CN103769173B - A kind of Application way of useless hydrotreating catalyst - Google Patents
A kind of Application way of useless hydrotreating catalyst Download PDFInfo
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Abstract
The invention discloses a kind of Application way of useless hydrotreating catalyst.The method utilizes useless hydrotreating catalyst to prepare propane partial oxidation acrolein catalyst and hydrotreating catalyst, not only make use of Mo, Co, Ni and alumina support in useless hydrotreating catalyst, and take full advantage of Ni and V that useless hydrotreating catalyst deposits, solve the pollution problem of dead catalyst, and economize on resources, increase the benefit, easily implement technically.
Description
Technical field
The present invention relates to a kind of Application way of useless hydrotreating catalyst, namely prepared the method for oxidation catalyst and hydrogenation catalyst by useless hydrotreating catalyst, particularly prepared the method for propane partial oxidation acrolein catalyst and hydrotreating catalyst by useless hydrotreating catalyst.
Background technology
The annual whole world all will produce a large amount of dead catalyst that cannot carry out regenerating, and wherein hydrogenation catalyst occupies sizable proportion.These dead catalyst generally abandon or are used as the filler of the industries such as building by enterprise, but there is very large problem in this: generally containing the metal values oxide such as molybdenum, tungsten, cobalt, nickel that total amount is 20wt% ~ 40wt% in hydrogenation catalyst, process like this can cause the wasting of resources; And due to the loss of metal can cause 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 current dead catalyst mainly comprises: (1) burns, (2) abrasive dust, (3) oxidizing roasting, and (4) alkaline leaching reclaims molybdenum, vanadium, (5) acidic leaching Call Provision, nickel, (6) waste sludge discharge etc.The metal reclaimed 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, have only reclaim wherein one or both; The rate of recovery is lower, and the usual rate of recovery only has 70% ~ 80%.Metal recovery processes is a kind ofly to select preferably for the catalyst really had no value for use, but himself benefit not obvious.Especially in China, because the price of hydrogenation catalyst carried metal is relatively cheap, thus extract from useless hydrogenation catalyst Footwall drift except environmental benefit better except, economic benefit is also not obvious.So, from the viewpoint of environment and economy, utilize dead catalyst for raw material be a desirable selection to generate other value product.
The hydrotreater of ask for something high activity and catalysts selective, after its catalysqt deactivation, the device of (or through regeneration) other lower requirement applicable uses.When hydrotreating catalyst, along with use, it is active, selective continuous decline to such an extent as to the hydrotreater of other low requirement also cannot use, and it still can be considered to recycle on some non-hydrogenation plant.CN1354039A describes 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 the catalyst poisoning to sulfur oxide generation better.CN1359751A describes a kind of Catalysts and its preparation method for removing dioxin, the dead catalyst preparation that this catalyst is discharged from oil plant hydro desulfurization by regeneration, have excellent in dioxin performance, and lower owing to having regenerated its preparation cost of dead catalyst.USP20050075528A1 describes a kind of technique using sulphur, nitrogen, aromatic hydrocarbons in dead catalyst adsorbing and removing oil product, and this technique uses NiMo/Al
2o
3and CoMo/Al
2o
3type hydrodesulfurization dead catalyst oil purification, without specially treated before using, need not heat during use.
Useless hydrogenation catalyst is also generally used for preparing new hydrogenation catalyst, but normally slop cut oil hydrogenation catalysts.Useless Hydrobon catalyst grinds by such as US4888316, adds salic material, through the processing procedure such as shaping, to make charcoal, obtains the Hydrobon catalyst that can continue to use.CN1552521A adds a small amount of active metal component then to regenerate in useless Hydrobon catalyst powder, obtains new Hydrobon catalyst.The change of said method to useless Hydrobon catalyst part is very little, and the catalyst of new same purposes is prepared according to the purposes of dead catalyst, by increasing the mode of Component Vectors 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, hinder the utilization of inner surface, 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 if for the preparation of new hydrogenation catalyst, also can make a big impact to catalyst performance, cause its rapid deactivation.
