CN103274887B - Method for synthesizing 1,3-butadiene by using Bi/Mo/Ce three-component composite oxide catalyst - Google Patents
Method for synthesizing 1,3-butadiene by using Bi/Mo/Ce three-component composite oxide catalyst Download PDFInfo
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Abstract
The invention discloses a method for synthesizing 1,3-butadiene by using a Bi/Mo/Ce three-component composite oxide catalyst, and particularly relates to a method for producing 1,3-butadiene through oxidative dehydrogenation of 1-butene by using the three-component catalyst. The method comprises the following specific steps: mixing iron salt, bismuth salt, cerium salt and deionized water according to a certain ratio, regulating the pH value with an alkaline solution, concentrating, filtering, drying, roasting, cooling, grinding, and screening to obtain the Bi/Mo/Ce three-component composite oxide catalyst. Different from the traditional bismuth-molybdenum catalyst, according to the invention, the high-activity and high-selectivity Bi/Mo/Fe/Ce three-component composite oxide catalyst for a 1,3-butadiene preparation process can be prepared by regulating the cerium metal content in the catalyst.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, particularly relate to the method for a kind of Bi/Mo/Ce three components composite oxide catalysts synthesis 1,3-butadiene.
Background technology
1,3-butadiene is the important basic raw material of petrochemical complex, especially the important source material monomer of synthetic rubber, resin, and the status in petrochemical industry olefin feedstock is only second to ethene and propylene.At present, the source of divinyl mainly contains two kinds, namely adopts extraction process extracting from split product C-4-fraction obtain and adopt oxydehydro process to be obtained by C-4-fraction oxydehydrogenations such as butylene.
In recent years, along with the fast development of synthetic rubber and resin industry causes the market requirement of divinyl day by day vigorous, and current divinyl obtains mainly through the extracting of naphtha cracking product, but due to the restriction of domestic petroleum naphtha amount and cracker, extraction process is produced divinyl and can not be satisfied the demands far away, butylene oxidation-dehydrogenation obtains divinyl can alleviate this demand relation, and meanwhile, Oxidative Dehydrogenation of Butene Into Butadiene is also significant for the comprehensive utilization of C-4-fraction resource.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, one Bi/Mo/Ce three components composite oxide catalysts is provided to synthesize 1, the method of 3-divinyl, this catalyzer is Bi-Mo-Ce three components O composite metallic oxide catalyst, and it has good catalytic activity and selectivity.
The technical solution adopted for the present invention to solve the technical problems is as follows.
The three components composite oxide catalysts prepared is placed in reactor, and gas mixture is imported in reactor, keep certain air speed and reaction bed temperature to react, obtain 1,3-butadiene product.
Described gas mixture comprises 1-butylene, air and water vapour, and mixed volume is than being 1:3 ~ 5:5 ~ 16;
Described certain air speed is 219 ~ 438h
-1, reaction bed temperature is set as 380 ~ 450 DEG C.
The described three components composite oxide catalysts that utilizes is prepared in the method for 1,3-butadiene, and experiment Raw gas adopts 1-butylene, and industrial application adopts n-butene or C
4mixture also can.
Three components composite oxide catalysts composition comprises Bi, Mo and Ce, and wherein the mol ratio of molybdenum and bismuth is 1:1, and the mol ratio of cerium and bismuth is 0.01 ~ 2:1.
In described catalyzer, the mol ratio of cerium and bismuth is for being preferably 0.1 ~ 1:1.
In described catalyzer, bismuth derives from bismuth salt, and this bismuth salt is Bismuth trinitrate; Molybdenum derives from molybdenum salt, and molybdenum salt is ammonium molybdate; Cerium derives from cerium salt, and cerium salt is ceric ammonium nitrate.
Described three components composite oxide catalysts preparation process comprises the steps:
The cerium salt of certain mass and deionized water are configured in container by step (1), molybdenum salt and deionized water are configured in another container, wherein bismuth salt is dissolved in containing in certain density salpeter solution, is dropwise added drop-wise in the solution containing cerium salt by bismuth salts solution, and fully stirs; Dropwise be added drop-wise in the solution of molybdenum salt by mixed solution after stirring, make the mol ratio of molybdenum and bismuth be 1:1, the mol ratio of cerium and bismuth is 0.1 ~ 1:1.
