CN105214728A - A kind of preparation method of non-loading type nickel molybdenum match hydrogenation catalyst - Google Patents
A kind of preparation method of non-loading type nickel molybdenum match hydrogenation catalyst Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of non-loading type nickel molybdenum match hydrogenation catalyst.Its technical scheme is: comprise step as follows: the aqueous solution of (1) preparation soluble molybdenum salt, be added dropwise to inorganic acid fluid, be warming up to more than 90 DEG C, add sulfide solution again, organic acid is added after solution changes color, through decrease temperature crystalline after reaction half an hour, finally obtain sulfur-bearing containing molybdenum anionic complex; (2) sulfur-bearing is dissolved in hot water containing molybdenum anionic complex, is added dropwise to soluble nickel salting liquid, reaction half an hour, cooling, filter, washing, dry, shaping, obtain non-loading type nickel molybdenum match hydrogenation catalyst.Beneficial effect is: invention increases the specific area of catalyst and the exposure ratio of active metal, is conducive to the activity improving catalyst; In addition, there is In-situ sulphiding phenomenon in this catalyst in hydrodesulfurization reaction process, do not need extra pre-vulcanization process, saves the energy, time cost.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst technical field, particularly a kind of preparation method of non-loading type nickel molybdenum match hydrogenation catalyst.
Background technology
Hydrogenation technique is the effective means improving oil quality, and technology most crucial in this technique is hydrogenation catalyst.Hydrogenation catalyst is divided into two classes, support type and non-loading type.Loaded catalyst is by active metal solution and carrier impregnation, drying and roasting form, content of metal is restricted (general load capacity is less than 30%), and carrier itself is not or have little catalytic activity, causes the activity of whole catalyst relatively low.In addition, there is stronger chemical interaction in carrier and active metal presoma, cause being difficult to complete cure in active metal sulfidation, catalytic activity reduces further.Therefore, at present, the research both at home and abroad for exploitation high activity unsupported catalyst is comparatively active, is also the research emphasis of numerous petroleum and petrochemical industry company.
The solution of the solution of at least one VIII non-noble metal compound with at least one group vib metallic compound contacts by CN101468309A, obtains slurries, then these slurries is carried out hydrothermal treatment consists.VIII base metal and the densification of group vib Metal Contact in this kind of catalyst, without pore creating material in catalyst.
CN103861609A preparation contains the acid solution A of at least one VIII non-noble metal compound and at least one group vib metallic compound and contains the alkaline solution B at least one silicon source or aluminium source, by two kinds of solution mixing, coprecipitation reaction, obtain slurries, aging, suction filtration, drying, shaping, roasting obtain catalyst.In this kind of catalyst, silicon source or aluminium source colloidal sol play glue combination effect, but to interact with active metal comparatively strong simultaneously, affects catalytic activity.
US4596785 discloses a kind of method utilizing the co-precipitation of metal sulfide to prepare hydrogenation catalyst.The method comprises at least one group vib metal sulfide and the non-noble metal sulfided thing mixing of at least one VIII, its preparation method is as follows: under the existence of the water-soluble vulcanizing agent of at least one, the ammonium salt of non-noble metal at least one VIII soluble salt aqueous solution and a kind of group vib metal cation of at least one is reacted, form the co-precipitation of sulfide, dry, roasting, obtains final catalyst.
The preparation of above-mentioned several catalyst all adopts coprecipitation, and hydrothermal treatment consists operating process is comparatively complicated, cost is higher, and part metals can be caused to lose, and metal recovery rate is low; Do not add the auxiliary agents such as organic acid in preparation process, pore-creating weak effect, mixed metal compositions pore structure specific area is little, and the using rate of metal of catalyst is not high, causes cost to increase; What is more important, in above-mentioned catalyst synthesis processes, do not add organic acid etc. can with the organic ligand of active metal generation chemical action, can not at molecule aspect effective expanded support group vib metal of unsupported catalyst and group VIII metal cluster, reacting from volatilization, selfdecomposition of the organic ligands such as organic acid can not be there is in subsequent high temperature processing procedure, in the inner spontaneous pore-creating of the metal atomic cluster of catalyst, the atom utilization of metal cannot be improved.
Summary of the invention
Object of the present invention is exactly in view of the foregoing defects the prior art has, provides a kind of preparation method of non-loading type nickel molybdenum match hydrogenation catalyst.
