CN108014831B - Catalyst for preparing butadiene by oxidative dehydrogenation of butylene - Google Patents

Catalyst for preparing butadiene by oxidative dehydrogenation of butylene Download PDF

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CN108014831B
CN108014831B CN201610964338.8A CN201610964338A CN108014831B CN 108014831 B CN108014831 B CN 108014831B CN 201610964338 A CN201610964338 A CN 201610964338A CN 108014831 B CN108014831 B CN 108014831B
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catalyst
oxidative dehydrogenation
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butadiene
nitrate
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CN108014831A (en
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樊志贵
吴文海
缪长喜
曾铁强
张新玉
姜冬宇
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • 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
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/843—Arsenic, antimony or bismuth
    • B01J23/8435—Antimony
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/843—Arsenic, antimony or bismuth
    • B01J23/8437—Bismuth
    • 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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
    • 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
    • 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 invention relates to a catalyst for preparing butadiene through oxidative dehydrogenation of butylene, which mainly solves the problems of high water ratio and high energy consumption in the prior art. The general formula of the catalyst structure adopted by the invention is ZnaAbMcFeOxWherein M is at least one element selected from Be, Mg, Ca, Sr, Mn, Ba, Cu, Co and Ni, and A is at least one element selected from P, Sb and Bi. The method comprises the following steps: precipitating a metal precursor and ammonia water or sodium hydroxide to generate slurry of an insoluble compound, washing, filtering, adding a binder, ball-milling, spray-drying, granulating, and roasting to obtain the catalyst. The catalyst prepared by the invention is used for the reaction of preparing butadiene by oxidative dehydrogenation of butylene, effectively reduces the reaction water ratio, has better activity when the water ratio is 4-8, and can be used in the industrial production of the catalyst for preparing butadiene by oxidative dehydrogenation of butylene.

Description

Catalyst for preparing butadiene by oxidative dehydrogenation of butylene
Technical Field
The invention relates to a catalyst for producing butadiene by oxidative dehydrogenation of butylene and a preparation method thereof; in particular to a catalyst for producing butadiene by oxidative dehydrogenation of butylene in a fluidized bed.
Background
Butadiene is a basic raw material of petrochemical industry, is an important monomer for producing synthetic rubber and other high-molecular synthetic materials, and can be copolymerized with various compounds to prepare various synthetic rubbers and synthetic resins. At present, butadiene mainly comprises two production methods, namely extraction separation of carbon four and butylene oxidation, which are used for preparing ethylene by steam cracking in a refinery. Almost all butadiene in China comes from carbon four extraction separation, the process is economically advantageous, but the butadiene is obtained as a byproduct of a cracking device of a refinery, the demand of the butadiene is continuously increased due to the rapid development of the rubber and resin industry in recent years, the long-term vigorous demand of the butadiene raw material is determined by the lightening of the oil refining raw material and the regional characteristics that China cannot plant rubber forests on a large scale, and the butadiene produced by the cracking device is difficult to meet the demand. The butylene oxidative dehydrogenation is a process taking butadiene as a target product, and can convert butylene used by civil fuel into butadiene with high added value.
Since the sixty years of the century, catalysts for producing butadiene by oxidative dehydrogenation of butene are catalyzed by catalysts of various metal oxide systems, and a Mo-Bi system, a Sn-P-Li system and a Fe acid salt system can be used for the oxidative dehydrogenation reaction of butene. But the Mo-Bi system has low selectivity and produces a large amount of organic oxygen-containing byproducts. The Sn-P-Li system has high activity, but has harsh operation conditions, high water-olefin ratio and high energy consumption. The iron-based catalyst has obvious advantages, such as high butadiene yield, less oxidation by-products, low water-olefin ratio and the like, and the spinel-type iron-based catalyst is most widely used at present. Compared with the prior molybdenum series, tin series, antimony series and other catalysts, the iron series catalyst has the advantages of mild reaction conditions, high catalytic activity, more specific selectivity and the like. AB2O4The catalyst for preparing butadiene by oxidative dehydrogenation of iron spinel butylene is firstly reported in USP3270080, and B02 catalyst for preparing butadiene by oxidative dehydrogenation of chromium-free iron butylene for adiabatic fixed bed is developed by synthetic rubber factories of Yanshan petrochemical company. The butylene oxidative dehydrogenation belongs to a strong exothermic reaction, and the heat transfer of the fixed bed reactor is difficult, so that the temperature of a catalyst bed layer is over-high, the temperature control is not facilitated, and the butylene oxidative dehydrogenation in the fluidized bed reactor is easy to transfer heat, so that isothermal operation can be realized, the service life of the catalyst is prolonged, and the utilization rate of the catalyst is improved. The institute of chemical and physical technology, Lanzhou, the Chinese academy invented butene oxidative dehydrogenation catalysts (CN1013247B, CN1072110A and CN 118) capable of being used in fluidized bed4705A) Although the catalyst has certain activity and selectivity when being used in a baffle fluidized bed, the catalyst has larger particle size, which results in lower butadiene yield and more serious catalyst loss, and CN201210241468.0 discloses a fluidized bed iron-based catalyst which achieves certain effects, but the technology has higher water-olefin ratio in the reaction process, larger energy consumption and reduced income.