Described cerium salt and the mol ratio of deionized water are 1:10 ~ 100;
Described molybdenum salt and the ratio of deionized water are 1:10 ~ 100;
The concentration of described salpeter solution is 5% ~ 50%: in bismuth salt and salpeter solution, the mol ratio of nitric acid is 1:5 ~ 50.
Above-mentioned solution is placed in the water-bath of 50 ~ 70 DEG C by step (2), dropwise drips with certain density ammoniacal liquor, regulates pH;
The massfraction of described ammonia soln is 25%; After regulating, pH value is 3 ~ 7;
After step (3) is extremely sticky by the solution stirring of step (2), transfer in baking oven dry.
Described dry time oven temperature be 60 ~ 150 DEG C;
Step (4) gained solid, after roasting, cooling, obtains 40 ~ 60 object Four composition catalyzer through grinding, screening.
Described maturing temperature is 300 ~ 700 DEG C, and roasting time is 2 ~ 6h.
Beneficial effect of the present invention:
The present invention's coprecipitation method, catalyst preparing uses Bi (NO
3)
35H
2o, (NH
4)
2mo
7o
24(NH
4)
2ce (NO
3)
6for presoma, the bismuth molybdenum catalyst that preparation Ce is element modified, this catalyzer has higher activity and selectivity.Use this catalyzer to carry out 1-butylene oxydehydrogenation and prepare 1,3-butadiene, its selectivity is up to more than 90%, and the yield of divinyl is for reaching more than 58%.
Specific implementation method
Below by embodiment, the present invention is described in further details.But described example is not construed as limiting the invention.
Embodiment 1
Kaolinite Preparation of Catalyst process
By 9.7g Bi (NO
3)
35H
2o is dissolved in 50mL containing in the salpeter solution of 10%, and this solution is designated as solution A, in 60 DEG C of water-baths, by 1.1g (NH
4)
2ce (NO
3)
6be dissolved in 200mL deionized water, this solution is designated as B solution, in 60 DEG C of water-baths, by 3.53g (NH
4)
2mo
7o
244H
2o is dissolved in 200mL deionized water, and this solution is designated as C solution, and wherein, the mol ratio of molybdenum and bismuth is 1:1, and the mol ratio of cerium and bismuth is 0.1:1.A dropwise drops in B, after fully stirring.Mixed solution B is dropwise dropped in C solution, after abundant stirring, dripping massfraction in C solution is the ammonia soln of 25%, and adjust ph is 5, after dropwising, continuation is stirred to sticky under the water-bath of 60 DEG C, dope is transferred in the loft drier of 60 DEG C dry, is being connected with 550 DEG C of roasting 2h in the tube furnace under oxygen atmosphere, grinding after cooling, screening obtains 40 ~ 60 object Four composition bismuth molybdenum catalysts, and catalyzer is designated as BiMoCe
0.1, airtight preservation.
Oxidative dehydrogenation process
Be in the stainless steel reactor of 8mm to internal diameter by above-mentioned for 1.5mL packed catalyst, adopt 1-butylene as unstripped gas, its percentage composition is 99.9%.Pass into air and water vapour, its composition is set as 1-butylene: air simultaneously: the mol ratio of water vapour is 1:4:10, and imported in reactor by this gas mixture, air speed is 327h
-1, reaction bed temperature is 440 DEG C and reacts, gas chromatographic analysis 2h, and the product reaction result after 10h is as follows:
| 2h | 10h | |
| 1-butylene transformation efficiency/% | 71.8 | 71.6 |
| 1,3-butadiene selectivity/% | 95.4 | 95.1 |
Embodiment 2
Kaolinite Preparation of Catalyst process
By 9.7gBi (NO
3)
35H
2o is dissolved in 50mL containing in the salpeter solution of 10%, and this solution is designated as solution A, in 70 DEG C of water-baths, by 2.19g (NH
4)
2ce (NO
3)
6be dissolved in 200mL deionized water, this solution is designated as B solution, in 70 DEG C of water-baths, by 3.53g (NH
4)
2mo
7o
244H
2o is dissolved in 200mL deionized water, and this solution is designated as C solution, and wherein, the mol ratio of molybdenum and bismuth is 1:1, and the mol ratio of cerium and bismuth is 0.2:1.A dropwise drops in B, after fully stirring.Mixed solution B is dropwise dropped in C solution, after abundant stirring, dripping massfraction in C solution is the ammonia soln of 25%, and adjust ph is 5, after dropwising, continuation is stirred to sticky under the water-bath of 70 DEG C, dope is transferred in the loft drier of 60 DEG C dry, is being connected with 500 DEG C of roasting 2h in the tube furnace under oxygen atmosphere, grinding after cooling, screening obtains 40 ~ 60 object Four composition bismuth molybdenum catalysts, and catalyzer is designated as BiMoCe
0.2, airtight preservation.