The preparation method of a kind of non-loading type nickel molybdenum match hydrogenation catalyst that the present invention mentions, its technical scheme is: comprise step as follows:
(1) prepare the aqueous solution of soluble molybdenum salt, be added dropwise to inorganic acid fluid, be warming up to more than 90 DEG C, then add sulfide solution, after solution changes color, add organic acid, through decrease temperature crystalline after reaction half an hour, finally obtain sulfur-bearing containing molybdenum anionic complex; Wherein, soluble molybdenum salt: sulfide: organic acid mol ratio is 1:2:0.5, the mass ratio of soluble molybdenum salt and inorganic acid is 3:2;
(2) sulfur-bearing is dissolved in hot water containing molybdenum anionic complex, is added dropwise to soluble nickel salting liquid, reaction half an hour, cooling, filter, washing, dry, shaping, obtain non-loading type nickel molybdenum match hydrogenation catalyst; Wherein, sulfur-bearing is 2:1 containing the mass ratio of molybdenum anionic complex and soluble nickel salt, and sulfur-bearing is 1:5 containing the mass ratio of molybdenum anionic complex and water.
Above-mentioned soluble molybdenum salt and the mass ratio of water are 1:20, form the aqueous solution of soluble molybdenum salt; Described soluble molybdenum salt is the one of sodium molybdate or ammonium molybdate, and sulfide is the one of vulcanized sodium or ammonium sulfide; Described soluble nickel salt is the one of nickel nitrate or nickel chloride.
Above-mentioned inorganic acid fluid is the one of hydrochloric acid or sulfuric acid.
Above-mentioned organic acid is the one of ethylenediamine tetra-acetic acid or cysteine.
General principle of the present invention is: under vulcanizing agent existence condition, molybdenum salt and organic acid generation coordination chemistry, organic acid is enable to rely on coordinate bond and molybdenum cluster to form equally distributed large molecular cluster in molecule aspect, namely containing molybdenum anionic complex, organic acid Long carbon chain structure can help molybdenum cluster molecule aspect mutually away from, between molybdenum and molybdenum atom, spacing increases; The effect of sulfide then makes anionic complex generation vulcanization reaction, containing in molybdenum anionic complex with molybdenum the part oxygen atom of mutual binding replaced by sulphur atom, define sulfur-bearing containing molybdenum anionic complex; Utilize coprecipitation reaction to be fitted together in molecule aspect containing molybdenum anionic complex and nickel ionizable metal salt by sulfur-bearing, define title complex.
The present invention compared with prior art, its beneficial effect is: nickel molybdenum match provided by the present invention is in the molecular structure containing organic acid, under the hot environment of hydrogenation catalyst, organic component can selfdecomposition, spontaneous formation between molybdenum is caused in catalyst molecule structure to decompose the orderly duct of the nanoscale vacated due to organism, and the gas such as carbon dioxide of being decomposed to form of organic acid can further pore-creating in catalyst granules, improve the specific area of catalyst and the exposure ratio of active metal, be conducive to the activity improving catalyst; In addition, due to nickel molybdenum match provided by the present invention vulcanizing treatment, the oxygen atom on organic acid carboxylic group is only had not replaced by sulphur atom, this kind of situation reduces active metal sulfuration difficulty, can make this catalyst, in hydrodesulfurization reaction process, In-situ sulphiding phenomenon occur, do not need extra pre-vulcanization process, save the energy, time cost.
Detailed description of the invention
The following examples will be further described the present invention:
Embodiment 1:
42g bis-molybdic acid hydrate sodium is dissolved in 800g water, drip 28ml hydrochloric acid, add 84g nine water cure sodium, be warming up to more than 90 DEG C, until solution become orange red after add 21g ethylenediamine tetra-acetic acid, reaction half an hour after again through decrease temperature crystalline, suction filtration, ethanol washing, drying at room temperature, obtain 47.4g sulfur-bearing containing molybdenum match, more above-mentioned sulfur-bearing is dissolved in 237g hot water containing molybdenum match; Taking 23.7g nickel nitrate is dissolved in 150g water, nickel nitrate solution is added sulfur-bearing containing in molybdenum match solution, stirs half an hour, the washing of suction filtration, ethanol, drying; Compressing tablet process is carried out at 30MPa; Granulation controls particle diameter at 20-30 order; Obtain non-loading type nickel molybdenum match hydrogenation catalyst F1.