Disclosure of Invention
The invention aims to solve the technical problems of high reaction temperature, high water-olefin ratio, high energy consumption and low catalyst activity of the catalyst in the prior art, and provides a novel catalyst for preparing butadiene by oxidative dehydrogenation of butylene. The catalyst has the advantages of low water ratio and high selectivity. The second technical problem to be solved by the present invention is to provide a method for preparing a catalyst corresponding to the first technical problem.
In order to solve one of the above technical problems, the technical solution adopted by the present invention is as follows: a catalyst for preparing butadiene by oxidative dehydrogenation of butylene has a general structural formula of ZnaAbMcFeOxWherein M is selected from at least one element of Be, Mg, Ca, Sr, Mn, Ba, Cu, Co and Ni, A is selected from at least one element of P, Sb and Bi, the ratio of a, b and c in the formula represents the atomic number ratio of Zn, A and M in the catalyst, wherein, a is more than 0 and less than 0.5, b is more than 0 and less than or equal to 0.3, c is more than 0 and less than 0.6, and the value of x meets the requirement of valence.
In the above technical scheme, M is at least one element selected from Be, Mg, Ca, Sr, Mn, Ba, Cu, Co and Ni, A is at least one element selected from P, Sb and Bi, and/or the molar ratio of P to at least one element selected from Sb and Bi is 1: 3. Wherein the ratio of a, b and c represents the atomic number ratio of Zn, A and M in the catalyst, wherein a is more than 0 and less than 0.5; preferably 0 < a < 0.4; more preferably 0.1 < a < 0.3; b is more than 0 and less than 0.5; preferably 0 < b < 0.5; more preferably 0 < b < 0.5; c is more than 0 and less than 0.6; preferably 0.1 < c < 0.5; more preferably 0.2 < c < 0.5. Wherein A is selected from at least one element of Sb and Bi and P; and/or the molar ratio of at least one element selected from Sb and Bi to P is 1: 3.
In the technical scheme, the catalyst preferably further comprises Re, and the molar ratio of Re to Fe is 0.01-0.1.
In order to solve the second technical problem, the invention adopts the following technical scheme: the preparation method of the catalyst for preparing butadiene by oxidative dehydrogenation of butene comprises the following steps:
(1) precipitating a metal precursor and ammonia water or sodium hydroxide at a pH of 7-11 to generate slurry of an insoluble compound, aging, washing and filtering; (2) washing, filtering, adding a binder and an acid containing A, fully stirring and then ball-milling; (3) spray drying and granulating the obtained slurry, and roasting to obtain a catalyst; preferably, the precipitation manner includes dropping the metal precursor into the alkali substance, dropping the alkali substance into the metal precursor, or dropping the metal precursor and the alkali substance together.
In the technical scheme, metal ion solution with required amount is prepared, ammonia water or sodium hydroxide solution is used as a precipitator, the precipitation mode comprises three modes of positive addition, reverse addition and concurrent addition, wherein the concurrent addition is optimal, the pH value of the precipitation end point is 8-9, the precipitation aging temperature is 20-60 ℃, after washing and filtering, a binder and phosphoric acid are added, and 1-5% of an organic binder and a proper amount of acid containing A are added. Finally, carrying out spray drying granulation on the obtained slurry, drying for 10-20 hours at 40-120 ℃, then roasting at 500-800 ℃ for 6-12 hours to obtain a catalyst, wherein the particles of the catalyst are smaller than 300 microns; preferably less than 250 microns; more preferably less than 200 microns.
Using butylene, oxygen-containing gas and water vapor as raw materials, and reacting at the temperature of 300-550 ℃ and the volume space velocity of 100-2000 h-1And the raw material and the catalyst react in a contact manner under the conditions that the molar ratio of the oxyalkylene is 0.2-1.5 and the molar ratio of the water to the oxyalkylene is 2-20 to obtain the butadiene.
