the content of CoO is 0.8 %, V
2o
5content be 1.6 %, Al
2o
3content be 92 %.The physico-chemical property of catalyst is listed in table 1.
The evaluation of catalyst is with embodiment 1, and the preparing propene by oxidative dehydrogenation of propane reaction result of catalyst is in table 2.
Embodiment 3
In embodiment 1, catalyst is changed into the useless hydrodesulfurization HDS MoCoNi/Al of fixed bed residual hydrogenation commercial plant
2o
3catalyst (containing Mo:15.6 wt%, Co:1.6 wt%, V:1.7 wt%, Ni:2.3 wt%, Al
2o
3: 68.5 wt%), the concentrated sulfuric acid changes mixed solution 350 mL of the 98 wt% concentrated sulfuric acids and 65 wt% red fuming nitric acid (RFNA)s into, and volume ratio is 1:1, NH
4vO
3change 5.5 g into, add cobalt nitrate 3.8 g, citric acid changes 15.4 g into, and boehmite changes 290 g into, and all the other are with embodiment 1, and gained catalyst is MoCoV/Al
2o
3.Take the weight of catalyst as benchmark, MoO
3content be 7.7 %, the content of CoO is 0.7 %, V
2o
5content be 1.6 %, Al
2o
3content be 90 %.The physico-chemical property of catalyst is listed in table 1.
The evaluation of catalyst is with embodiment 1, and the preparing propene by oxidative dehydrogenation of propane reaction result of catalyst is in table 2.
Embodiment 4
In embodiment 3, mixed acid is changed into mixed solution 450 mL of 35 wt% concentrated hydrochloric acids and 65 wt% red fuming nitric acid (RFNA)s, volume ratio is 1:1, NH
4vO
3change vanadic sulfate 5.06 g into, citric acid changes tartaric acid 7.2 g into, and boehmite changes 290 g into, and all the other are with embodiment 3, and gained catalyst is MoCoV/Al
2o
3.Take the weight of catalyst as benchmark, MoO
3content be 7.5 %, the content of CoO is 1.0 %, V
2o
5content be 2.3 %, Al
2o
3content be 89.2 %.The physico-chemical property of catalyst is listed in table 1.
The evaluation of catalyst is with embodiment 1, and the preparing propene by oxidative dehydrogenation of propane reaction result of catalyst is in table 2.
Comparative example 1
By boehmite roasting 4 h at 600 ℃, make Al
2o
3carrier.
By 10.9 g ammonium heptamolybdates, 4.4 g cobalt nitrates and 3.5 g NH
4vO
3be dissolved in 150 mL water, be made into mixed solution.By 100 g Al
2o
3carrier is placed in mixed solution 12 h, then at 70 ℃, solution is stirred to evaporate to dryness, and solids is at 110 ℃ of dry 8 h, and roasting 4 h at 600 ℃, obtain final catalyst MoCoV/Al after compression molding
2o
3.Take the weight of catalyst as benchmark, MoO
3content be 7.5 %, the content of CoO is 1.0 %, V
2o
5content be 2.3 %, Al
2o
3content be 89.2 %.The physico-chemical property of catalyst is listed in table 1.
The evaluation of catalyst is with embodiment 1, and the preparing propene by oxidative dehydrogenation of propane reaction result of catalyst is in table 2.
The physico-chemical property of the each routine catalyst of table 1
| Embodiment | Specific area, m 2/g | Pore volume, mL/g |
| Embodiment 1 | 185 | 0.45 |
| Embodiment 2 | 203 | 0.50 |
| Embodiment 3 | 180 | 0.46 |
| Embodiment 4 | 183 | 0.47 |
| Comparative example 1 | 165 | 0.52 |
The preparing propene by oxidative dehydrogenation of propane reaction result of the each routine catalyst of table 2
| Embodiment | Conversion of propane, % | Propylene Selectivity, mol% |
| Embodiment 1 | 33 | 45.3 |
| Embodiment 2 | 24 | 50.6 |
| Embodiment 3 | 30 | 46.1 |
| Embodiment 4 | 28 | 55.4 |
| Comparative example 1 | 25 | 55.1 |
Claims (14)
1. a preparation method for oxidative dehydrogenation of propane catalyst, comprising:
(1) waste residue oil Hydrobon catalyst is ground;
(2) in step (1), add strong inorganic acid, solids removed by filtration insoluble matter after reaction;
(3) in the filtrate obtaining to step (2), add organic acid;
(4) boehmite is joined in the solution that step (3) obtains, heating is stirred to solution evaporate to dryness, obtains solids;
(5) the solids that step (4) obtains obtains oxidative dehydrogenation of propane catalyst through super-dry, roasting, moulding.
2. in accordance with the method for claim 1, it is characterized in that described waste residue oil Hydrobon catalyst is take aluminium oxide as carrier, active metal component contains Mo and Co.
3. according to the method described in claim 1 or 2, it is characterized in that, in described waste residue oil Hydrobon catalyst, containing active metal Mo and Co in more than oxide 13 wt%.
