CN103769134A - Preparation method of catalyst for partial oxidation of isobutene to prepare methylacrolein - Google Patents
Preparation method of catalyst for partial oxidation of isobutene to prepare methylacrolein Download PDFInfo
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Abstract
The invention discloses a preparation method of a catalyst for partial oxidation of isobutene to prepare methylacrolein. The preparation method comprises the following steps: grinding waste hydro-treatment catalysts, adding a strong inorganic acid to dissolve the catalyst powder, filtering, adding an alkaline solution into the filtrate to adjusting the pH value of the filtrate to a range of 9.0 to 12.0, then dissolving a Bi precursor into a nitric acid solution, adding the nitric acid solution into the filtrate, adjusting the pH value of the solution to a range of 7.0 to 9.0 to generate precipitant, filtering, washing, drying, and burning the precipitant, and finally forming so as to obtain the catalyst. The preparation method recycles the active metals in waste hydro-treatment catalysts, and at the same time takes the deposited Fe, Ni and V, and the added Bi as the active metal components, and Al2O3 in waste hydro-treatment catalysts as the carrier of the catalyst to prepare a catalyst, which has the advantages of large specific surface area and high activity and is used for partial oxidation of isobutene to prepare methylacrolein. The preparation method has the advantages of simpleness and easy operation, and can fully utilize the carriers and metals in waste hydro-treatment catalysts.
Description
Technical field
The present invention relates to a kind of method of being prepared oxidation catalyst by dead catalyst, particularly prepared the method for isobutene partial oxidation MAL catalyst by useless 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.Enterprise generally abandons these dead catalyst or is used as the filler of the industries such as building, but there is very large problem in this: in hydrogenation catalyst, generally contain the metal values oxides such as molybdenum that total amount is 20 wt%～40 wt%, tungsten, cobalt, nickel, so processing can cause the wasting of resources; And because the loss meeting 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, (3) oxidizing roasting, (4) alkaline leaching reclaims molybdenum, vanadium, (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.
MAL is the intermediate of the important fine chemical products such as synthetic medicine, agricultural chemicals, dyestuff, is also the important intermediate of synthesize methyl acrylic acid and methyl methacrylate simultaneously.Methyl methacrylate is a kind of important organic chemical industry's intermediate, can be used for producing lucite, plastic modifier, senior environmental protection coating material and binding agent etc., is widely used in the fields such as national defence, building and fine chemistry industry.At present, the traditional handicraft of industrial production methyl methacrylate is mainly the Acetone cyanohydrin method take acetone and hypertoxic hydrogen cyanide as raw material, and course of reaction also will be used sulfuric acid and the caustic soda of highly corrosive, and accessory substance is many, and cost of material is high, serious environment pollution.Technique by isobutylene oxidation legal system for methyl methacrylate, because of advantages such as raw material sources are extensive, atom utilization is high, environmental pollution is little, in C 4 fraction, contain a large amount of isobutenes, producing methyl methacrylate take isobutene as raw material is the optimization utilization of hybrid C 4 resource, is the most competitive process route in environmental protection and economic aspect.Compared with current industrial conventional method, the method all has significant advantage at aspects such as the green degree of reaction raw materials, catalyst performance, production process, and the atom utilization of whole technique can reach 74%.And selective isobutene oxidation to prepare MAL be the committed step of preparing methyl methacrylate.At present, the catalyst of isobutylene oxidation MAL processed, mainly take molybdenum-bismuth system as main, adopts coprecipitation and infusion process preparation conventionally.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of preparation method of isobutene partial oxidation MAL catalyst.The method can effectively be utilized useless hydrotreating catalyst, obtain high performance isobutene partial oxidation MAL catalyst, Mo, Co, Ni and alumina support in useless hydrotreating catalyst are not only utilized, and take full advantage of Fe, the Ni and the V that on useless hydrotreating catalyst, deposit, solve the pollution problem of dead catalyst, and economize on resources, increase the benefit, easily implement technically.
The preparation method of described isobutene partial oxidation MAL catalyst, comprising:
(1) hydrotreating catalyst that will give up grinds;
(2) in step (1), add strong inorganic acid to dissolve, solids removed by filtration insoluble matter;
(3) in the filtrate obtaining to step (2), add alkaline solution, regulator solution pH value is 9.0 ~ 12.0;
(4) precursor of Bi is dissolved in to salpeter solution, joins in the mixture that step (3) obtains, control pH 7.0 ~ 9.0, produce precipitation, by sediment filter, washing, dry, roasting, then moulding obtains catalyst.