In the technical scheme, the preferable water-olefin molar ratio is 4-12; more preferably, the water-olefin molar ratio is 4-8; and/or the reaction temperature is 300-500 ℃; and/or the volume space velocity is 200-1000 h-1The preferred volume space velocity is 200-500 h-1(ii) a And/or the molar ratio of oxyalkylene is 0.6 to 0.9.
According to the technical scheme, when the water-olefin molar ratio is 4-12, particularly when the water-olefin molar ratio is low, the catalytic activity of butylene oxidative dehydrogenation is good, the conversion rate of butylene can reach more than 68%, and a good technical effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
230.8 g of magnesium nitrate, 178.5 g of zinc nitrate and 1532.3 g of iron nitrate were dissolved in 3L of distilled water, 15% aqueous ammonia was added dropwise with rapid stirring, the precipitation end point pH was 9.0, the mixture was stirred at 50 ℃ for 30 minutes, allowed to stand at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 35.8 g of phosphoric acid, 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 750 ℃ to obtain a catalyst sample.
[ example 2 ]
243.6 g of magnesium nitrate, 238.0 g of zinc nitrate and 1725.3 g of iron nitrate were dissolved in 3L of distilled water, and 15% aqueous ammonia solution was added dropwise with rapid stirring, the precipitation end point pH was 8.0, and the mixture was stirred at 50 ℃ for 30 minutes, left standing at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 54.6 g of phosphoric acid, 600 g of 2% glycerol solution and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 650 ℃ to obtain a catalyst sample.
[ example 3 ]
200.6 g of magnesium nitrate, 119.00 g of zinc nitrate and 1345.3 g of iron nitrate were dissolved in 3L of distilled water, and 15% aqueous ammonia solution was added dropwise with rapid stirring, the precipitation end point pH was 9.0, and the mixture was stirred at 50 ℃ for 30 minutes, left standing at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 39.2 g of phosphoric acid, 600 g of 2% glycerol solution and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, transferring into a muffle furnace, and roasting for 10 hours at the furnace temperature of 650 ℃ to obtain a catalyst sample.
[ example 4 ]
89.7 g of magnesium nitrate, 482.9 g of zinc nitrate, 72.5 g of copper nitrate and 1534.5 g of iron nitrate were dissolved in 3L of distilled water, and a 15% aqueous ammonia solution was added dropwise with rapid stirring, the pH at the end of precipitation was 9.0, and the mixture was stirred at 40 ℃ for 30 minutes, left standing at 40 ℃ for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 53.6 g of phosphoric acid, 30 g of methylcellulose and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 120 ℃ for 12 hours, transferring into a muffle furnace, and roasting for 6 hours at the furnace temperature of 650 ℃ to obtain a catalyst sample.
[ example 5]
179.5 g of magnesium nitrate, 348.7 g of zinc nitrate, 58.2 g of nickel nitrate and 1345.1 g of iron nitrate were dissolved in 3L of distilled water, and 3M sodium hydroxide solution was added dropwise with rapid stirring, with a precipitation end pH of 9.0, at 30 ℃ for 30 minutes with stirring, left standing at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 86.4 g of phosphoric acid, 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 650 ℃ to obtain a catalyst sample.
[ example 6 ]
52.3 g of barium nitrate, 341.2 g of magnesium nitrate, 236.7 g of zinc nitrate and 1432.5 g of iron nitrate were dissolved in 3L of distilled water to prepare a mother liquor, the mother liquor and a 15% ammonia solution were simultaneously added dropwise with rapid stirring until the final pH of the precipitate became 9.0, the precipitate was aged, stirred at 40 ℃ for 30 minutes, allowed to stand at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration became less than 1000 ppm. Adding 58.6 g of phosphoric acid, 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 650 ℃ to obtain a catalyst sample.
[ example 7 ]
50.8 g of strontium nitrate, 413.7 g of magnesium nitrate, 142.8 g of zinc nitrate and 1268.7 g of ferric nitrate were dissolved in 3L of distilled water to prepare a mother liquor, the mother liquor and a 15% ammonia aqueous solution were simultaneously dropped while stirring rapidly, the final pH of the precipitate was 9.0, the precipitate was aged, stirred at 40 ℃ for 30 minutes, allowed to stand at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 47.6 g of phosphoric acid, 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 650 ℃ to obtain a catalyst sample.
