CN107308942A - The catalyst and its method of preparing butadiene with butylene oxo-dehydrogenation - Google Patents
The catalyst and its method of preparing butadiene with butylene oxo-dehydrogenation Download PDFInfo
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- CN107308942A CN107308942A CN201610408635.4A CN201610408635A CN107308942A CN 107308942 A CN107308942 A CN 107308942A CN 201610408635 A CN201610408635 A CN 201610408635A CN 107308942 A CN107308942 A CN 107308942A
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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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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Abstract
The present invention relates to a kind of catalyst of preparing butadiene with butylene oxo-dehydrogenation and its method, the problem of catalyst cost is higher, catalyst activity is relatively low in the prior art is mainly solved.The present invention is by using a kind of catalyst of preparing butadiene with butylene oxo-dehydrogenation, and the general structure of the catalyst is ZnxMgyFe2O4, x is between 0.5 1, and ferric nitrate, zinc nitrate and magnesium nitrate are configured to solution by y between 0.1 0.5 according to certain mol proportion, are added ammoniacal liquor and are co-precipitated, and then through the step such as aging, drying, calcining, broken, obtains being modified iron acid zinc catalyst；Under the catalyst existence condition, butylene, oxygen and vapor are passed through according to a certain percentage, the technical scheme that the reaction product with higher butadiene selective can be obtained at a temperature of appropriate reaction preferably solves above mentioned problem, available in the preparation of butylene oxidation-dehydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of catalyst of preparing butadiene with butylene oxo-dehydrogenation and its method.
Background technology
Butadiene is the chemical products raw material with high added value, and the status in chemicals production is only second to ethene and third
Alkene.Butadiene is the primary raw material of synthetic rubber, can produce butadiene rubber, butadiene-styrene rubber, nitrile rubber, neoprene, third
A variety of rubber products such as alkene nitrile-butadiene-styrene, SBS elastomer, can also be used to produce Buddhist nun
Dragon 66, adiponitrile, a variety of Organic chemical products such as hexamethylene diamine and it is used as binding agent and gasoline additive etc..
Meanwhile, abundant butane and butene component are there is in China's refinery gas, oil liquefied gas, its is cheap,
The overwhelming majority is burnt up as fuel, and resource utilization is low.And by oxydehydro process by the low butylene of added value, butane-component
It is a kind of economic, efficient and environmental protection Utilizing Resource Pattern to be converted into the high product butadiene of added value.
Butylene oxidation-dehydrogenation catalyst mainly has bismuth molybdate series, mixed oxide Fe-Sb series, iron system spinel series
And nickel calcium phosphate series etc., the wherein iron system butylene oxidation denitrating catalyst of China's independent research, such as patent CN1184705,
CN1072110 and CN1033013, applied to fluidized-bed reactor, with higher butadiene selective and yield, but exists and urges
The problem of agent abrasion is more serious, patent CN103055890B is applied to insulation fix bed Fe-series catalyst, Dante two
Alkene yield is relatively low, and highest is only capable of reaching 72%.
The content of the invention
One of technical problems to be solved by the invention are that catalyst cost is higher in the prior art, catalyst activity is relatively low
The problem of there is provided a kind of catalyst of new preparing butadiene with butylene oxo-dehydrogenation.This method has that catalyst cost is relatively low, urge
The higher advantage of agent activity.The two of the technical problems to be solved by the invention are to provide a kind of corresponding with one of solving the problems, such as
Preparing butadiene with butylene oxo-dehydrogenation method.
One of to solve the above problems, the technical solution adopted by the present invention is as follows：A kind of butylene oxidation-dehydrogenation catalyst, institute
The general structure for stating catalyst is ZnxMgyFezO4, x is between 0.5-1, and z is between 2-2.5 between 0.1-0.5 by y, wherein x+
Y=1；
In above-mentioned technical proposal, it is preferable that the preparation process of catalyst includes：(1) by ferric nitrate, zinc nitrate and magnesium nitrate
It is dissolved in water, obtains nitrate solution；(2) ammonia spirit is added dropwise in nitrate solution and precipitated；(3) precipitation terminates
The heat ageing 20-40min at 70-80 DEG C, stands and is filtered after 0.5-2h afterwards；(4) filter cake being filtrated to get is done at 90-120 DEG C
Dry 10-14h；(5) calcined at 600-700 DEG C and the catalyst is obtained after 8-12h, cooling.
In above-mentioned technical proposal, it is highly preferred that ammonia spirit mass fraction is 20-30%, titration end-point pH is 8-9.