Summary of the invention
In order to overcome weak point of the prior art, the invention provides a kind of Application way of useless hydrotreating catalyst.The method utilizes useless hydrotreating catalyst to prepare propane partial oxidation acrolein catalyst and hydrotreating catalyst, the method not only make use of Mo, Co, Ni and alumina support in useless hydrotreating catalyst, and take full advantage of Ni and V that useless hydrotreating catalyst deposits, solve the pollution problem of dead catalyst, and economize on resources, increase the benefit, easily implement technically.
The Application way of described useless hydrotreating catalyst, comprising:
(1) useless hydrotreating catalyst is ground;
(2) join in ammoniacal liquor soak obtaining dead catalyst powder in step (1), then filter, obtain filtrate A and solid insoluble B;
(3) solid insoluble B is joined in strong inorganic acid dissolve, after filtration, obtain liquor C;
(4) in filtrate A, add the presoma of tellurium, obtain solution D, in liquor C, add the presoma of molybdenum, obtain solution E;
(5) with solution D oxide impregnation silicon carrier, heating is stirred to solution evaporate to dryness, obtains solids, drying, roasting, shaping after namely obtain propane partial oxidation acrolein catalyst;
(6) in solution E, add alkaline solution, adjust ph to 6.0 ~ 10.0, heating be stirred to solution evaporate to dryness, obtain solids, drying, roasting, shaping after namely obtain hydrotreating catalyst.
Propane partial oxidation acrolein catalyst described in step (5), with the weight of catalyst for benchmark, MoO
3content be 3% ~ 12%, V
2o
5content be 0.5% ~ 2.5%, TeO
3content be 1.4% ~ 3.5%, SiO
2content be 82% ~ 95%.
Hydrotreating catalyst described in step (6), with the weight of catalyst for benchmark, MoO
3the content of content to be the content of 5% ~ 30%, CoO be 0% ~ 5%, NiO be 1.0% ~ 3.5%, Al
2o
3content be 62% ~ 94%.
The described useless hydrotreating catalyst of step (1) refers to and does not reach former reaction requirement, or the catalyst for hydrotreatment of residual oil that the fixed bed of complete deactivation or ebullated bed use is not had due to grating reason, take aluminium oxide as carrier, containing active metal Mo, Co etc., be generally residuum hydrodesulfurization catalyst and/or residuum hydrogenating and metal-eliminating catalyst.
In step (1), useless hydrotreating catalyst first removes the oil on catalyst surface through extracting before pulverizing, carries out high-temperature roasting process after drying, to remove the material such as carbon elimination and sulphur.Sintering temperature is 300 DEG C ~ 600 DEG C, roasting 2h ~ 6h.
In step (1), useless hydrotreating catalyst grinds to 120 orders, preferably more than 200 orders.
The concentration of the ammonia spirit described in step (2) is generally 20wt% ~ 40wt%, and immersion process needs to stir and heating, and soak time 2h ~ 8h, temperature is at 40 DEG C ~ 80 DEG C.
Strong inorganic acid described in step (3), one or more mixed acid in preferred red fuming nitric acid (RFNA), the concentrated sulfuric acid, concentrated hydrochloric acid, are 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 30wt% ~ 100wt%, and wherein the concentration of concentrated hydrochloric acid is at more than 30wt%, and the concentration of red fuming nitric acid (RFNA) is at more than 50wt%, and the concentration of the concentrated sulfuric acid is at more than 50wt%.The addition of strong inorganic acid, makes the volume ratio of strong inorganic acid and dead catalyst be 1:1 ~ 1:10.
Need heating in useless hydrotreating catalyst course of dissolution described in step (3), temperature, at 40 DEG C ~ 80 DEG C, needs strong stirring in course of dissolution.
Described in step (4), the precursor of tellurium is telluric acid, and the presoma of molybdenum is one or more in ammonium heptamolybdate, ammonium tetramolybdate.
Described in step (5), carrier is silica, needs to flood 5h ~ 10h, at temperature 50 C ~ 80 DEG C, be stirred to the whole evaporate to dryness of solution.
Drying condition described in step (5) is dry 4h ~ 12h at 60 DEG C ~ 120 DEG C, and roasting condition is roasting 2h ~ 6h at 400 DEG C ~ 700 DEG C.