[ example 8 ]
Dissolving 81.5 g of cobalt nitrate, 135.9 g of magnesium nitrate, 64.3 g of zinc nitrate and 1356.4 g of ferric nitrate in 3L of distilled water to prepare a mother liquor, simultaneously dropping the mother liquor and a 15% ammonia solution while stirring rapidly, aging the precipitate until the final pH is 9.0, stirring at 40 ℃ for 30 minutes, standing at room temperature for 2 hours, filtering the obtained slurry, and washing until the nitrate ion concentration is less than 1000 ppm. Adding 21.6 g of phosphoric acid, 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 650 ℃ to obtain a catalyst sample.
[ example 9 ]
87.4 g of calcium nitrate, 128.2 g of magnesium nitrate, 202.3 g of zinc nitrate and 1453.9 g of iron nitrate were dissolved in 3L of distilled water to prepare a mother liquor, the mother liquor and a 15% aqueous ammonia solution were simultaneously dropped while stirring rapidly, the precipitation end point pH was 9.0, the precipitate was aged, stirred at 40 ℃ for 30 minutes, allowed to stand at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 17.6 g of phosphoric acid, 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 650 ℃ to obtain a catalyst sample.
[ example 10 ]
Dissolving 101.5 g of copper nitrate, 93.1 g of nickel nitrate, 166.6 g of zinc nitrate and 1325.4 g of ferric nitrate in 3L of distilled water to prepare a mother liquor, simultaneously dropping the mother liquor and a 15% ammonia solution while stirring rapidly, aging the precipitate until the final pH is 9.0, stirring at 40 ℃ for 30 minutes, standing at room temperature for 2 hours, filtering the obtained slurry, and washing until the nitrate ion concentration is less than 1000 ppm. Adding 49.2 g of phosphoric acid, 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 650 ℃ to obtain a catalyst sample.
[ example 11 ]
58.0 g of copper nitrate, 54.9 g of barium nitrate, 297.5 g of zinc nitrate and 1536.4 g of iron nitrate were dissolved in 3L of distilled water to prepare a mother liquor, the mother liquor and a 15% aqueous ammonia solution were simultaneously dropped while stirring rapidly, the precipitation end point pH was 9.0, the precipitate was aged, stirred at 40 ℃ for 30 minutes, allowed to stand at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 46.9 g of phosphoric acid, 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 650 ℃ to obtain a catalyst sample.
[ example 12 ]
157.0 g of nickel nitrate, 163.0 g of cobalt nitrate, 238.0 g of zinc nitrate and 1332.3 g of iron nitrate were dissolved in 3L of distilled water to prepare a mother liquor, the mother liquor and a 15% aqueous ammonia solution were simultaneously dropped while stirring rapidly, the final pH of the precipitate was 9.0, the precipitate was aged, stirred at 50 ℃ for 30 minutes, allowed to stand at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 153.7 g of bismuth nitrate, 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere molding in a spray dryer, drying at 90 ℃ for 12 hours, transferring into a muffle furnace, roasting for 6 hours, and performing furnace temperature 650 ℃ to obtain a catalyst sample.
[ example 13 ]
48.3 g of copper nitrate, 99.2 g of calcium nitrate, 142.8 g of zinc nitrate and 1268.9 g of iron nitrate were dissolved in 3L of distilled water to prepare a mother liquor, the mother liquor and a 15% aqueous ammonia solution were simultaneously dropped while stirring rapidly, the final pH of the precipitate was 9.0, the precipitate was aged, stirred at 50 ℃ for 30 minutes, allowed to stand at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 121.3 g of antimony nitrate, 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 650 ℃ to obtain a catalyst sample.
[ example 14 ]
58.2 g of cobalt nitrate, 29.9 g of beryllium nitrate, 153.9 g of magnesium nitrate, 130.9 g of zinc nitrate and 1352.8 g of ferric nitrate were dissolved in 3L of distilled water to prepare a mother liquor, the mother liquor and a 15% aqueous ammonia solution were simultaneously added dropwise with rapid stirring until the end point of precipitation pH was 9.0, the precipitate was aged, stirred at 50 ℃ for 30 minutes, allowed to stand at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 46.9 g of phosphoric acid, 100 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 650 ℃ to obtain a catalyst sample.
