CN107159204A - A kind of dehydrogenation reaction catalyst of preparing styrene from ethylbenzene and preparation method thereof - Google Patents
A kind of dehydrogenation reaction catalyst of preparing styrene from ethylbenzene and preparation method thereof Download PDFInfo
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- CN107159204A CN107159204A CN201710448057.1A CN201710448057A CN107159204A CN 107159204 A CN107159204 A CN 107159204A CN 201710448057 A CN201710448057 A CN 201710448057A CN 107159204 A CN107159204 A CN 107159204A
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- ethylbenzene
- dehydrogenation reaction
- reaction catalyst
- preparing styrene
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Organic Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
This application discloses dehydrogenation reaction catalyst of a kind of preparing styrene from ethylbenzene and preparation method thereof, by weight including 120 230 parts of rhenium salt, 200 270 parts of 18 water aluminum nitrate, 70 163 parts of potassium hydroxide, 13 65 parts of potassium carbonate, 140 195 parts of ammoniacal liquor, 34 96 parts of graphite, 256 294 parts of peat, 163 184 parts of hydrobromic acid, 40 60 parts of diethylene glycol dimethyl ether.Thus, the dehydrogenation reaction catalyst of the preparing styrene from ethylbenzene of the present invention is in the production process of preparing styrene from ethylbenzene, it need to only put into and a small amount of just be greatly improved the conversion ratio of ethylbenzene, the yield of styrene and also improve therewith, by low production cost, the preparation process of this catalyst is few simultaneously, and simple and easy to apply, feasibility is high.
Description
Technical field
The present invention relates to dehydrogenation reaction catalyst, more particularly to a kind of preparing styrene from ethylbenzene dehydrogenation reaction catalyst and its
Preparation method.
Background technology
Reactant chemical reaction rate (improve or reduce) can be changed in chemical reaction without changing chemical balance, and this
The material that the quality and chemical property of body all do not change before and after chemical reaction is catalyst.Dehydrogenation reaction catalyst can
It is divided into two common classifications, one is simple dehydrogenation reaction catalyst, is worked under heated, another is oxidative dehydrogenation catalysis
Agent.
The dehydrogenation of the hydrocarbon gas is carried out at least 550 DEG C of high temperature.Because catalytic reaction occurs in high temperature, it is accompanied by side reaction
Such as thermal decomposition and coke generation.The degree of the side reaction is the key factor of the selectivity and activity that determine catalyst.In the pair
Among reaction, coke reaction of formation makes catalytically-active materials be covered by coke, and its obstruction is contacted with reactant, unacceptable reduction
Overall reaction conversion ratio.In addition, the progress generated with coke, the access aperture of catalyst is blocked, therefore causes and be present in hole
Active material it is useless, thoroughly accelerate the inactivation of catalyst.
The content of the invention
It is an object of the invention to provide dehydrogenation reaction catalyst of a kind of preparing styrene from ethylbenzene and preparation method thereof, solve above-mentioned
One or more in prior art problem.
According to an aspect of the present invention there is provided a kind of dehydrogenation reaction catalyst of preparing styrene from ethylbenzene, wrap by weight
Include 120-230 parts of rhenium salt, 200-270 parts of 18 water aluminum nitrate, 70-163 parts of potassium hydroxide, 13-65 parts of potassium carbonate, ammoniacal liquor 140-
195 parts, 34-96 parts of graphite, 256-294 parts of peat, 163-184 parts of hydrobromic acid, 40-60 parts of diethylene glycol dimethyl ether.
In some embodiments：The ammonia concn is 32%.
In some embodiments：The graphite can be substituted by iron powder.
In some embodiments：The rhenium salt is perrhenic acid ammonium salt or perrhenic acid.