Described in step (6), alkaline solution is ammoniacal liquor or ammonium bicarbonate soln, and concentration is generally 15wt% ~ 30wt%, and temperature, at 40 DEG C ~ 80 DEG C, needs to stir.
Drying condition described in step (6) is dry 4h ~ 12h at 60 DEG C ~ 120 DEG C, and roasting condition is roasting 2h ~ 6h at 400 DEG C ~ 700 DEG C.
In the inventive method, also can supplement according to the content of Metals from Spent Catalysts Mo, Co, V, Ni and the composition of new Kaolinite Preparation of Catalyst as required, can add the precursor of active metal Mo, Co, V or Ni in the solution D of step (4) or solution E, 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.Also Al can be added in step (6)
2o
3presoma, one or more namely in aluminum nitrate, aluminum sulfate, aluminium chloride.
Method of the present invention compared with prior art, has the following advantages and feature:
1, the inventive method to the physical property (specific surface, pore volume and aperture) of useless hydrotreating catalyst and mechanical property requirements lower, be specially adapted to recycle and do not reached former reaction requirement, or there is no catalyst for hydrotreatment of residual oil that the fixed bed of complete deactivation or ebullated bed use due to grating reason.
2, the inventive method takes full advantage of metal M o, Co and Ni in useless hydrotreating catalyst, also take full advantage of deposition V and Ni on a catalyst simultaneously, as the active metal component of propane partial oxidation acrolein catalyst and hydrotreating catalyst, also take full advantage of the carrier of alumina catalyst support as hydrotreating catalyst of dead catalyst simultaneously, realize the comprehensive utilization of metal and carrier on dead catalyst, improve resource utilization, save great amount of cost.
3, the present invention is by dead catalyst obtained propane partial oxidation acrolein catalyst and hydrotreating catalyst simultaneously.Ammonia spirit soaks dead catalyst, Mo and V is made to be dissolved in solution, after adding a small amount of active component Te, just obtain the active metal ammonia solution of propane oxidation catalyst, because ammonia and active metal interact, facilitate active metal better to disperse on carrier, improve the decentralization of active metal, improve the activity and selectivity of propane oxidation catalyst.Dead catalyst solid insoluble is joined in strong inorganic acid solution, remaining metal Co, Ni and alumina catalyst support in catalyst are dissolved to be entered in solution, then adding alkaline solution regulates solution in certain pH value scope, aluminium can be made first to become aluminum hydroxide precipitation, after heating is stirred to solution evaporate to dryness, reactive metal deposits is on the surface of alumina support, this avoid active metal, to enter caltalyst in a large number mutually inner, improve the utilization rate of active metal, make hydrotreatment agent have good catalytic activity.
4, the present invention can obtain propane oxidation catalyst and hydrotreating catalyst by dead catalyst simultaneously, and technology is novel, reasonable flowsheet structure, and method is simple, and operation easy to implement, energy consumption is low.
Detailed description of the invention
The solution of the present invention and effect is further illustrated below by specific embodiment.
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 after obtaining process after drying, roasting, useless HDS catalyst is (containing Mo:12.7wt%, Co:2.2wt%, V:2.4wt%, Ni:1.7wt%, Fe:0.15wt%, Al
2o
3: 71.6wt%), catalyst is ground to 200 orders (referring to by 200 mesh sieves), take powder weight 100 grams, add the ammoniacal liquor 200mL that concentration is 25wt%, stir at 60 DEG C and soak 6h, filter and obtain filtrate A and solid insoluble B, solid insoluble B is joined in 98wt% concentrated sulfuric acid 250mL, at 50 DEG C, constant temperature stirs, until solid almost all dissolves, filters and obtains liquor C.In filtrate A, add telluric acid 6.89g, after stirring and dissolving, obtain solution D, in liquor C, add ammonium heptamolybdate 24.2g, after stirring and dissolving, obtain solution E.Join in solution D by Support Silica 260g, dipping 8h, is stirred to the whole evaporate to dryness of solution under temperature 60 C.Then dry 8h at 110 DEG C, gained solid is roasting 4h at 600 DEG C, namely obtains final propane oxidation catalyst MoVTe/SiO after compression molding
2.In solution E, add the ammoniacal liquor that concentration is 20wt%, adjust ph to 8.0, at 60 DEG C, heating is stirred to solution evaporate to dryness, then dry 8h at 110 DEG C, and gained solid is roasting 4h at 600 DEG C, namely obtains final hydrotreating catalyst MoCoNi/Al after extruded moulding
2o
3.At propane oxidation catalyst MoVTe/SiO
2in, with the weight of catalyst for benchmark, MoO
3content be 6.7%, V
2o
5content be 1.5%, TeO
3content be 1.8%, SiO
2content be 90%.At hydrotreating catalyst MoCoNi/Al
2o
3in, with the weight of catalyst for benchmark, MoO
3the content of content to be the content of 20%, CoO be 2.9%, NiO be 2.3%, Al
2o
3content be 74.8%.The physico-chemical property of catalyst lists in table 1.