4. in accordance with the method for claim 1, it is characterized in that step (1) adds waste residue oil Hydrobon catalyst.
5. in accordance with the method for claim 1, it is characterized in that in described oxidative dehydrogenation of propane catalyst, take the weight of catalyst as benchmark, MoO
3content be 2.7 % ~ 9.6 %, the content of CoO is 0.2 % ~ 1.9 %, V
2o
5content be 0.9 % ~ 3.7 %, Al
2o
3content be 85.0 % ~ 96.0 %.
6. in accordance with the method for claim 1, it is characterized in that: in step (1), dead catalyst is first removed the oil on catalyst surface through extracting before pulverizing, after being dried, carry out high-temperature roasting processing, wherein, sintering temperature is 300 ℃ ~ 600 ℃, and roasting time is 2.0 h～6.0 h.
7. it is characterized in that in accordance with the method for claim 1: in step (1), dead catalyst grinds to more than 120 orders.
8. in accordance with the method for claim 1, it is characterized in that: the strong inorganic acid described in step (2) is one or more mixed acid in red fuming nitric acid (RFNA), the concentrated sulfuric acid, concentrated hydrochloric acid, the concentration of strong inorganic acid is 30 wt%～100 wt%.
9. it is characterized in that in accordance with the method for claim 8: the strong inorganic acid described in step (2) is the concentrated sulfuric acid or red fuming nitric acid (RFNA) and concentrated hydrochloric acid mixed acid or red fuming nitric acid (RFNA) and concentrated sulfuric acid mixed acid.
10. in accordance with the method for claim 1, it is characterized in that: the addition of strong inorganic acid, making the volume ratio of strong inorganic acid and dead catalyst is 1:1 ~ 1:10, and the boehmite adding in step (4) is not exclusively dissolved.
11. in accordance with the method for claim 1, it is characterized in that: described in step (2), in dead catalyst course of dissolution, control temperature at 40 ℃ ~ 80 ℃, and in course of dissolution strong stirring.
12. in accordance with the method for claim 1, it is characterized in that: organic acid described in step (3) is one or more in citric acid, tartaric acid, malic acid, and in organic acid and oxidative dehydrogenation of propane catalyst, the mol ratio of Mo is 0.2 ~ 0.8.
13. in accordance with the method for claim 1, it is characterized in that: boehmite described in step (4) joins in the solution that step (3) obtains, and at temperature 50 C ~ 80 ℃, is stirred to solution evaporate to dryness.
14. in accordance with the method for claim 1, it is characterized in that: the described drying condition of step (5) is dry 4 h ~ 12 h at 60 ℃ ~ 120 ℃, and roasting condition is roasting 2 h ~ 6 h at 400 ℃ ~ 700 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105727978A (en) * | 2014-12-06 | 2016-07-06 | 中国石油化工股份有限公司 | Preparation method of catalyst for ethane oxidative dehydrogenation to ethylene |
| CN106669847A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of aluminum oxide carrier |
| CN111905838A (en) * | 2020-08-19 | 2020-11-10 | 中化泉州石化有限公司 | Method for preparing hydrodemetallization catalyst by using residual oil hydrogenation deactivated catalyst |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944081B (en) * | 2016-01-07 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of preparation method for catalyst for preparing propene by oxidative dehydrogenation of propane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020183580A1 (en) * | 1999-08-27 | 2002-12-05 | Huntsman Petrochemical Corporation | Advances in dehydrogenation catalysis |
| CN101147865A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Method for preparing hydrogenation refined catalyst from waste catalyst |
| CN102441443A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing hydrogenation catalyst from waste catalyst mixture |
-
2012
- 2012-10-24 CN CN201210409562.2A patent/CN103769136B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020183580A1 (en) * | 1999-08-27 | 2002-12-05 | Huntsman Petrochemical Corporation | Advances in dehydrogenation catalysis |
| CN101147865A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Method for preparing hydrogenation refined catalyst from waste catalyst |
| CN102441443A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing hydrogenation catalyst from waste catalyst mixture |
Non-Patent Citations (1)
| Title |
|---|
| 韩智三等: "Mo-V-Co-O催化剂的丙烷氧化脱氢性能研究", 《厦门大学学报(自然科学版)》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105727978A (en) * | 2014-12-06 | 2016-07-06 | 中国石油化工股份有限公司 | Preparation method of catalyst for ethane oxidative dehydrogenation to ethylene |
| CN105727978B (en) * | 2014-12-06 | 2018-01-16 | 中国石油化工股份有限公司 | A kind of method for preparing catalyst for making ethylene from ethane oxidative dehydrogenation |
| CN106669847A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Preparation method of aluminum oxide carrier |
| CN106669847B (en) * | 2015-11-09 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of preparation method of alumina support |
| CN111905838A (en) * | 2020-08-19 | 2020-11-10 | 中化泉州石化有限公司 | Method for preparing hydrodemetallization catalyst by using residual oil hydrogenation deactivated catalyst |
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| CN103769136B (en) | 2015-10-21 |
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