Embodiment 2:
40g bis-molybdic acid hydrate sodium is dissolved in 800g water, drip 28ml sulfuric acid, add 80g nine water cure sodium, be warming up to more than 90 DEG C, until solution become orange red after add 20g cysteine, reaction half an hour after again through decrease temperature crystalline, suction filtration, ethanol washing, drying at room temperature, obtain 45.5g sulfur-bearing containing molybdenum match, more above-mentioned sulfur-bearing is dissolved in 227.5g hot water containing molybdenum match; Taking 22.75g nickel chloride is dissolved in 150g water, nickel chloride solution is added sulfur-bearing containing in molybdenum match solution, stirs half an hour, the washing of suction filtration, ethanol, drying; Compressing tablet process is carried out at 30MPa; Granulation controls particle diameter at 20-30 order; Obtain non-loading type nickel molybdenum match hydrogenation catalyst F2.
Embodiment 3:
15.7g ammonium molybdate is dissolved in 300g water, drip 10ml hydrochloric acid, add 80g nine water cure sodium, be warming up to more than 90 DEG C, until solution become orange red after add 29.5g bis-ethylenediamine hydrate tetraacethyl disodium, reaction half an hour after again through decrease temperature crystalline, suction filtration, ethanol washing, drying at room temperature, obtain 44.3g sulfur-bearing containing molybdenum match, more above-mentioned sulfur-bearing is dissolved in 250g hot water containing molybdenum match; Taking 25.8g nickel nitrate is dissolved in 150g water, nickel nitrate solution is added sulfur-bearing containing in molybdenum match solution, stirs half an hour, the washing of suction filtration, ethanol, drying; Compressing tablet process is carried out at 30MPa; Granulation controls particle diameter at 20-30 order; Obtain catalyst F3.
Embodiment 4:
38.4g bis-molybdic acid hydrate sodium is dissolved in 800g water, drip 28ml hydrochloric acid, add 80g nine water cure sodium, be warming up to more than 90 DEG C, until solution become orange red after add 48g mono-hydration Cys salt, reaction half an hour after again through decrease temperature crystalline, suction filtration, ethanol washing, drying at room temperature, obtain 37.6g sulfur-bearing containing molybdenum match, more above-mentioned sulfur-bearing is dissolved in 200g hot water containing molybdenum match; Taking 25.8g nickel nitrate is dissolved in 150g water, nickel nitrate solution is added sulfur-bearing containing in molybdenum match solution, stirs half an hour, the washing of suction filtration, ethanol, drying; Compressing tablet process is carried out at 30MPa; Granulation controls particle diameter at 20-30 order; Obtain catalyst F4.
Embodiment 5:
The present embodiment illustrates the preparation method of comparative catalyst.
19.2g sodium molybdate is dissolved in 400g water, drips 10ml hydrochloric acid, add 40g nine water cure sodium, be warming up to more than 90 DEG C, until solution become orange red after keep reaction half an hour after; Taking 12.9g nickel nitrate is dissolved in 80g water, is added by nickel nitrate solution in above-mentioned solution, stirs half an hour, ageing 24 hours, the washing of suction filtration, ethanol, drying; Compressing tablet process is carried out at 30MPa; Granulation controls particle diameter at 20-30 order; Obtain catalyst F5.
Embodiment 6:
The present embodiment illustrates the evaluation method of catalyst of the present invention.
Catalyst activity evaluation be 10ml high pressure micro-anti-in carry out.Model compound raw material consists of: the toluene of 2% dibenzothiophenes (DBT) (about 3630ppm sulphur).Raw material adopts plunger displacement pump to pump into, and product is isolated after gas and liquid through high and low pressure separator, and product liquid flows into and connects sample tank.This reaction does not need pre-sulfiding step, raw material (model compound) direct injected, stablizes sampling in 6 hours after being warming up to 340 DEG C, analyzes with gas chromatograph (Agilent7890 capillary chromatograph, fid detector).Reaction condition: liquid hourly space velocity (LHSV) 2.0h
-1, hydrogen-oil ratio 300:1, reaction pressure 5.0MPa.Shown in the reaction evaluating result table 1 of several catalyst.
The result of table 1 illustrates the comparative catalyst that the hydrodesulfurization activity of prepared catalyst of the present invention is significantly higher than conventional method and prepares.
Table 1 catalyst activity evaluation result of the present invention
The above, be only part preferred embodiment of the present invention, any those of ordinary skill in the art all may utilize the technical scheme correct of above-mentioned elaboration or are revised as equivalent technical scheme.Therefore, any simple modification of carrying out according to technical scheme of the present invention or substitute equivalents, belong to the scope of protection of present invention to the greatest extent.