Oxidative dehydrogenation process
Be in the stainless steel reactor of 8mm to internal diameter by above-mentioned for 1.5mL packed catalyst, adopt 1-butylene as unstripped gas, its percentage composition is 99.9%.Pass into air and water vapour, its composition is set as 1-butylene: air simultaneously: the mol ratio of water vapour is 1:4:5, and imported in reactor by this gas mixture, air speed is 436h
-1, reaction bed temperature is 440 DEG C and reacts, gas chromatographic analysis 2h, and the product reaction result after 10h is as follows:
| 2h | 10h | |
| 1-butylene transformation efficiency/% | 76.8 | 76.6 |
| 1,3-butadiene selectivity/% | 96.7 | 96.8 |
Embodiment 3
Kaolinite Preparation of Catalyst process
By 9.7g Bi (NO
3)
35H
2o is dissolved in 50mL containing in the salpeter solution of 10%, and this solution is designated as solution A, in 60 DEG C of water-baths, by 3.29g (NH
4)
2ce (NO
3)
6be dissolved in 200mL deionized water, this solution is designated as B solution, in 60 DEG C of water-baths, by 3.53g (NH
4)
2mo
7o
244H
2o is dissolved in 200mL deionized water, and this solution is designated as C solution, and wherein, the mol ratio of molybdenum and bismuth is 1:1, and the mol ratio of cerium and bismuth is 0.3:1.A dropwise drops in B, after fully stirring.Mixed solution B is dropwise dropped in C solution, after abundant stirring, dripping massfraction in C solution is the ammonia soln of 25%, and adjust ph is 5, after dropwising, continuation is stirred to sticky under the water-bath of 60 DEG C, dope is transferred in the loft drier of 60 DEG C dry, is being connected with 550 DEG C of roasting 2h in the tube furnace under oxygen atmosphere, grinding after cooling, screening obtains 40 ~ 60 object Four composition bismuth molybdenum catalysts, and catalyzer is designated as BiMoCe
0.3, airtight preservation.
Oxidative dehydrogenation process
Be in the stainless steel reactor of 8mm to internal diameter by above-mentioned for 1.5mL packed catalyst, adopt 1-butylene as unstripped gas, its percentage composition is 99.9%.Pass into air and water vapour, its composition is set as 1-butylene: air simultaneously: the mol ratio of water vapour is 1:4:10, and imported in reactor by this gas mixture, air speed is 327h
-1, reaction bed temperature is 440 DEG C and reacts, gas chromatographic analysis 2h, and the product reaction result after 10h is as follows:
| 2h | 10h | |
| 1-butylene transformation efficiency/% | 74.8 | 74.6 |
| 1,3-butadiene selectivity/% | 96.4 | 96.1 |
Embodiment 4
Kaolinite Preparation of Catalyst process
By 9.7g Bi (NO
3)
35H
2o is dissolved in 50mL containing in the salpeter solution of 10%, and this solution is designated as solution A, in 60 DEG C of water-baths, by 4.39g (NH
4)
2ce (NO
3)
6be dissolved in 200mL deionized water, this solution is designated as B solution, in 60 DEG C of water-baths, by 3.53g (NH
4)
2mo
7o
244H
2o is dissolved in 200mL deionized water, and this solution is designated as C solution, and wherein, the mol ratio of molybdenum and bismuth is 1:1, and the mol ratio of cerium and bismuth is 0.4:1.A dropwise drops in B, after fully stirring.Mixed solution B is dropwise dropped in C solution, after abundant stirring, dripping massfraction in C solution is the ammonia soln of 25%, and adjust ph is 5, after dropwising, continuation is stirred to sticky under the water-bath of 60 DEG C, dope is transferred in the loft drier of 60 DEG C dry, is being connected with 550 DEG C of roasting 2h in the tube furnace under oxygen atmosphere, grinding after cooling, screening obtains 40 ~ 60 object Four composition bismuth molybdenum catalysts, and catalyzer is designated as BiMoCe
0.4, airtight preservation.