In above-mentioned technical proposal, it is preferable that the mass ratio of ferric nitrate, zinc nitrate and magnesium nitrate is 848-929：223-297：
26-64。
In above-mentioned technical proposal, it is preferable that the mass fraction of nitrate is 35-45% in nitrate solution.
For solve the above problems two, the technical solution adopted by the present invention is as follows：A kind of Oxidative Dehydrogenation of Butene is for fourth two
The method of alkene, reactor is passed through by the mixture of butylene, air, vapor, with the catalyst described in claim 1 in effective bar
Reacted under part, reactor outlet obtains butadiene product；The condition for validity is：Reaction gauge pressure is 0-0.5MPa, reaction
300-360 DEG C of temperature, oxygen alkene mol ratio is 0.7-1.1, and water alkene mol ratio is 10-20, and butylene mass space velocity is 300-400h-1。
In above-mentioned technical proposal, it is preferable that reactor is fixed bed；Catalyst described in claim 1 is loaded into reaction
Device, is first passed through air at 360-400 DEG C and catalyst is activated.
In above-mentioned technical proposal, it is preferable that be passed through air capacity and loaded catalyst that reactor carries out activation of catalyst
Volume be 200-400:1.
Groped using butylene oxidation-dehydrogenation catalyst preparation condition and reaction condition made from the method for this patent, obtained
Higher catalytic activity and butadiene selective were obtained, under optimum reaction condition, the catalyst prepared using this patent method,
Raw material is cheap and easy to get, and preparation method is simple, and higher catalytic activity, butene conversion can be obtained under relatively low reaction temperature
More than 90% can be reached with butadiene selective, butadiene yield achieves preferable technique effect up to more than 80%.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Embodiment
Embodiment 1
Take 80.0gFe (NO3)3·9H2O, 29.7gZn (NO3)·9H2O,26.0gMg(NO3)2·6H2O is dissolved in 500mL steamings
In distilled water, 25% ammoniacal liquor is instilled while stirring at room temperature, control precipitation terminal pH=8.0-9.0 precipitates 1h, after precipitation terminates
The aging 30min in 70 DEG C of water-baths, stands after 1h and filters, neutrality is then washed to distillation, filter cake is at 100 DEG C at room temperature again
12h is dried in baking oven, is then calcined at 650 DEG C and sieving is crushed after 10h, natural cooling, takes 20-60 mesh to be used for activity rating.
Catalyst is loaded into fixed bed reactors, be first passed through air at 400 DEG C activates to catalyst, is passed through reaction
It is 300 that device, which carries out the air capacity of activation of catalyst and the volume of loaded catalyst,.Then it is passed through according to certain flow ratio
Butylene, air, the mixture of vapor, reactor outlet obtain butadiene product；In normal pressure, 340 DEG C of temperature, oxygen alkene ratio (oxygen
The mol ratio of gas and butylene) 1.0, water alkene ratio (mol ratio of vapor and butylene) 20, butylene air speed 300h-1Under conditions of, obtain
Butene conversion is obtained up to 85.1%, butadiene selective is up to 90.3%, and butadiene yield is up to 76.8%.
Embodiment 2
According to the condition and step described in embodiment 1,80.0gFe (NO are taken3)3·9H2O, 53.5gZn (NO3)2·9H2O,
5.1gMg(NO3)2It is dissolved in 500mL distilled water, instills 25% ammoniacal liquor, control precipitation terminal pH=while stirring at room temperature
8.0-9.0, precipitates 1h, the aging 30min in 75 DEG C of water-baths again after precipitation terminates, and stands filtered after 1h at room temperature, Ran Houyong
Distillation is washed to neutrality, and filter cake is dried 12h in 100 DEG C of baking ovens, crushed after then calcining 10h, natural cooling at 650 DEG C
Sieve, takes 20-60 mesh to be used for activity rating.
It is 0.5MPa in reaction gauge pressure, 340 DEG C of temperature, oxygen alkene compares 1.0, and water alkene compares 20, butylene air speed 300h-1Condition
Under, butene conversion is obtained up to 87.8%, and butadiene selective is up to 86.4%, and butadiene yield is up to 75.9%.