Present invention also offers a kind of preparation method of the dehydrogenation reaction catalyst of above-mentioned preparing styrene from ethylbenzene, including with
Lower step:
Step one:Rhenium salt and 18 water aluminum nitrate are dissolved in Enough Dl water, reaction temperature is promoted to after 55 DEG C,
Potassium hydroxide, potassium carbonate, peat, hydrobromic acid, diethylene glycol dimethyl ether are sequentially added, ammoniacal liquor is subsequently added, regulation pH value is 7.2-
7.6, when precipitation completely after, persistently stir 2.5h, treat slurry liquid aging 90h, it is standby；
Step 2:At a temperature of 550 DEG C, the spray drying of slurry is carried out, then with 370 in controlled atmosphere vacuum drying oven
10h is dried at a temperature of DEG C, obtained black powder is added in kneading machine and mediates 3h and adds enough water, by wet pastel
Taken out from kneading machine, finally mix, get product with graphite in ribbon mixer.
The dehydrogenation reaction catalyst of the preparing styrene from ethylbenzene of the present invention needs to throw in the production process of preparing styrene from ethylbenzene, only
Enter it is a small amount of be just greatly improved the conversion ratio of ethylbenzene, the yield of styrene and also improve therewith, by low production cost, while this
The preparation process of catalyst is few, and simple and easy to apply, feasibility is high.
Embodiment
The present invention is described in further detail below by embodiment.
Embodiment 1：
The dehydrogenation reaction catalyst of preparing styrene from ethylbenzene, by weight including 195 parts of rhenium salt, 242 parts of 18 water aluminum nitrate,
142 parts of potassium hydroxide, 57 parts of potassium carbonate, 176 parts of ammoniacal liquor, 83 parts of graphite, 256 parts of peat, 163 parts of hydrobromic acid, diethylene glycol dimethyl
40 parts of ether.
Wherein, the ammonia concn is 32%；The graphite can be substituted by iron powder；The rhenium salt be perrhenic acid ammonium salt or
Perrhenic acid.
The preparation method of the dehydrogenation reaction catalyst of preparing styrene from ethylbenzene of the present invention：Comprise the following steps:
Step one:Rhenium salt and 18 water aluminum nitrate are dissolved in Enough Dl water, reaction temperature is promoted to after 55 DEG C,
Potassium hydroxide, potassium carbonate, peat, hydrobromic acid, diethylene glycol dimethyl ether are sequentially added, ammoniacal liquor is subsequently added, regulation pH value is 7.2,
When precipitation completely after, persistently stir 2.5h, treat slurry liquid aging 90h, it is standby；
Step 2:At a temperature of 550 DEG C, the spray drying of slurry is carried out, then with 370 in controlled atmosphere vacuum drying oven
10h is dried at a temperature of DEG C, obtained black powder is added in kneading machine and mediates 3h and adds enough water, by wet pastel
Taken out from kneading machine, finally mix, get product with graphite in ribbon mixer.
Embodiment 2：
The dehydrogenation reaction catalyst of preparing styrene from ethylbenzene, by weight including 194 parts of rhenium salt, 221 parts of 18 water aluminum nitrate,
143 parts of potassium hydroxide, 54 parts of potassium carbonate, 147 parts of ammoniacal liquor, 86 parts of graphite, 272 parts of peat, 177 parts of hydrobromic acid, diethylene glycol dimethyl
50 parts of ether.
Wherein, the ammonia concn is 36%；The graphite can be substituted by iron powder；The rhenium salt be perrhenic acid ammonium salt or
Perrhenic acid.
The preparation method of the dehydrogenation reaction catalyst of preparing styrene from ethylbenzene of the present invention：Comprise the following steps:
Step one:Rhenium salt and 18 water aluminum nitrate are dissolved in Enough Dl water, reaction temperature is promoted to after 55 DEG C,
Potassium hydroxide, potassium carbonate, peat, hydrobromic acid, diethylene glycol dimethyl ether are sequentially added, ammoniacal liquor is subsequently added, regulation pH value is 7.4,
When precipitation completely after, persistently stir 3h, treat slurry liquid aging 80h, it is standby；
Step 2:At a temperature of 530 DEG C, the spray drying of slurry is carried out, then with 350 in controlled atmosphere vacuum drying oven
12h is dried at a temperature of DEG C, obtained black powder is added in kneading machine and mediates 3h and adds enough water, by wet pastel
Taken out from kneading machine, finally mix, get product with graphite in ribbon mixer.