Wherein the described useless hydrotreating catalyst of step (1) refers to and does not reach former reaction requirement, or due to grating is former thereby there is no the fixed bed of complete deactivation or ebullated bed on the catalyst for hydrotreatment of residual oil that uses, take aluminium oxide as carrier, containing active metal Mo, be generally residuum hydrodesulfurization catalyst, the residuum hydrogenating and metal-eliminating catalysts such as MoCo, MoNiCo, MoNi.
Described isobutene partial oxidation MAL catalyst, take the weight of catalyst as benchmark, MoO
3content be 17 % ~ 26 %, Bi
2o
3content be 2 % ~ 6 %, the content of CoO is 4 % ~ 9 %, V
2o
5content be 3 % ~ 11 %, Fe
2o
3content be 0.3 % ~ 1.5 %, the content of NiO is 1.2 % ~ 4.8 %, Al
2o
3content be 50 % ~ 70 %.
In step (1), useless hydrotreating catalyst is 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.Sintering temperature is 300 ℃ ~ 600 ℃, roasting 2 h～6 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, the volume ratio that makes strong inorganic acid and dead catalyst is 1:1 ~ 1:10.
Described in step (2), in useless hydrotreating catalyst course of dissolution, need heating, temperature, at 40 ℃ ~ 80 ℃, needs strong stirring in course of dissolution.
Described in step (3), alkaline solution is ammoniacal liquor, sal volatile or ammonium bicarbonate soln, and step (3) hierarchy of control temperature is at 40 ℃ ~ 80 ℃.
The precursor of Bi described in step (4) is one or more in bismuth nitrate, bismuth oxide.
Concentration of nitric acid described in step (4) is 20 wt% ~ 40 wt%.
In the middle precipitation process of step (4), temperature is at 40 ℃ ~ 80 ℃.After precipitation finishes at 50 ℃ ~ 70 ℃ aging 1 h ~ 3 h, mixture filters, and washs by deionized water.
Sediment described in step (4) after washing is dry 5 h ~ 10 h at 80 ℃ ~ 120 ℃, roasting 2 h ~ 6 h at 500 ℃ ~ 700 ℃.
In the inventive method, also can supplement according to the composition of the content of Metals from Spent Catalysts Mo, Co, V, Ni, Fe and the Kaolinite Preparation of Catalyst of wanting as required, one or more of precursor that add Mo, Co, V, Ni, Fe in step (3), 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; The precursor of V is one or more in ammonium metavanadate, vanadic anhydride; The precursor of Ni is one or more in nickel nitrate, nickel chloride; The precursor of Fe is one or more in ferric nitrate, iron chloride.
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 useless hydrotreating 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.
2, the inventive method takes full advantage of metal M o, Co, Ni and the carrier A l in useless hydrotreating catalyst
2o
3simultaneously also take full advantage of Fe, the Ni and the V that are deposited on catalyst, as active metal and the carrier of isobutene partial oxidation MAL catalyst, can realize the comprehensive utilization of metal and carrier on dead catalyst, improve resource utilization, saved great amount of cost.
3, the present invention by adding strong inorganic acid solution in dead catalyst, metal and alumina catalyst support dissolving in catalyst are entered in solution, add alkaline solution regulator solution in certain pH value scope, aluminium can all be precipitated, then add the precursor acid solution of Bi, then active metal is all precipitated, avoided active metal to enter in a large number caltalyst inner mutually, so not only improve the utilization rate of active metal, and improved the catalytic activity of catalyst.
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.Wt% is mass fraction.
Embodiment 1
(1) preparation of catalyst, step is as follows:
Select the useless hydrodesulfurization MoCo/Al of fixed bed residual hydrogenation commercial plant
2o
3catalyst, removes 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%, Fe:0.15 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, until solid almost all dissolves, filter and collect filtrate, in filtrate, add 13.7 g cobalt nitrates, 0.58 g nickel nitrate, 2.95 g ferric nitrate, after stirring and dissolving, add ammoniacal liquor to regulate pH value to 8.0, 8.2 g bismuth nitrates are dissolved in the salpeter solution of 50 mL 40 wt% simultaneously, then join in filtrate, produce precipitation at once, after aging 4 h, by sedimentation and filtration, with deionized water washing 3 times, filter cake is dry 8 h at 110 ℃, roasting 4 h at 600 ℃, after compression molding, obtain final catalyst MoBiCoVFeNi/Al
2o
3.Take the weight of catalyst as benchmark, MoO
3content be 18.0 %, Bi
2o
3content be 3.6 %, the content of CoO is 5.8 %, V
2o
5content be 3.9 %, Fe
2o
3content be 0.8 %, the content of NiO is 2.2 %, Al
2o
3content be 65.7 %.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 i-C
4h
8: Air=1.0:15.0, flow velocity: 30 mL/min, air speed: 3600 mLh
-1g
cat -1, 380 ℃ of reaction temperatures, the gas chromatograph on-line analysis of unstripped gas and product.The isobutene partial oxidation MAL reaction result of catalyst is in table 2.