Embodiment 3
According to the condition and step described in embodiment 1,80.0gFe (NO are taken3)3·9H2O, 44.6gZn (NO3)2·9H2O,
12.8gMg(NO3)2It is dissolved in 500mL distilled water, instills 25% ammoniacal liquor, control precipitation terminal pH=while stirring at room temperature
8.0-9.0, precipitates 1h, the aging 30min in 77 DEG C of water-baths again after precipitation terminates, and stands filtered after 1h at room temperature, Ran Houyong
Distillation is washed to neutrality, and filter cake is dried 12h in 100 DEG C of baking ovens, crushed after then calcining 10h, natural cooling at 650 DEG C
Sieve, takes 20~60 mesh to be used for activity rating.
In normal pressure, 340 DEG C of temperature, oxygen alkene compares 1.0, and water alkene compares 20, butylene air speed 300h-1Under conditions of, obtain butylene and turn
Rate is up to 88.0%, and butadiene selective is up to 90.7%, butadiene yield 79.8%.
Embodiment 4
According to the condition and step described in embodiment 1,101.0gFe (NO are taken3)3·9H2O, 44.6gZn (NO3)2·9H2O,
12.8gCu(NO3)2It is dissolved in 500mL distilled water, instills 20% ammoniacal liquor, control precipitation terminal pH=while stirring at room temperature
8.0-9.0, precipitates 1h, the aging 20min in 77 DEG C of water-baths again after precipitation terminates, and stands filtered after 0.5h at room temperature, then
Neutrality is washed to distillation, filter cake dries 10h in 120 DEG C of baking ovens, then calcines and crushed after 12h, natural cooling at 600 DEG C
Sieving, takes 20-60 mesh to be used for activity rating.
It is 0.2MPa in reaction gauge pressure, 340 DEG C of temperature, oxygen alkene compares 1.0, and water alkene compares 20, butylene air speed 300h-1Condition
Under, butene conversion is obtained up to 89.4%, and butadiene selective is up to 89.8%, butadiene yield 80.3%.
Embodiment 5
According to the condition and step described in embodiment 1,92.9gFe (NO are taken3)3·9H2O, 44.6gZn (NO3)2·9H2O,
12.8gCu(NO3)2It is dissolved in 500mL distilled water, instills 30% ammoniacal liquor, control precipitation terminal pH=while stirring at room temperature
8.0-9.0, precipitates 1h, the aging 40min in 77 DEG C of water-baths again after precipitation terminates, and stands filtered after 2h at room temperature, Ran Houyong
Distillation is washed to neutrality, and filter cake is dried 14h in 90 DEG C of baking ovens, crushed after then calcining 8h, natural cooling at 700 DEG C
Sieve, takes 20-60 mesh to be used for activity rating.
In normal pressure, 340 DEG C of temperature, oxygen alkene compares 1.0, and water alkene compares 20, butylene air speed 300h-1Under conditions of, obtain butylene and turn
Rate is up to 90.3%, and butadiene selective is up to 92.7%, butadiene yield 83.8%.
Embodiment 6
According to the condition and step described in embodiment 5, simply it is passed through reactor and carries out the air capacity of activation of catalyst with urging
The volume of agent loadings is 300.320 DEG C of reaction temperature, oxygen alkene compares 1, and water alkene compares 20, butylene air speed 300h-1Under conditions of, obtain
Butene conversion is obtained up to 86.4%, butadiene selective is up to 94.1%, butadiene yield 81.3%.
Embodiment 7
According to the condition and step described in embodiment 5, simply it is passed through reactor and carries out the air capacity of activation of catalyst with urging
The volume of agent loadings is 300.360 DEG C of reaction temperature, oxygen alkene compares 1, and water alkene compares 20, butylene air speed 300h-1Under conditions of, obtain
Butene conversion is obtained up to 92.3%, butadiene selective is up to 86.5%, butadiene yield 79.8%.
Embodiment 8
According to the condition and step described in embodiment 5, simply it is passed through reactor and carries out the air capacity of activation of catalyst with urging
The volume of agent loadings is 300.340 DEG C of reaction temperature, oxygen alkene compares 0.7, and water alkene compares 20, butylene air speed 300h-1Under conditions of,
Butene conversion is obtained up to 85.2%, butadiene selective is up to 92.4%, butadiene yield 78.7%.
Embodiment 9
According to the condition and step described in embodiment 5, simply it is passed through reactor and carries out the air capacity of activation of catalyst with urging
The volume of agent loadings is 300.340 DEG C of reaction temperature, oxygen alkene compares 1, and water alkene compares 10, butylene air speed 300h-1Under conditions of, obtain
Butene conversion is obtained up to 85.8%, butadiene selective is up to 88.6%, butadiene yield 76.0%.