(2) evaluating catalyst
Propane oxidation catalyst performance evaluation is carried out on atmospheric fixed bed micro-reaction equipment, catalyst loading amount 0.1g, reaction gas composition C
3h
8: Air=1.0:4.0, flow velocity: 12mL/min, air speed: 7200mLh
-1gcat.
-1, reaction temperature 540 DEG C, the gas chromatograph on-line analysis of unstripped gas and product.The propane partial oxidation acrolein reaction of catalyst the results are shown in Table 2.
Hydrotreating catalyst autoclave carries out activity rating, and the physicochemical property of raw material used is in table 3, and appreciation condition is in table 4, and with the activity of comparative example for 100, the evaluation result after other and comparative example expression activitiy is in table 5.
Table 3 feedstock oil character
| Project | Feedstock oil |
| Sulphur, wt% | 3.24 |
| Carbon residue, % | 18.69 |
| Nickel+vanadium+iron, μ g/g | 238 |
Process conditions evaluated by table 4 autoclave
| Condition | |
| Reaction temperature, DEG C | 430 |
| Reaction pressure, MPa | 15 |
| Reaction time, min | 60 |
Embodiment 2
In embodiment 1, the concentrated sulfuric acid is changed into the mixed solution 300mL of the 98wt% concentrated sulfuric acid and 65wt% nitric acid, volume ratio is 2:1, and Support Silica changes 156g into, adds aluminum nitrate 235g, the other the same as in Example 1 in liquor C, obtained propane oxidation catalyst MoVTe/SiO
2with hydrotreating catalyst MoCoNi/Al
2o
3.At propane oxidation catalyst MoVTe/SiO
2in, with the weight of catalyst for benchmark, MoO
3content be 10.3%, V
2o
5content be 2.3%, TeO
3content be 2.9%, SiO
2content be 84.5%.At hydrotreating catalyst MoCoNi/Al
2o
3in, with the weight of catalyst for benchmark, MoO
3the content of content to be the content of 15%, CoO be 2.2%, NiO be 1.7%, Al
2o
3content be 81.1%.The physico-chemical property of catalyst lists in table 1.
The evaluation of catalyst is with embodiment 1, and evaluation result is in table 2 and table 5.