Oxidative dehydrogenation process
Be in the stainless steel reactor of 8mm to internal diameter by above-mentioned for 1mL packed catalyst, adopt 1-butylene as unstripped gas, its percentage composition is 99.9%.Pass into air and water vapour, its composition is set as 1-butylene: air simultaneously: the mol ratio of water vapour is 1:4:5, and imported in reactor by this gas mixture, air speed is 436h
-1, reaction bed temperature is 440 DEG C and reacts, gas chromatographic analysis 2h, and the product reaction result after 10h is as follows:
| 2h | 10h | |
| 1-butylene transformation efficiency/% | 67.8 | 68.1 |
| 1,3-butadiene selectivity/% | 95.6 | 95.5 |
Embodiment 5
Kaolinite Preparation of Catalyst process
By 9.7g Bi (NO
3)
35H
2o is dissolved in 50mL containing in the salpeter solution of 10%, and this solution is designated as solution A, in 60 DEG C of water-baths, by 6.58g (NH
4)
2ce (NO
3)
6be dissolved in 200mL deionized water, this solution is designated as B solution, in 60 DEG C of water-baths, by 3.53g (NH
4)
2mo
7o
244H
2o is dissolved in 200mL deionized water, and this solution is designated as C solution, and wherein, the mol ratio of molybdenum and bismuth is 1:1, and the mol ratio of cerium and bismuth is 0.6:1.A dropwise drops in B, after fully stirring.Mixed solution B is dropwise dropped in C solution, after abundant stirring, dripping massfraction in C solution is the ammonia soln of 25%, and adjust ph is 5, after dropwising, continuation is stirred to sticky under the water-bath of 60 DEG C, dope is transferred in the loft drier of 60 DEG C dry, is being connected with 550 DEG C of roasting 2h in the tube furnace under oxygen atmosphere, grinding after cooling, screening obtains 40 ~ 60 object Four composition bismuth molybdenum catalysts, and catalyzer is designated as BiMoCe
0.6, airtight preservation.
Oxidative dehydrogenation process
Be in the stainless steel reactor of 8mm to internal diameter by above-mentioned for 1mL packed catalyst, adopt 1-butylene as unstripped gas, its percentage composition is 99.9%.Pass into air and water vapour, its composition is set as 1-butylene: air simultaneously: the mol ratio of water vapour is 1:4:15, and imported in reactor by this gas mixture, air speed is 436h
-1, reaction bed temperature is 440 DEG C and reacts, gas chromatographic analysis 2h, and the product reaction result after 10h is as follows:
| 2h | 10h | |
| 1-butylene transformation efficiency/% | 65.7 | 65.4 |
| 1,3-butadiene selectivity/% | 94.6 | 94.7 |
Embodiment 6
Kaolinite Preparation of Catalyst process
By 9.7gBi (NO
3)
35H
2o is dissolved in 50mL containing in the salpeter solution of 10%, and this solution is designated as solution A, in 60 DEG C of water-baths, by 10.96g (NH
4)
2ce (NO
3)
6be dissolved in 200mL deionized water, this solution is designated as B solution, in 60 DEG C of water-baths, by 3.53g (NH
4)
2mo
7o
244H
2o is dissolved in 200mL deionized water, and this solution is designated as C solution, and wherein, the mol ratio of molybdenum and bismuth is 1:1, and the mol ratio of cerium and bismuth is 1:1.A dropwise drops in B, after fully stirring.Mixed solution B is dropwise dropped in C solution, after abundant stirring, dripping massfraction in C solution is the ammonia soln of 25%, and adjust ph is 5, after dropwising, continuation is stirred to sticky under the water-bath of 60 DEG C, is transferred to by dope in the loft drier of 60 DEG C dry, is being connected with 550 DEG C of roasting 2h in the tube furnace under oxygen atmosphere, grinding after cooling, screening obtains 40 ~ 60 object Four composition bismuth molybdenum catalysts, and catalyzer is designated as BiMoCe, airtight preservation.