Comparative example
Take 82gFe (NO3)3·9H2O, 26.3gZn (NO3)·9H2O is dissolved in 500mL distilled water, at room temperature while stirring
The ammoniacal liquor of instillation 25%, control precipitation terminal pH=8.0-9.0, precipitates 1h, the aging in 70 DEG C of water-baths again after precipitation terminates
30min, is stood after 1h and filters at room temperature, and neutrality is then washed to distillation, and filter cake dries 12h in 100 DEG C of baking ovens, then
Calcined at 650 DEG C and sieving is crushed after 10h, natural cooling, take 20-60 mesh to be used for activity rating.
Catalyst is loaded into fixed bed reactors, be first passed through air at 400 DEG C activates to catalyst, is passed through reaction
It is 300 that device, which carries out the air capacity of activation of catalyst and the volume of loaded catalyst,.Then it is passed through according to certain flow ratio
Butylene, air, the mixture of vapor, reactor outlet obtain butadiene product；In normal pressure, 340 DEG C of temperature, oxygen alkene ratio (oxygen
The mol ratio of gas and butylene) 1.0, water alkene ratio (mol ratio of vapor and butylene) 20, butylene air speed 300h-1Under conditions of, obtain
Butene conversion is obtained up to 79.3%, butadiene selective is up to 84.7%, and butadiene yield is up to 67.2%.
Claims (8)
1. a kind of catalyst of preparing butadiene with butylene oxo-dehydrogenation, the general structure of the catalyst is ZnxMgyFeZO4, x exists
Between 0.5-1, y is between 0.1-0.5, and z is between 2-2.5, wherein x+y=1.
2. the catalyst of preparing butadiene with butylene oxo-dehydrogenation according to claim 1, it is characterised in that the catalyst
Preparation process includes：(1) ferric nitrate, zinc nitrate and magnesium nitrate are dissolved in water, obtain nitrate solution；(2) it is ammoniacal liquor is molten
Liquid is added dropwise in nitrate solution and precipitated；(3) precipitation terminate after at 70-80 DEG C heat ageing 20-40min, stand 0.5-
Filtered after 2h；(4) filter cake being filtrated to get dries 10-14h at 90-120 DEG C；(5) 8-12h is calcined at 600-700 DEG C, it is cold
But the catalyst is obtained afterwards.
3. the catalyst of preparing butadiene with butylene oxo-dehydrogenation according to claim 2, it is characterised in that ammonia spirit quality
Fraction is 20-30%, and titration end-point pH is 8-9.
4. the catalyst of preparing butadiene with butylene oxo-dehydrogenation according to claim 2, it is characterised in that ferric nitrate, zinc nitrate
And the mass ratio of magnesium nitrate is 808-1010：149-297：26-128.
5. the catalyst of preparing butadiene with butylene oxo-dehydrogenation according to claim 2, it is characterised in that in nitrate solution
The mass fraction of nitrate is 27-32%.
6. a kind of method of preparing butadiene with butylene oxo-dehydrogenation, reactor is passed through by the mixture of butylene, air, vapor,
Reacted with the catalyst described in claim 1 under condition for validity, reactor outlet obtains butadiene product；It is described effective
Condition is：Reaction gauge pressure is 0-0.5MPa, and 300-360 DEG C of reaction temperature, oxygen alkene mol ratio is 0.7-1.1, and water alkene mol ratio is
10-20, butylene mass space velocity is 300-400h-1。
7. the method for preparing butadiene with butylene oxo-dehydrogenation according to claim 6, it is characterised in that reactor is fixed bed；
Catalyst described in claim 1 is loaded into reactor, be first passed through air at 360-400 DEG C activates to catalyst.
8. the method for preparing butadiene with butylene oxo-dehydrogenation according to claim 6, it is characterised in that be passed through reactor progress
The air capacity of activation of catalyst and the volume ratio of loaded catalyst are 200-400:1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111302885A (en) * | 2020-03-02 | 2020-06-19 | 齐鲁工业大学 | Method for efficiently synthesizing ethylene and 1, 3-butadiene by bioethanol one-pot method |
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2016
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| CN111302885A (en) * | 2020-03-02 | 2020-06-19 | 齐鲁工业大学 | Method for efficiently synthesizing ethylene and 1, 3-butadiene by bioethanol one-pot method |
| CN111302885B (en) * | 2020-03-02 | 2022-11-04 | 齐鲁工业大学 | Method for efficiently synthesizing ethylene and 1,3-butadiene by bioethanol one-pot method |
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