Claims (5)
1. a preparation method for non-loading type nickel molybdenum match hydrogenation catalyst, is characterized in that: comprise step as follows:
(1) prepare the aqueous solution of soluble molybdenum salt, be added dropwise to inorganic acid fluid, be warming up to more than 90 DEG C, then add sulfide solution, after solution changes color, add organic acid, through decrease temperature crystalline after reaction half an hour, finally obtain sulfur-bearing containing molybdenum anionic complex; Wherein, soluble molybdenum salt: sulfide: organic acid mol ratio is 1:2:0.5, the mass ratio of soluble molybdenum salt and inorganic acid is 3:2;
(2) sulfur-bearing is dissolved in hot water containing molybdenum anionic complex, is added dropwise to soluble nickel salting liquid, reaction half an hour, cooling, filter, washing, dry, shaping, obtain non-loading type nickel molybdenum match hydrogenation catalyst; Wherein, sulfur-bearing is 2:1 containing the mass ratio of molybdenum anionic complex and soluble nickel salt, and sulfur-bearing is 1:5 containing the mass ratio of molybdenum anionic complex and water.
2. the preparation method of non-loading type nickel molybdenum match hydrogenation catalyst according to claim 1, is characterized in that: described soluble molybdenum salt and the mass ratio of water are 1:20, forms the aqueous solution of soluble molybdenum salt; Described soluble molybdenum salt is the one of sodium molybdate or ammonium molybdate, and sulfide is the one of vulcanized sodium or ammonium sulfide; Described soluble nickel salt is the one of nickel nitrate or nickel chloride.
3. the preparation method of non-loading type nickel molybdenum match hydrogenation catalyst according to claim 1, is characterized in that: described inorganic acid fluid is the one of hydrochloric acid or sulfuric acid.
4. the preparation method of non-loading type nickel molybdenum match hydrogenation catalyst according to claim 1, is characterized in that: described organic acid is the one of ethylenediamine tetra-acetic acid or cysteine.
5. the preparation method of non-loading type nickel molybdenum match hydrogenation catalyst according to claim 1, is characterized in that: described sodium molybdate adopts two molybdic acid hydrate sodium.
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| CN106238076A (en) * | 2016-07-27 | 2016-12-21 | 广东工业大学 | A kind of preparation method of the oxygen doping molybdenum bisuphide Hydrobon catalyst of nickel-loaded |
| CN109569664A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Sulfurized hydrogenation catalyst and its preparation method and application |
| CN109569662A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Sulfurized hydrogenation catalyst and its preparation method and application |
| CN113426463A (en) * | 2021-07-01 | 2021-09-24 | 中国石油大学(华东) | In-situ preparation and application of high-efficiency non-supported porous sulfurized nickel-molybdenum catalyst |
| CN115532309A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Preparation method and application of oil-soluble catalyst for slurry bed hydrogenation |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106238076A (en) * | 2016-07-27 | 2016-12-21 | 广东工业大学 | A kind of preparation method of the oxygen doping molybdenum bisuphide Hydrobon catalyst of nickel-loaded |
| CN106238076B (en) * | 2016-07-27 | 2019-01-22 | 广东工业大学 | A kind of preparation method of the oxygen doping molybdenum disulfide Hydrobon catalyst of nickel-loaded |
| CN109569664A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Sulfurized hydrogenation catalyst and its preparation method and application |
| CN109569662A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Sulfurized hydrogenation catalyst and its preparation method and application |
| CN109569662B (en) * | 2017-09-29 | 2022-03-11 | 中国石油化工股份有限公司 | Vulcanized hydrogenation catalyst, and preparation method and application thereof |
| CN109569664B (en) * | 2017-09-29 | 2022-03-11 | 中国石油化工股份有限公司 | Vulcanized hydrogenation catalyst, and preparation method and application thereof |
| CN115532309A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Preparation method and application of oil-soluble catalyst for slurry bed hydrogenation |
| CN115532309B (en) * | 2021-06-30 | 2023-10-13 | 中国石油化工股份有限公司 | Preparation method and application of oil-soluble catalyst for slurry bed hydrogenation |
| CN113426463A (en) * | 2021-07-01 | 2021-09-24 | 中国石油大学(华东) | In-situ preparation and application of high-efficiency non-supported porous sulfurized nickel-molybdenum catalyst |
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