Embodiment 2
The catalyst using in embodiment 1 is ground to 200 orders (referring to by 200 mesh sieves), take 100 grams of powder weight, add mixed solution 300 mL of the 98 wt% concentrated sulfuric acids and 65 wt% nitric acid, volume ratio is 2:1, at 50 ℃, constant temperature stirs, until solid almost all dissolves, filter and collect filtrate, in filtrate, add ammonium heptamolybdate 6.9 g, ammonium metavanadate 1.05 g, cobalt nitrate 21.8 g, nickel nitrate 3.8 g, ferric nitrate 4.56 g, after stirring and dissolving, add ammoniacal liquor to regulate pH value to 9.0, 10.7 g bismuth nitrates are dissolved in the salpeter solution of 50 mL 40 wt% simultaneously, then join in filtrate, produce precipitation at once, after aging 4 h, by sedimentation and filtration, with deionized water washing 3 times, filter cake is dry 8 h at 110 ℃, roasting 4 h at 600 ℃, after compression molding, obtain final catalyst MoBiCoVFeNi/Al
2o
3.Take the weight of catalyst as benchmark, MoO
3content be 20.7 %, Bi
2o
3content be 4.3 %, the content of CoO is 7.1 %, V
2o
5content be 4.3 %, Fe
2o
3content be 0.9 %, the content of NiO is 2.7 %, Al
2o
3content be 60 %.The physico-chemical property of catalyst is listed in table 1.
The evaluation of catalyst is with embodiment 1, and the isobutene partial oxidation MAL 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%, Fe:0.21 wt%, Al
2o
3: 68.5 wt%), catalyst is ground to 200 orders (referring to by 200 mesh sieves), take 100 grams of powder weight, add mixed solution 350 mL of the 98 wt% concentrated sulfuric acids and 65 wt% red fuming nitric acid (RFNA)s, volume ratio is 1:1, at 50 ℃, constant temperature stirs, until solid almost all dissolves, filter and collect filtrate, in filtrate, add cobalt nitrate 15.4 g, nickel nitrate 0.87 g, ferric nitrate 3.7 g, after stirring and dissolving, add ammoniacal liquor to regulate pH value to 10.0, 10.2 g bismuth nitrates are dissolved in the salpeter solution of 50 mL 40 wt% simultaneously, then join in filtrate, produce precipitation at once, after aging 4 h, by sedimentation and filtration, with deionized water washing 3 times, filter cake is dry 8 h at 110 ℃, roasting 4 h at 600 ℃, after compression molding, obtain final catalyst MoBiCoVFeNi/Al
2o
3.Take the weight of catalyst as benchmark, MoO
3content be 21.3 %, Bi
2o
3content be 4.5 %, the content of CoO is 5.4 %, V
2o
5content be 2.7 %, Fe
2o
3content be 0.9 %, the content of NiO is 2.8 %, Al
2o
3content be 62.4 %.The physico-chemical property of catalyst is listed in table 1.
The evaluation of catalyst is with embodiment 1, and the isobutene partial oxidation MAL reaction result of catalyst is in table 2.
Embodiment 4
The catalyst using in embodiment 3 is ground to 200 orders (referring to by 200 mesh sieves), take 100 grams of powder weight, add mixed solution 450 mL of 35 wt% concentrated hydrochloric acids and 65 wt% red fuming nitric acid (RFNA)s, volume ratio is 1:1, at 50 ℃, constant temperature stirs, until solid almost all dissolves, filter and collect filtrate, in filtrate, add ammonium heptamolybdate 7.5 g, ammonium metavanadate 2.4 g, cobalt nitrate 31.1 g, nickel nitrate 3.8 g, ferric nitrate 5.3 g, after stirring and dissolving, add ammoniacal liquor to regulate pH value to 11.0, 13 g bismuth nitrates are dissolved in the salpeter solution of 50 mL 40 wt% simultaneously, then join in filtrate, produce precipitation at once, after aging 4 h, by sedimentation and filtration, with deionized water washing 3 times, filter cake is dry 8 h at 110 ℃, roasting 4 h at 600 ℃, after compression molding, obtain final catalyst MoBiCoVFeNi/Al
2o
3.Take the weight of catalyst as benchmark, MoO
3content be 23.6 %, Bi
2o
3content be 5.0 %, the content of CoO is 8.1 %, V
2o
5content be 4.0 %, Fe
2o
3content be 1.1 %, the content of NiO is 3.0 %, Al
2o
3content be 55.2 %.The physico-chemical property of catalyst is listed in table 1.