Embodiment 3：
The dehydrogenation reaction catalyst of preparing styrene from ethylbenzene, by weight including 167 parts of rhenium salt, 256 parts of 18 water aluminum nitrate,
107 parts of potassium hydroxide, 43 parts of potassium carbonate, 167 parts of ammoniacal liquor, 81 parts of graphite, 266 parts of peat, 179 parts of hydrobromic acid, diethylene glycol dimethyl
48 parts of ether.
Wherein, the ammonia concn is 30%；The graphite can be substituted by iron powder；The rhenium salt be perrhenic acid ammonium salt or
Perrhenic acid.
The preparation method of the dehydrogenation reaction catalyst of preparing styrene from ethylbenzene of the present invention：Comprise the following steps:
Step one:Rhenium salt and 18 water aluminum nitrate are dissolved in Enough Dl water, reaction temperature is promoted to after 60 DEG C,
Potassium hydroxide, potassium carbonate, peat, hydrobromic acid, diethylene glycol dimethyl ether are sequentially added, ammoniacal liquor is subsequently added, regulation pH value is 7.6,
When precipitation completely after, persistently stir 2h, treat slurry liquid aging 100h, it is standby；
Step 2:At a temperature of 560 DEG C, the spray drying of slurry is carried out, then with 400 in controlled atmosphere vacuum drying oven
9.5h is dried at a temperature of DEG C, obtained black powder is added in kneading machine and mediates 3h and adds enough water, by wet pasty state
Thing takes out from kneading machine, is finally mixed in ribbon mixer with graphite, gets product.
Embodiment 4：
The dehydrogenation reaction catalyst of preparing styrene from ethylbenzene, by weight including 230 parts of rhenium salt, 240 parts of 18 water aluminum nitrate,
135 parts of potassium hydroxide, 55 parts of potassium carbonate, 165 parts of ammoniacal liquor, 95 parts of graphite, 294 parts of peat, 184 parts of hydrobromic acid, diethylene glycol dimethyl
60 parts of ether.
Wherein, the ammonia concn is 36%；The graphite can be substituted by iron powder；The rhenium salt be perrhenic acid ammonium salt or
Perrhenic acid.
The preparation method of the dehydrogenation reaction catalyst of preparing styrene from ethylbenzene of the present invention：Comprise the following steps:
Step one:Rhenium salt and 18 water aluminum nitrate are dissolved in Enough Dl water, reaction temperature is promoted to after 55 DEG C,
Potassium hydroxide, potassium carbonate, peat, hydrobromic acid, diethylene glycol dimethyl ether are sequentially added, ammoniacal liquor is subsequently added, regulation pH value is 7.5,
When precipitation completely after, persistently stir 3.5h, treat slurry liquid aging 87h, it is standby；
Step 2:At a temperature of 550 DEG C, the spray drying of slurry is carried out, then with 400 in controlled atmosphere vacuum drying oven
10.5h is dried at a temperature of DEG C, obtained black powder is added in kneading machine and mediates 3h and adds enough water, by wet pasty state
Thing takes out from kneading machine, is finally mixed in ribbon mixer with graphite, gets product
It is as follows that the product of above-described embodiment and conventional emulsifier dissolve in water scattered effect test for agricultural chemicals：
Wherein, inventor show that the dehydrogenation reaction catalyst of preparing styrene from ethylbenzene of the invention exists by substantial amounts of experiment
In the production process of preparing styrene from ethylbenzene, a small amount of conversion ratio, yield of styrene for being just greatly improved ethylbenzene need to be only put into
Improve therewith, by low production cost, while the preparation process of this catalyst is few, simple and easy to apply, feasibility is high.
Described above is only one embodiment of the present invention, it is noted that to those skilled in the art,
Without departing from the concept of the premise of the invention, some similar modification and improvement can also be made, these also should be regarded as this
Within the protection domain of invention.