[ example 15 ]
69.8 g of nickel nitrate, 116.5 g of cobalt nitrate, 15.1 g of manganese nitrate, 153.9 g of magnesium nitrate, 186.2 g of zinc nitrate and 1534.1 g of iron nitrate were dissolved in 3L of distilled water to prepare a mother liquor, the mother liquor and a 15% aqueous ammonia solution were simultaneously dropped while stirring rapidly, the precipitation end point pH was 9.0, the precipitate was aged, stirred at 40 ℃ for 30 minutes, allowed to stand at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 55.7 g of phosphoric acid, 300 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 650 ℃ to obtain a catalyst sample.
[ example 16 ]
48.3 g of copper nitrate, 99.2 g of calcium nitrate, 142.8 g of zinc nitrate and 1268.9 g of iron nitrate were dissolved in 3L of distilled water to prepare a mother liquor, the mother liquor and a 15% aqueous ammonia solution were simultaneously dropped while stirring rapidly, the final pH of the precipitate was 9.0, the precipitate was aged, stirred at 50 ℃ for 30 minutes, allowed to stand at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 41.8 g of phosphoric acid, 37.2 g of antimony nitrate, 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying for 12 hours at 90 ℃, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 650 ℃ to obtain a catalyst sample.
[ example 17 ]
48.3 g of copper nitrate, 99.2 g of calcium nitrate, 142.8 g of zinc nitrate and 1268.9 g of iron nitrate were dissolved in 3L of distilled water to prepare a mother liquor, the mother liquor and a 15% aqueous ammonia solution were simultaneously dropped while stirring rapidly, the final pH of the precipitate was 9.0, the precipitate was aged, stirred at 50 ℃ for 30 minutes, allowed to stand at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 41.8 g of phosphoric acid, 58.6 g of bismuth nitrate, 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying for 12 hours at 90 ℃, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 650 ℃ to obtain a catalyst sample.
[ example 18 ]
200.6 g of magnesium nitrate, 119.00 g of zinc nitrate and 1345.3 g of iron nitrate were dissolved in 3L of distilled water, and 15% aqueous ammonia solution was added dropwise with rapid stirring, the precipitation end point pH was 9.0, and the mixture was stirred at 50 ℃ for 30 minutes, left standing at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 39.2 g of phosphoric acid into the active component slurry, drying at 90 ℃ for 12 hours, transferring into a muffle furnace, roasting for 10 hours at the furnace temperature of 650 ℃, obtaining a catalyst sample, and screening for later use.
[ example 19 ]
230.8 g of magnesium nitrate, 178.5 g of zinc nitrate, 23 g of ammonium perrhenate and 1532.3 g of iron nitrate were dissolved in 3L of distilled water, a 15% aqueous ammonia solution was added dropwise with rapid stirring, the precipitation end point pH was 9.0, the mixture was stirred at 50 ℃ for 30 minutes, allowed to stand at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 35.8 g of phosphoric acid, 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 750 ℃ to obtain a catalyst sample.
[ example 20 ]
230.8 g of magnesium nitrate, 178.5 g of zinc nitrate, 230 g of ammonium perrhenate and 1532.3 g of iron nitrate were dissolved in 3L of distilled water, a 15% aqueous ammonia solution was added dropwise with rapid stirring, the precipitation end point pH was 9.0, the mixture was stirred at 50 ℃ for 30 minutes, allowed to stand at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 35.8 g of phosphoric acid, 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, performing ball milling for 2 hours at room temperature to obtain the slurry, performing microsphere formation in a spray dryer, drying at 90 ℃ for 12 hours, then transferring into a muffle furnace for roasting for 6 hours, and performing furnace temperature 750 ℃ to obtain a catalyst sample.
Comparative example 1
200.6 g of magnesium nitrate, 119.00 g of zinc nitrate and 1345.3 g of iron nitrate were dissolved in 3L of distilled water, and 15% aqueous ammonia solution was added dropwise with rapid stirring, the precipitation end point pH was 9.0, and the mixture was stirred at 50 ℃ for 30 minutes, left standing at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, ball-milling for 2 hours at room temperature to obtain the slurry, forming microspheres in a spray dryer, drying for 12 hours at 90 ℃, then transferring into a muffle furnace to roast for 6 hours, and obtaining a catalyst sample at the furnace temperature of 650 ℃.