The evaluation of catalyst is with embodiment 1, and the isobutene partial oxidation MAL reaction result of catalyst is in table 2.
Embodiment 5
In embodiment 1, catalyst is changed into the useless HDM HDM MoNi/Al of fixed bed residual hydrogenation commercial plant
2o
3catalyst (containing Mo:6.5 wt%, Ni:4.9 wt%, V:7.5 wt%, Fe:0.39 wt%, Al
2o
3: 69.9 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, until solid almost all dissolves, filter and collect filtrate, in filtrate, add ammonium heptamolybdate 18.1 g, cobalt nitrate 32 g, ferric nitrate 2.75 g, after stirring and dissolving, add ammoniacal liquor to regulate pH value to 10.0, 10.7 g bismuth nitrates are dissolved in the salpeter solution of 50 mL 40 wt% simultaneously, then join in filtrate, produce precipitation at once, after aging 4 h, by sedimentation and filtration, with deionized water washing 3 times, filter cake is dry 8 h at 110 ℃, roasting 4 h at 600 ℃, after compression molding, obtain final catalyst MoBiCoVFeNi/Al
2o
3.Take the weight of catalyst as benchmark, MoO
3content be 18.7 %, Bi
2o
3content be 4.0 %, the content of CoO is 6.4 %, V
2o
5content be 10.6 %, Fe
2o
3content be 0.9 %, the content of NiO is 4.8 %, Al
2o
3content be 54.6 %.The physico-chemical property of catalyst is listed in table 1.
The evaluation of catalyst is with embodiment 1, and the isobutene partial oxidation MAL reaction result of catalyst is in table 2.
Comparative example 1
Ammonium heptamolybdate 26.2 g and ammonium metavanadate 5.5 g are dissolved in 40 mL water, make solution A; Citric acid 28 g are dissolved in 40 mL water, then add bismuth nitrate 9 g, cobalt nitrate 27.6 g, ferric nitrate 4.6 g and nickel nitrate 10.5 g, after dissolving, make solution B; Solution A and solution B mixing are made to solution C.Alumina support 60 g are placed in to mixed solution C 12 h, then at 70 ℃, solution are stirred to evaporate to dryness, solids is at 110 ℃ of dry 8 h, and roasting 4 h at 600 ℃, obtain final catalyst MoBiCoVFeNi/Al
2o
3.Take the weight of catalyst as benchmark, MoO
3content be 20.7 %, Bi
2o
3content be 4.3 %, the content of CoO is 7.1 %, V
2o
5content be 4.3 %, Fe
2o
3content be 0.9 %, the content of NiO is 2.7 %, Al
2o
3content be 60 %.The physico-chemical property of catalyst is listed in table 1.
The evaluation of catalyst is with embodiment 1, and the isobutene partial oxidation MAL 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 | 168 | 0.33 |
| Embodiment 2 | 157 | 0.30 |
| Embodiment 3 | 155 | 0.32 |
| Embodiment 4 | 142 | 0.26 |
| Embodiment 5 | 144 | 0.28 |
| Comparative example 1 | 140 | 0.35 |
The isobutene partial oxidation MAL reaction result of the each routine catalyst of table 2
| Embodiment | Isobutene conversion, % | MAL is selective, mol% |
| Embodiment 1 | 83 | 87.1 |
| Embodiment 2 | 89 | 91.2 |
| Embodiment 3 | 86 | 90.5 |
| Embodiment 4 | 91 | 92.1 |
| Embodiment 5 | 85 | 87.8 |
| Comparative example 1 | 87 | 90.8 |
Claims (14)
1. a preparation method for isobutene partial oxidation MAL catalyst, comprising:
(1) hydrotreating catalyst that will give up grinds;
(2) in step (1), add strong inorganic acid to dissolve, solids removed by filtration insoluble matter;
(3) in the filtrate obtaining to step (2), add alkaline solution, regulator solution pH value is 9.0 ~ 12.0;
(4) precursor of Bi is dissolved in to salpeter solution, joins in the mixture that step (3) obtains, control pH 7.0 ~ 9.0, produce precipitation, by sediment filter, washing, dry, roasting, then moulding obtains catalyst.