Claims (5)
1. a kind of dehydrogenation reaction catalyst of preparing styrene from ethylbenzene, it is characterised in that：By weight include 120-230 parts of rhenium salt,
200-270 parts of 18 water aluminum nitrate, 70-163 parts of potassium hydroxide, 13-65 parts of potassium carbonate, 140-195 parts of ammoniacal liquor, graphite 34-96
Part, 256-294 parts of peat, 163-184 parts of hydrobromic acid, 40-60 parts of diethylene glycol dimethyl ether.
2. a kind of dehydrogenation reaction catalyst of preparing styrene from ethylbenzene according to claim 1, it is characterised in that：The ammoniacal liquor
Concentration is 32%.
3. a kind of dehydrogenation reaction catalyst of preparing styrene from ethylbenzene according to claim 1, it is characterised in that：The graphite
It can be substituted by iron powder.
4. a kind of dehydrogenation reaction catalyst of preparing styrene from ethylbenzene according to claim 1, it is characterised in that：The rhenium salt
For perrhenic acid ammonium salt or perrhenic acid.
5. a kind of method for the dehydrogenation reaction catalyst for preparing any one of claim 1-4 institutes preparing styrene from ethylbenzene, its feature exists
In comprising the following steps:
Step one:Rhenium salt and 18 water aluminum nitrate are dissolved in Enough Dl water, reaction temperature is promoted to after 55 DEG C, successively
Potassium hydroxide, potassium carbonate, peat, hydrobromic acid, diethylene glycol dimethyl ether are added, ammoniacal liquor is subsequently added, regulation pH value is 7.2-7.6,
When precipitation completely after, persistently stir 2.5h, treat slurry liquid aging 90h, it is standby；
Step 2:At a temperature of 550 DEG C, the spray drying of slurry is carried out, then with 370 DEG C of temperature in controlled atmosphere vacuum drying oven
The lower drying 10h of degree, obtained black powder is added in kneading machine and mediates 3h and add enough water, by wet pastel from pinching
Taken out with machine, finally mix, get product with graphite in ribbon mixer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710448057.1A CN107159204A (en) | 2017-06-14 | 2017-06-14 | A kind of dehydrogenation reaction catalyst of preparing styrene from ethylbenzene and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710448057.1A CN107159204A (en) | 2017-06-14 | 2017-06-14 | A kind of dehydrogenation reaction catalyst of preparing styrene from ethylbenzene and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1244138A (en) * | 1994-12-14 | 2000-02-09 | 国际壳牌研究有限公司 | Dehydrogenation catalyst and process |
| CN1270851A (en) * | 1999-02-10 | 2000-10-25 | Basf公司 | Catalyst for preparing styrene by ethyl benzene dehydrogenation |
| CN1298323A (en) * | 1998-04-01 | 2001-06-06 | 苏德一化学公司 | Dehydrogenation catalysts comprising at least iron, alkali metal and a noble metal |
| CN1997448A (en) * | 2004-06-24 | 2007-07-11 | 苏德-化学公司 | Catalyst for the dehydrogenation of ethyl benzene to styrene prepared with a high purity iron precursor |
| CN101992092A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Catalyst for preparing styrene by dehydrogenizing ethylbenzene and preparation method thereof |
-
2017
- 2017-06-14 CN CN201710448057.1A patent/CN107159204A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1244138A (en) * | 1994-12-14 | 2000-02-09 | 国际壳牌研究有限公司 | Dehydrogenation catalyst and process |
| CN1298323A (en) * | 1998-04-01 | 2001-06-06 | 苏德一化学公司 | Dehydrogenation catalysts comprising at least iron, alkali metal and a noble metal |
| CN1270851A (en) * | 1999-02-10 | 2000-10-25 | Basf公司 | Catalyst for preparing styrene by ethyl benzene dehydrogenation |
| CN1997448A (en) * | 2004-06-24 | 2007-07-11 | 苏德-化学公司 | Catalyst for the dehydrogenation of ethyl benzene to styrene prepared with a high purity iron precursor |
| CN101992092A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Catalyst for preparing styrene by dehydrogenizing ethylbenzene and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 韩长日等: "《化工小商品生产法》", 31 August 1996, 湖南科学技术出版社 * |
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Application publication date: 20170915 |