CN108031478A - Metal sulphide catalyst and preparation method thereof - Google Patents
Metal sulphide catalyst and preparation method thereof Download PDFInfo
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- CN108031478A CN108031478A CN201711361480.4A CN201711361480A CN108031478A CN 108031478 A CN108031478 A CN 108031478A CN 201711361480 A CN201711361480 A CN 201711361480A CN 108031478 A CN108031478 A CN 108031478A
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- raw material
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- metal sulphide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
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Abstract
The present invention relates to a kind of metal sulphide catalyst and preparation method thereof, which includes S1, provides fcc raw material, and fcc raw material includes raw material containing molybdenum, containing cobalt raw material, activated carbon, sulfide solution and complexing agent；S2, mix the raw material containing molybdenum, containing cobalt raw material and complexing agent in a heated condition, obtains catalyst precursor solution；S3, add the activated carbon into the catalyst precursor solution, is dispersed with stirring uniformly, obtains containing carbon solution；S4, to it is described contain carbon solution in add sulfide solution, filtration drying obtains the metal sulphide catalyst after reaction.The preparation method adds activated carbon thereto by preparing catalyst precursor solution in a heated condition, and followed by vulcanization, last filtration drying obtains metal sulphide catalyst.The preparation method technique is simple, efficient, and can prepare metal sulphide catalyst on a large scale.Meanwhile preparation-obtained metal sulphide catalyst performance is good, there is larger application prospect and use value.
Description
Technical field
The present invention relates to a kind of metal sulphide catalyst and preparation method thereof.
Background technology
Cobalt-molybdenum series catalyst has prominent sulfur tolerance, it is suitable for coal, the synthesis ammonia that heavy oil (or residual oil) is raw material
Factory；In no H2S or few H2In the environment of S, expression activitiy is poor, be generally unsuitable for using light oil, natural gas as raw material synthesis ammonia
Factory.With the development of the energy-saving work of fertilizer industry in recent years, Co-Mo sulfur-tolerant wide temperature shift catalyst obtains more and more
The favor of producer.
Therefore, how cobalt sulfide-molybdenum catalyst that yield is high, performance is good is prepared by simple technique becomes present
Problem encountered.
The content of the invention
It is an object of the invention to provide a kind of metal sulphide catalyst and preparation method thereof, which can be with simple
Technique, higher efficiency metal sulphide catalyst of good performance is prepared.
To reach above-mentioned purpose, the present invention provides following technical solution：A kind of preparation method of metal sulphide catalyst, bag
Include following steps：
S1, provide fcc raw material, the fcc raw material include raw material containing molybdenum, containing cobalt raw material, activated carbon, sulfide solution with
And complexing agent；
S2, mix the raw material containing molybdenum, containing cobalt raw material and complexing agent in a heated condition, and it is molten to obtain catalyst precarsor
Liquid；
S3, add the activated carbon into the catalyst precursor solution, is dispersed with stirring uniformly, obtains containing carbon solution；
S4, to it is described contain in carbon solution add sulfide solution, filtration drying obtains metal sulphide catalysis after reaction
Agent.
Further, the sulfide solution selection includes any of thiosulfate or thiosulfates or more
Kind.
Further, the complexing agent is the organic complexing agent containing carboxylic acid structure.
Further, the mass fraction of the organic complexing agent is 10 to 60wt%.
Further, the organic complexing agent, which is selected from, includes pyruvic acid, levulic acid, 4- acetoxybutanoic acids, 1,3- acetone
Dicarboxylic acids, 3- oxopropanoic acids, 4- ketobutyric acids, 2,3- diformyls succinic acid, 5- oxopentanoic acids, 4-oxopentanoic acid, sulfydryl second
Any of acid, glyoxylic acid ethyl ester or hydroxyacetic acid organic complexing agent.
Further, in the catalyst precursor solution, the content of the activated carbon is 10 to 30wt%.
Further, in the catalyst precursor solution, the ratio containing cobalt raw material and the raw material containing molybdenum is 0.3
To 0.8.
Further, in the catalyst precursor solution, the ratio containing cobalt raw material and the raw material containing molybdenum is 0.4
To 0.6.
Further, it is described to be selected from containing cobalt raw material including the carbonate containing cobalt element, nitrate, sulfate, acetate, chlorine
Appointing in compound, hydroxide, acetoacetate, acetylacetonate, glycinate, naphthenate, oxide or carboxylate
It is one or more；The raw material containing molybdenum be selected from including the carbonate containing molybdenum element, nitrate, sulfate, acetate, chloride,
Any of hydroxide, acetoacetate, acetylacetonate, glycinate, naphthenate, oxide or carboxylate or
It is a variety of.