2. in accordance with the method for claim 1, it is characterized in that described useless hydrotreating catalyst is residuum hydrodesulfurization catalyst and/or residuum hydrogenating and metal-eliminating catalyst.
3. in accordance with the method for claim 1, it is characterized in that described isobutene partial oxidation MAL catalyst, take the weight of catalyst as benchmark, MoO
3content be 17 % ~ 26 %, Bi
2o
3content be 2 % ~ 6 %, the content of CoO is 4 % ~ 9 %, V
2o
5content be 3 % ~ 11 %, Fe
2o
3content be 0.3 % ~ 1.5 %, the content of NiO is 1.2 % ~ 4.8 %, Al
2o
3content be 50 % ~ 70 %.
4. in accordance with the method for claim 1, it is characterized in that in step (1), useless hydrotreating catalyst is first removed the oil on catalyst surface through extracting before pulverizing, after dry, carry out high-temperature roasting processing, sintering temperature is 300 ℃ ~ 600 ℃, roasting 2 h～6 h.
5. in accordance with the method for claim 1, it is characterized in that in step (1), useless hydrotreating catalyst grinds to more than 120 orders.
6. 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.
7. in accordance with the method for claim 1, it is characterized in that 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.
8. the concentration that in accordance with the method for claim 1, it is characterized in that the strong inorganic acid described in step (2) is 30 wt%～100 wt%; The addition of strong inorganic acid, the volume ratio that makes strong inorganic acid and dead catalyst is 1:1 ~ 1:10.
9. in accordance with the method for claim 1, it is characterized in that in useless hydrotreating catalyst course of dissolution, needing heating described in step (2), temperature, at 40 ℃ ~ 80 ℃, needs strong stirring in course of dissolution.
10. in accordance with the method for claim 1, it is characterized in that described in step (3), alkaline solution is ammoniacal liquor, sal volatile or ammonium bicarbonate soln, step (3) hierarchy of control temperature is at 40 ℃ ~ 80 ℃.
11. in accordance with the method for claim 1, and the precursor that it is characterized in that Bi described in step (4) is one or more in bismuth nitrate, bismuth oxide; The concentration of step (4) nitric acid used is 20wt% ~ 40wt%.
12. in accordance with the method for claim 1, it is characterized in that in step (4) in precipitation process that temperature is at 40 ℃ ~ 80 ℃, after precipitation finishes at 50 ℃ ~ 70 ℃ aging 1 h ~ 3 h, and then filter.
13. in accordance with the method for claim 1, it is characterized in that dry 5 h ~ 10 h at 80 ℃ ~ 120 ℃ of the sediment after washing described in step (4), roasting 2 h ~ 6 h at 500 ℃ ~ 700 ℃.
14. according to the method described in claim 1 or 3, it is characterized in that: in step (3), add one or more of precursor of Mo, Co, V, Ni, Fe, 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; The precursor of V is one or more in ammonium metavanadate, vanadic anhydride; The precursor of Ni is one or more in nickel nitrate, nickel chloride; The precursor of Fe is one or more in ferric nitrate, iron chloride.
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| CN113694913A (en) * | 2020-05-22 | 2021-11-26 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN116144930A (en) * | 2023-02-15 | 2023-05-23 | 北京科技大学 | Method for preparing hydrogenation catalyst precursor from waste hydrogenation catalyst |
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| US20040199008A1 (en) * | 2001-03-21 | 2004-10-07 | Hiroto Kasuga | Catalyst for preparation of unsaturated aldehyde and unsaturated carboxylic acid |
| CN1697694A (en) * | 2003-11-14 | 2005-11-16 | 三菱化学株式会社 | Process for producing composite oxide catalyst |
| CN102316978A (en) * | 2008-12-12 | 2012-01-11 | 巴斯夫欧洲公司 | Produce the method for geometry catalyst formed body K continuously |
| 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 |
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| US20040199008A1 (en) * | 2001-03-21 | 2004-10-07 | Hiroto Kasuga | Catalyst for preparation of unsaturated aldehyde and unsaturated carboxylic acid |
| CN1697694A (en) * | 2003-11-14 | 2005-11-16 | 三菱化学株式会社 | Process for producing composite oxide catalyst |
| CN102316978A (en) * | 2008-12-12 | 2012-01-11 | 巴斯夫欧洲公司 | Produce the method for geometry catalyst formed body K continuously |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113694913A (en) * | 2020-05-22 | 2021-11-26 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN113694913B (en) * | 2020-05-22 | 2024-03-08 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN116144930A (en) * | 2023-02-15 | 2023-05-23 | 北京科技大学 | Method for preparing hydrogenation catalyst precursor from waste hydrogenation catalyst |
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