Embodiment 3
The useless hydrodesulfurization MoCoNi/Al of fixed bed residual hydrogenation commercial plant
2o
3catalyst is (containing Mo:15.6wt%, Co:1.6wt%, V:1.7wt%, Ni:2.3wt%, Fe:0.21wt%, Al
2o
3: 68.5wt%), catalyst is ground to 200 orders (referring to by 200 mesh sieves), take powder weight 100 grams, add the ammoniacal liquor 200mL that concentration is 25wt%, stir at 60 DEG C and soak 6h, filtration obtains filtrate A and solid insoluble B, solid insoluble B is joined the mixed solution 350mL of the 98wt% concentrated sulfuric acid and 65wt% red fuming nitric acid (RFNA), volume ratio is 1:1, and at 50 DEG C, constant temperature stirs, until solid almost all dissolves, filter and obtain liquor C.In filtrate A, add ammonium metavanadate 1.75g, telluric acid 8.45g, obtains solution D after stirring and dissolving, adds ammonium heptamolybdate 30.9g, obtain solution E after stirring and dissolving in liquor C.Join in solution D by Support Silica 240g, dipping 8h, is stirred to the whole evaporate to dryness of solution under temperature 60 C.Then dry 8h at 110 DEG C, gained solid is roasting 4h at 600 DEG C, namely obtains final propane oxidation catalyst MoVTe/SiO after compression molding
2.In solution E, add the ammoniacal liquor that concentration is 20wt%, adjust ph to 9.0, at 60 DEG C, heating is stirred to solution evaporate to dryness, then dry 8h at 110 DEG C, and gained solid is roasting 4h at 600 DEG C, namely obtains final hydrotreating catalyst MoCoNi/Al after extruded moulding
2o
3.At propane oxidation catalyst MoVTe/SiO
2in, with the weight of catalyst for benchmark, MoO
3content be 8.5%, V
2o
5content be 1.6%, TeO
3content be 2.4%, SiO
2content be 87.5%.At hydrotreating catalyst MoCoNi/Al
2o
3in, with the weight of catalyst for benchmark, MoO
3the content of content to be the content of 25%, CoO be 2.0%, NiO be 2.9%, Al
2o
3content be 70.1%.The physico-chemical property of catalyst lists in table 1.
The evaluation of catalyst is with embodiment 1, and evaluation result is in table 2 and table 5.
Embodiment 4
In embodiment 3, the mixed solution of the 98wt% concentrated sulfuric acid and 65wt% nitric acid is changed into the mixed solution 450mL of 35wt% concentrated hydrochloric acid and 65wt% red fuming nitric acid (RFNA), volume ratio is 1:1, Support Silica changes 480g into, aluminum nitrate 777g is added in liquor C, the other the same as in Example 1, obtained propane oxidation catalyst MoVTe/SiO
2with hydrotreating catalyst MoCoNi/Al
2o
3.At propane oxidation catalyst MoVTe/SiO
2in, with the weight of catalyst for benchmark, MoO
3content be 4.5%, V
2o
5content be 0.9%, TeO
3content be 1.6%, SiO
2content be 93%.At hydrotreating catalyst MoCoNi/Al
2o
3in, with the weight of catalyst for benchmark, MoO
3the content of content to be the content of 12%, CoO be 1.0%, NiO be 1.4%, Al
2o
3content be 85.6%.The physico-chemical property of catalyst lists in table 1.
The evaluation of catalyst is with embodiment 1, and evaluation result is in table 2 and table 5.
Embodiment 5
The useless HDM HDMMoNi/Al of fixed bed residual hydrogenation commercial plant
2o
3catalyst is (containing Mo:6.5wt%, Ni:4.9wt%, V:7.5wt%, Fe:0.39wt%, Al
2o
3: 69.9wt%), catalyst is ground to 200 orders (referring to by 200 mesh sieves), take powder weight 100 grams, add the ammoniacal liquor 200mL that concentration is 25wt%, stir at 60 DEG C and soak 6h, filter and obtain filtrate A and solid insoluble B, solid insoluble B is joined 98wt% concentrated sulfuric acid 250mL, at 50 DEG C, constant temperature stirs, until solid almost all dissolves, filters and obtains liquor C.In filtrate A, add ammonium heptamolybdate 78.9g, telluric acid 26.4g, obtains solution D after stirring and dissolving, adds ammonium heptamolybdate 30.3g and 1462g aluminum nitrate, obtain solution E after stirring and dissolving in liquor C.Join in solution D by Support Silica 1000g, dipping 8h, is stirred to the whole evaporate to dryness of solution under temperature 60 C.Then dry 8h at 110 DEG C, gained solid is roasting 4h at 600 DEG C, namely obtains final propane oxidation catalyst MoVTe/SiO after compression molding
2.In solution E, add the ammoniacal liquor that concentration is 20wt%, adjust ph to 9.0, at 60 DEG C, heating is stirred to solution evaporate to dryness, then dry 8h at 110 DEG C, and gained solid is roasting 4h at 600 DEG C, namely obtains final hydrotreating catalyst MoCoNi/Al after extruded moulding
2o
3.At propane oxidation catalyst MoVTe/SiO
2in, with the weight of catalyst for benchmark, MoO
3content be 6.5%, V
2o
5content be 1.2%, TeO
3content be 1.8%, SiO
2content be 90.5%.At hydrotreating catalyst MoCoNi/Al
2o
3in, with the weight of catalyst for benchmark, MoO
3content be the content of 8%, NiO be 2.1%, Al
2o
3content be 89.9%.The physico-chemical property of catalyst lists in table 1.