Further, in step S4, further include and carry out heat at a temperature of 100 to 800 DEG C to the product after filtration drying
Processing.
To reach above-mentioned purpose, present invention also offers a kind of preparation method institute by metal sulphide catalyst as mentioned
Obtained metal sulphide catalyst.
The beneficial effects of the present invention are：The preparation method of the metal sulphide catalyst of the present invention passes through in a heated condition
Catalyst precursor solution is prepared, and adds activated carbon thereto, followed by vulcanization, last filtration drying obtains metal sulphide
Catalyst.The preparation method technique is simple, efficient, and can prepare metal sulphide catalyst on a large scale.Meanwhile prepared obtain
Metal sulphide catalyst performance it is good, there is larger application prospect and use value.
Described above is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be practiced according to the content of specification, below with presently preferred embodiments of the present invention and coordinate attached drawing describe in detail as after.
Brief description of the drawings
Fig. 1 is the process step figure of the preparation method of the metal sulphide catalyst shown in the present invention.
Embodiment
With reference to the accompanying drawings and examples, the embodiment of the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but is not limited to the scope of the present invention.
Fig. 1 is referred to, the preparation method of the metal sulphide catalyst shown in the present invention comprises the following steps：
S1, provide fcc raw material, the fcc raw material include raw material containing molybdenum, containing cobalt raw material, activated carbon, sulfide solution with
And complexing agent, wherein, the sulfide solution selection includes any of thiosulfate or thiosulfates or a variety of, institute
State and be selected from containing cobalt raw material including the carbonate containing cobalt element, nitrate, sulfate, acetate, chloride, hydroxide, acetyl
Any of acetate, acetylacetonate, glycinate, naphthenate, oxide or carboxylate are a variety of, described to contain molybdenum
Raw material be selected from including the carbonate containing molybdenum element, nitrate, sulfate, acetate, chloride, hydroxide, acetoacetate,
Any of acetylacetonate, glycinate, naphthenate, oxide or carboxylate are a variety of, the organic complexing agent
Selected from including pyruvic acid, levulic acid, 4- acetoxybutanoic acids, 1,3- acetone dicarboxylic acids, 3- oxopropanoic acids, 4- ketobutyric acids, 2,
Any in 3- diformyls succinic acid, 5- oxopentanoic acids, 4-oxopentanoic acid, thioacetic acid, glyoxylic acid ethyl ester or hydroxyacetic acid
Kind organic complexing agent, the complexing agent are the organic complexing agent containing carboxylic acid structure, and the mass fraction of the organic complexing agent is 10
To 60wt%；
S2, mix the raw material containing molybdenum, containing cobalt raw material and complexing agent in a heated condition, and it is molten to obtain catalyst precarsor
Liquid, wherein, the content of the activated carbon is 10 to 30wt%, the ratio containing cobalt raw material and the raw material containing molybdenum be 0.3 to
0.8, it is preferably 0.4 to 0.6；
S3, add the activated carbon into the catalyst precursor solution, is dispersed with stirring uniformly, obtains containing carbon solution；
S4, to it is described contain carbon solution in add sulfide solution, filtration drying and the temperature at 100 to 800 DEG C after reaction
Under be heat-treated, obtain the metal sulphide catalyst.
Below in conjunction with specific embodiments come to the present invention illustrated in further detail.
Ammonium heptamolybdate, four acetate hydrate cobalts and 50% glyoxylic acid solution are hydrated by four to mix in a heated condition, are made
It is standby to obtain catalyst precursor solution, wherein, the ratio of Mo and Co are 2：1.Then carbon black is added into the precursor solution, is stirred
Add thiosulfate solution after being uniformly dispersed in batches under conditions of 70 DEG C, add four times altogether, each 7.5ml.When last
When once adding thiosulfate solution, solution is warming up to 100 DEG C, and keep temperature 1h.Then by solution filtration drying
And be heat-treated in the environment of 150 DEG C, obtain metal sulphide catalyst.
In summary：Before the preparation method of the metal sulphide catalyst of the present invention by preparing catalyst in a heated condition
Liquid solution, and activated carbon is added thereto, followed by vulcanization, last filtration drying obtains metal sulphide catalyst.The system
Preparation Method technique is simple, efficient, and can prepare metal sulphide catalyst on a large scale.Meanwhile preparation-obtained metal sulphide
Catalyst performance is good, has larger application prospect and use value.