Oxidative dehydrogenation process
Be in the stainless steel reactor of 8mm to internal diameter by above-mentioned for 2mL packed catalyst, adopt 1-butylene as unstripped gas, its percentage composition is 99.9%.Pass into air and water vapour, its composition is set as 1-butylene: air simultaneously: the mol ratio of water vapour is 1:5:15, and imported in reactor by this gas mixture, air speed is 218h
-1, reaction bed temperature is 440 DEG C and reacts, gas chromatographic analysis 2h, and the product reaction result after 10h is as follows:
| 2h | 10h | |
| 1-butylene transformation efficiency/% | 63.2 | 63.1 |
| 1,3-butadiene selectivity/% | 92.4 | 92.3 |
Above content is in conjunction with concrete preferred implementation further description made for the present invention; can not assert that the specific embodiment of the present invention is only limitted to this; for general technical staff of the technical field of the invention; under the prerequisite departing from the present invention's design; some simple deductions and replacement can also be made, all should be considered as belonging to the protection domain of the present invention by submitted to claims determination patent.
Claims (1)
1., by the method for Bi/Mo/Ce three components composite oxide catalysts synthesis 1,3-butadiene, it is characterized in that:
The three components composite oxide catalysts prepared is placed in reactor, and gas mixture is imported in reactor, keep certain air speed and reaction bed temperature to react, obtain 1,3-butadiene product;
Described gas mixture comprises 1-butylene, air and water vapour, and mixed volume is than being 1:3 ~ 5:5 ~ 16;
Described certain air speed is 219 ~ 438h
-1, reaction bed temperature is set as 380 ~ 450 DEG C;
Described three components composite oxide catalysts composition comprises Bi, Mo and Ce, and wherein the mol ratio of molybdenum and bismuth is 1:1, and the mol ratio of cerium and bismuth is 0.1 ~ 1:1;
The synthesis of described three components composite oxide catalysts comprises the steps:
The cerium salt of certain mass and deionized water are configured in container by step (1), molybdenum salt and deionized water are configured in another container, wherein bismuth salt is dissolved in containing in certain density salpeter solution, is dropwise added drop-wise in the solution containing cerium salt by bismuth salts solution, and fully stirs; Dropwise be added drop-wise in the solution of molybdenum salt by mixed solution after stirring, make the mol ratio of molybdenum and bismuth be 1:1, the mol ratio of cerium and bismuth is 0.1 ~ 1:1;
Above-mentioned solution is placed in the water-bath of 50 ~ 70 DEG C by step (2), dropwise drips with certain density ammoniacal liquor, regulates pH;
After step (3) is extremely sticky by the solution stirring of step (2), transfer in baking oven dry;
Step (4) gained solid, after roasting, cooling, obtains 40 ~ 60 object three components composite oxide catalysts through grinding, screening;
Described cerium salt and the mol ratio of deionized water are 1:10 ~ 100; Described molybdenum salt and the ratio of deionized water are 1:10 ~ 100; The concentration of described salpeter solution is 5% ~ 50%: in bismuth salt and salpeter solution, the mol ratio of nitric acid is 1:5 ~ 50;
The massfraction of described ammonia soln is 25%; After regulating, pH value is 3 ~ 7;
Described dry time oven temperature be 60 ~ 150 DEG C;
Described maturing temperature is 300 ~ 700 DEG C, and roasting time is 2 ~ 6h;
In described catalyzer, bismuth derives from bismuth salt, and this bismuth salt is Bismuth trinitrate; Molybdenum derives from molybdenum salt, and molybdenum salt is ammonium molybdate; Cerium derives from cerium salt, and cerium salt is ceric ammonium nitrate.
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| CN103483130B (en) * | 2013-09-23 | 2015-05-20 | 浙江大学 | Method for synthesizing 1,3-butadiene by adopting Bi/Mo/La/Fe four-component composite oxide catalyst |
| CN113019442B (en) * | 2019-12-09 | 2022-05-17 | 中国科学院大连化学物理研究所 | Supported catalyst for preparing acrylic acid by propylene oxidation and preparation and application thereof |
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