Comparative example 2
157.0 g of nickel nitrate, 163.0 g of cobalt nitrate, 238.0 g of zinc nitrate and 1332.3 g of iron nitrate were dissolved in 3L of distilled water to prepare a mother liquor, the mother liquor and a 15% aqueous ammonia solution were simultaneously dropped while stirring rapidly, the final pH of the precipitate was 9.0, the precipitate was aged, stirred at 50 ℃ for 30 minutes, allowed to stand at room temperature for 2 hours, and the resulting slurry was filtered and washed until the nitrate ion concentration was less than 1000 ppm. Adding 200 g of 10% PVA and deionized water into the active component slurry to prepare slurry, controlling the solid content to be 30%, stirring for about 10 minutes, ball-milling for 2 hours at room temperature to obtain the slurry, forming microspheres in a spray dryer, drying for 12 hours at 90 ℃, then transferring into a muffle furnace to roast for 6 hours, and obtaining a catalyst sample at the furnace temperature of 650 ℃.
Comparative example 3
Compared with CN96113127.6, the catalyst of example 10 is reacted in a fluidized bed reactor, the volume space velocity of butylene is 400h < -1 >, the volume ratio of oxygen to butylene is 0.65, the molar ratio of water to olefin is 6, the reaction temperature is 340 ℃, and the results are shown in Table 1.
Comparative example 4
Compared with CN201310334136.1 which describes that the catalyst of example 7 is adopted, the volume space velocity of the reaction butylene is 400h in the fluidized bed reactor-1The molar ratio of oxygen to butene was 0.65, the molar ratio of water to olefin was 6, and the reaction temperature was 340 ℃ with the results shown in Table 1.
The catalysts prepared in examples 1-17 and comparative examples I, II and III were reacted in a fluidized bed reactor, the catalysts prepared in example 18 and comparative example IV were evaluated in a fixed bed reactor, and the space velocity of butene was 400h-1The volume ratio of oxygen to butene was 0.65, the water-olefin molar ratio was 6, and the reaction temperature was 340 ℃ as shown in Table 1.
TABLE 1
Figure BDA0001144640680000101
Figure BDA0001144640680000111
[ examples 19 to 25]
The catalyst prepared in example 3 was reacted under different conditions, and the evaluation results and the reaction conditions are shown in Table 2.
TABLE 2
Figure BDA0001144640680000112

Claims (10)

1. A catalyst for preparing butadiene by oxidative dehydrogenation of butylene, wherein the structural formula of the catalyst is Zn0.16P0.08Mg0.24FeOxAnd the value of x meets the requirement of valence; wherein the catalyst also comprises Re, and the molar ratio of Re to Fe is 0.01-0.1.
2. The catalyst for the oxidative dehydrogenation of butene to butadiene according to claim 1 wherein the particles of the catalyst are less than 300 microns.
3. The catalyst for the oxidative dehydrogenation of butene to butadiene according to claim 1 wherein the particles of the catalyst are less than 250 microns.
4. The catalyst for the oxidative dehydrogenation of butene to butadiene according to claim 1 wherein the particles of the catalyst are less than 200 microns.
5. The method for preparing the catalyst for preparing butadiene through oxidative dehydrogenation of butene as claimed in any one of claims 1 to 4, wherein the preparation method comprises the following steps: (1) precipitating a metal precursor and ammonia water or sodium hydroxide at a pH of 7-11 to generate slurry of an insoluble compound, aging, washing and filtering; (2) washing, filtering, adding a binder and an acid containing A, fully stirring and then ball-milling; (3) and carrying out spray drying granulation on the obtained slurry, and roasting to obtain the catalyst.
6. The method of claim 5, wherein the precipitation method comprises dropping the metal precursor into the alkaline substance, dropping the alkaline substance into the metal precursor, or dropping the metal precursor and the alkaline substance together.
7. A method for preparing butadiene through oxidative dehydrogenation of butylene takes butylene, oxygen-containing gas and water vapor as raw materials, and the reaction temperature is 300-550 ℃, and the volume space velocity is 100-2000 h-1The molar ratio of oxyalkylene is 0.2-1.5, and the oxyalkylene isAnd (3) carrying out contact reaction on the raw material and the catalyst according to any one of claims 1 to 4 under the condition that the molar ratio is 2-20 to obtain butadiene.
8. The method for preparing butadiene through oxidative dehydrogenation of butene according to claim 7, wherein the molar ratio of water to olefin is 4-12; the reaction temperature is 300-500 ℃; the volume space velocity is 200-1000 h-1(ii) a The molar ratio of the oxygen to the olefin is 0.6 to 0.9.
9. The method for preparing butadiene through oxidative dehydrogenation of butene according to claim 7, wherein the molar ratio of water to olefin is 4-8.
10. The method for preparing butadiene through oxidative dehydrogenation of butene according to claim 7, wherein the volume space velocity is 200-500 h-1。
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