Each technical characteristic of embodiment described above can be combined arbitrarily, to make description succinct, not to above-mentioned reality
Apply all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, the scope that this specification is recorded all is considered to be.
Embodiment described above only expresses the several embodiments of the present invention, its description is more specific and detailed, but simultaneously
Cannot therefore it be construed as limiting the scope of the patent.It should be pointed out that come for those of ordinary skill in the art
Say, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of preparation method of metal sulphide catalyst, it is characterised in that comprise the following steps：
S1, provide fcc raw material, and the fcc raw material includes raw material containing molybdenum, containing cobalt raw material, activated carbon, sulfide solution and network
Mixture；
S2, mix the raw material containing molybdenum, containing cobalt raw material and complexing agent in a heated condition, obtains catalyst precursor solution；
S3, add the activated carbon into the catalyst precursor solution, is dispersed with stirring uniformly, obtains containing carbon solution；
S4, to it is described contain carbon solution in add sulfide solution, filtration drying obtains the metal sulphide catalyst after reaction.
2. the preparation method of metal sulphide catalyst as claimed in claim 1, it is characterised in that the sulfide solution selection
Including any of thiosulfate or thiosulfates or a variety of.
3. the preparation method of metal sulphide catalyst as claimed in claim 1, it is characterised in that the complexing agent is containing carboxylic acid
The organic complexing agent of structure.
4. the preparation method of metal sulphide catalyst as claimed in claim 3, it is characterised in that the matter of the organic complexing agent
It is 10 to 60wt% to measure fraction.
5. the preparation method of the metal sulphide catalyst as described in claim 3 or 4, it is characterised in that the organic complexing agent
Selected from including pyruvic acid, levulic acid, 4- acetoxybutanoic acids, 1,3- acetone dicarboxylic acids, 3- oxopropanoic acids, 4- ketobutyric acids, 2,
Any in 3- diformyls succinic acid, 5- oxopentanoic acids, 4-oxopentanoic acid, thioacetic acid, glyoxylic acid ethyl ester or hydroxyacetic acid
Kind organic complexing agent.
6. the preparation method of metal sulphide catalyst as claimed in claim 1, it is characterised in that molten in the catalyst precarsor
In liquid, the content of the activated carbon is 10 to 30wt%.
7. the preparation method of metal sulphide catalyst as claimed in claim 1, it is characterised in that molten in the catalyst precarsor
In liquid, the ratio containing cobalt raw material and the raw material containing molybdenum is 0.3 to 0.8.
8. the preparation method of metal sulphide catalyst as claimed in claim 7, it is characterised in that molten in the catalyst precarsor
In liquid, the ratio containing cobalt raw material and the raw material containing molybdenum is 0.4 to 0.6.
9. the preparation method of the metal sulphide catalyst as described in claim 1 or 7 or 8, it is characterised in that described to contain cobalt raw material
Selected from including the carbonate containing cobalt element, nitrate, sulfate, acetate, chloride, hydroxide, acetoacetate, acetyl
Any of acetone solvate, glycinate, naphthenate, oxide or carboxylate are a variety of；The raw material containing molybdenum is selected from bag
Include the carbonate containing molybdenum element, nitrate, sulfate, acetate, chloride, hydroxide, acetoacetate, acetylacetonate
Any of thing, glycinate, naphthenate, oxide or carboxylate are a variety of.
A kind of 10. vulcanization as obtained by the preparation method of metal sulphide catalyst as claimed in any one of claims 1-9 wherein
Metallic catalyst.
Priority Applications (1)
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|---|---|---|---|
| CN201711361480.4A CN108031478A (en) | 2017-12-18 | 2017-12-18 | Metal sulphide catalyst and preparation method thereof |
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| CN201711361480.4A CN108031478A (en) | 2017-12-18 | 2017-12-18 | Metal sulphide catalyst and preparation method thereof |
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| CN201711361480.4A Withdrawn CN108031478A (en) | 2017-12-18 | 2017-12-18 | Metal sulphide catalyst and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109987692A (en) * | 2019-04-02 | 2019-07-09 | 温州医科大学 | The method of Fenton-like enhancing processing organic wastewater based on acetaldehyde acid construct |
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Application publication date: 20180515 |