The evaluation of catalyst is with embodiment 1, and evaluation result is in table 2 and table 5.
Comparative example 1
29.6g ammonium heptamolybdate, 5.6g ammonium metavanadate and 8.4g telluric acid are dissolved in 100mL water, are made into mixed solution.By 240gSiO
2carrier (specific area 370m
2/ g) be placed in mixed solution 12h, then at 70 DEG C, solution is stirred evaporate to dryness, solids is at 110 DEG C of dry 8h, and roasting 4h at 600 DEG C, obtains final catalyst MoVTe/SiO
2.With the weight of catalyst for benchmark, MoO
3content be 8.5%, V
2o
5content be 1.6%, TeO
3content be 2.4%, SiO
2content be 87.5%.The physico-chemical property of catalyst lists in table 1.
The evaluation of catalyst is with embodiment 1, and evaluation result is in table 2.
Comparative example 2
24.2g ammonium heptamolybdate, 10.9g cobalt nitrate and 8.6g nickel nitrate are dissolved in 100mL water, are made into mixed solution.By 71.6g alumina support (specific area 250m
2/ g) be placed in mixed solution 12h, then at 70 DEG C, solution is stirred evaporate to dryness, solids is at 110 DEG C of dry 8h, and roasting 4h at 600 DEG C, obtains final hydrotreating catalyst MoCoNi/Al
2o
3.With the weight of catalyst for benchmark, MoO
3the content of content to be the content of 20%, CoO be 2.9%, NiO be 2.3%, Al
2o
3content be 74.8%.The physico-chemical property of catalyst lists in table 1.
The evaluation of catalyst is with embodiment 1, and evaluation result is in table 5.
The physico-chemical property of each routine catalyst of table 1
| Embodiment | Catalyst | Specific area, m 2/g | Pore volume, mL/g |
| Embodiment 1 | Catalyst MoVTe/SiO 2 | 296 | 0.75 |
| Embodiment 1 | Catalyst MoCoNi/Al 2O 3 | 210 | 0.48 |
| Embodiment 2 | Catalyst MoVTe/SiO 2 | 268 | 0.68 |
| Embodiment 2 | Catalyst MoCoNi/Al 2O 3 | 226 | 0.51 |
| Embodiment 3 | Catalyst MoVTe/SiO 2 | 285 | 0.72 |
| Embodiment 3 | Catalyst MoCoNi/Al 2O 3 | 180 | 0.44 |
| Embodiment 4 | Catalyst MoVTe/SiO 2 | 326 | 0.81 |
| Embodiment 4 | Catalyst MoCoNi/Al 2O 3 | 235 | 0.53 |
| Embodiment 5 | Catalyst MoVTe/SiO 2 | 305 | 0.77 |
| Embodiment 5 | Catalyst MoNi/Al 2O 3 | 246 | 0.56 |
| Comparative example 1 | Catalyst MoVTe/SiO 2 | 283 | 0.71 |
| Comparative example 2 | Catalyst MoCoNi/Al 2O 3 | 200 | 0.50 |
The propane partial oxidation acrolein reaction result of each routine catalyst of table 2
| Embodiment | Conversion of propane, % | Acrolein selectivity, mol% |
| Embodiment 1 | 25.7 | 39.8 |
| Embodiment 2 | 30.1 | 37.6 |
| Embodiment 3 | 28.7 | 42.8 |
| Embodiment 4 | 24.2 | 40.1 |
| Embodiment 5 | 26.1 | 40.5 |
| Comparative example 1 | 26.8 | 41.2 |
Table 5 hydrotreating catalyst reaction result
| Embodiment | 500 DEG C of conversion ratios, % | Desulfurization degree, wt% |
| Embodiment 1 | 105 | 103 |
| Embodiment 2 | 98 | 97 |
| Embodiment 3 | 112 | 109 |
| Embodiment 4 | 94 | 92 |
| Embodiment 5 | 88 | 87 |
| Comparative example 2 | 100 | 100 |
Claims (6)
1. an Application way for useless hydrotreating catalyst, comprising:
(1) useless hydrotreating catalyst is ground; Described useless hydrotreating catalyst is waste residue oil Hydrobon catalyst and/or waste residue oil Hydrodemetalation catalyst;
(2) join in ammoniacal liquor soak obtaining dead catalyst powder in step (1), then filter, obtain filtrate A and solid insoluble B;
(3) in filtrate A, add the presoma of tellurium, obtain solution D;
(4) with solution D oxide impregnation silicon carrier, heating is stirred to solution evaporate to dryness, obtains solids, drying, roasting, shaping after namely obtain propane partial oxidation acrolein catalyst; Wherein, dip time is 5h ~ 10h, at temperature 50 C ~ 80 DEG C, be stirred to the whole evaporate to dryness of solution; Described drying condition is dry 4h ~ 12h at 60 DEG C ~ 120 DEG C, and roasting condition is roasting 2h ~ 6h at 400 DEG C ~ 700 DEG C;
Propane partial oxidation acrolein catalyst described in step (4), with the weight of catalyst for benchmark, MoO
3content be 3% ~ 12%, V
2o
5content be 0.5% ~ 2.5%, TeO
3content be 1.4% ~ 3.5%, SiO
2content be 82% ~ 95%.
2. in accordance with the method for claim 1, it is characterized in that in step (1), useless hydrotreating catalyst first removes the oil on catalyst surface through extracting before pulverizing, carry out high-temperature roasting process after drying, sintering temperature is 300 DEG C ~ 600 DEG C, and roasting time is 2h ~ 6h.
3. in accordance with the method for claim 1, it is characterized in that in step (1), useless hydrotreating catalyst grinds to 120 orders.
4. in accordance with the method for claim 1, it is characterized in that the concentration of the ammonia spirit described in step (2) is 20wt% ~ 40wt%, immersion process needs to stir and heating, and soak time 2h ~ 8h, temperature is 40 DEG C ~ 80 DEG C.
5. in accordance with the method for claim 1, it is characterized in that the presoma of tellurium described in step (3) is telluric acid.
6. in accordance with the method for claim 1, it is characterized in that: supplement according to the content of Metals from Spent Catalysts Mo, V and the composition of new Kaolinite Preparation of Catalyst, in the solution D of step (3), add the presoma of active metal Mo or V, wherein the presoma of Mo is one or more in ammonium heptamolybdate, ammonium tetramolybdate; The presoma of V is one or more in ammonium metavanadate, vanadic anhydride.
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| CN105642305B (en) * | 2014-12-06 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of method for preparing catalyst for hydrogen production from methane vapor reforming |
| CN105727975B (en) * | 2014-12-06 | 2018-01-16 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for making ethylene from ethane oxidative dehydrogenation |
| CN105727979B (en) * | 2014-12-06 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of method for preparing catalyst for preparing propene by oxidative dehydrogenation of propane |
| CN105727977B (en) * | 2014-12-06 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of synthesis gas methanation substitutes the method for preparing catalyst of natural gas |
| 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 |
| CN106944137B (en) * | 2016-01-07 | 2019-07-12 | 中国石油化工股份有限公司 | The utilization method of useless hydrogenation catalyst |
| CN116139851B (en) * | 2023-01-18 | 2024-09-10 | 国家能源集团科技环保有限公司 | Resource utilization method of waste denitration catalyst |
| CN116144930B (en) * | 2023-02-15 | 2024-07-16 | 北京科技大学 | Method for preparing hydrogenation catalyst precursor from waste hydrogenation catalyst |
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| CN100594062C (en) * | 2006-09-20 | 2010-03-17 | 中国石油化工股份有限公司 | Method for preparing hydrogenation refined catalyst from waste catalyst |
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