CN107537535B - Catalyst for preparing butadiene by oxidative dehydrogenation of butylene under low water ratio condition and preparation method and process method thereof - Google Patents
Catalyst for preparing butadiene by oxidative dehydrogenation of butylene under low water ratio condition and preparation method and process method thereof Download PDFInfo
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Abstract
4 a b cthe invention relates to a catalyst for preparing butadiene by oxidative dehydrogenation of butylene under the condition of low water ratio, a preparation method and a process method thereof, and mainly solves the problems of high steam unit consumption, large wastewater generation amount and high energy consumption in the existing production process for preparing butadiene by oxidative dehydrogenation of butylene under the condition of low water ratio.
Description
Technical Field
The invention relates to a catalyst for preparing butadiene by oxidative dehydrogenation of butylene under the condition of low water ratio, and a preparation method and a process method thereof.
Background
The main application field of 1,3-butadiene is the production of synthetic rubbers such as butadiene rubber, styrene butadiene rubber, ABS, SBS, nitrile butadiene rubber and the like, and also the production of other products such as adiponitrile (nylon 66 monomer), sulfolane, anthraquinone, tetrahydrofuran and the like. Worldwide butadiene consumption was about 1056.2 ten thousand tons in 2012. Butadiene plays an important role in petrochemical olefin feedstocks.
The production method of butadiene mainly comprises two production methods of carbon four extraction separation and butylene oxidative dehydrogenation for preparing ethylene by steam cracking and coproducing. Currently, the vast majority of butadiene production in the world is done by the pyrolysis carbon four extraction process. Due to the vigorous development of the shale gas revolution in the United states, light hydrocarbons are more adopted as cracking raw materials by the ethylene cracking unit in the United states, and light raw materials are adopted by over 60 percent of ethylene production capacity in North America. In order to reduce production costs, ethylene cracking companies in asian regions such as china, korea, etc. have been increasing the proportion of light hydrocarbons in cracking feedstocks in recent years, and the lightening of ethylene plant feedstocks has led to a continuous tightening of the global butadiene supply. With the rapid development of the synthetic rubber and resin industry and the wider and wider application of butadiene, the market demand of butadiene is continuously increased, and the butadiene raw material is in short supply. In general, it is expected that in the next few years, the worldwide production of butadiene will increase at a rate of less than 3% per year, while the rate of butadiene consumption will increase by far more than 3%, demand will increase faster than the rate of energy production, and the shortage will be a normalized trend in the future.
In recent years, as butadiene obtained by adopting a cracking carbon four-extraction process can not meet the market demand gradually, people begin to pay attention to the research of butylene oxidative dehydrogenation technology. The carbon four-fraction of the refinery contains a large amount of butylene, the carbon four-fraction has low use added value as civil fuel, and the high-selectivity conversion of the butylene into butadiene has obvious economic benefit and has important significance for the comprehensive utilization of carbon four-fraction resources. The process route for producing butadiene by oxidative dehydrogenation of butylene has great application prospect.
oxidative dehydrogenation of butene is a strongly exothermic reaction, and in order to achieve a good catalytic effect, a large amount of water vapor is generally required to be mixed into a reaction raw material as a diluent gas and a heat carrier.
The Oxo-D process of the American TPC group (formerly Texas Petrochemical) and the O-X-D process of Philips are typical processes for preparing butadiene through oxidative dehydrogenation of butene. These processes use a ferrite catalyst, with a molar ratio of water vapor to butenes of about 10: 1.
The processes for preparing butadiene by oxidative dehydrogenation of butylene, which have been used for industrial production in China, mainly comprise an adiabatic fixed bed reaction process adopting a B-02 iron-based catalyst and a fluidized bed reaction process adopting an H-198 iron-based catalyst as a representative. Higher water-to-olefin ratios are required for both reaction processes, with the B-02 adiabatic fixed bed process using a steam to butene molar ratio of about 16: 1; the H-198 fluidized bed reaction process employs a steam to butene molar ratio of about 10: 1.
The ferrite catalyst based on spinel structure is a better catalyst for preparing butadiene by oxidative dehydrogenation of butylene (USP3270080, CN1088624C, CN1072110, CN1184705 and the like), but has the problem of large steam consumption. The existing production process for preparing butadiene by oxidative dehydrogenation of butylene has high steam unit consumption, large wastewater generation amount and high energy consumption, and the amount of steam needs to be reduced as much as possible along with the improvement of the requirements on environmental protection, energy conservation and emission reduction. However, the current relevant patent literature reports that the research on the low water ratio catalyst for preparing butadiene by oxidative dehydrogenation of butene has less mention. The development of high-activity and low-water-ratio catalysts is the key of the low-water-ratio and low-energy-consumption butylene oxidative dehydrogenation technology.
Disclosure of Invention
The invention aims to solve the technical problems of high steam unit consumption, large waste water generation amount and high energy consumption in the existing production process of preparing butadiene by oxidative dehydrogenation of butylene, and provides a novel catalyst for preparing butadiene by oxidative dehydrogenation of butylene under the condition of low water ratio.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a catalyst for preparing butadiene by oxidative dehydrogenation of butylene under the condition of low water ratio comprises the following components:
a) BiPO 4 is used as a main active component;
b) An oxide of A, B, C component is taken as an auxiliary agent, and the auxiliary agent and BiPO 4 are calculated by molar ratio to form a composition with a chemical formula of BiPA a B b C c O x, wherein:
A is selected from at least one of Fe or Cr;
b is selected from at least one of Zn, Mg or Co;
C is selected from at least one of lanthanide;
the value range of a is 0.01-1;
The value range of b is 0.01-1;
the value range of c is 0-0.5;
x is the total number of oxygen atoms required to satisfy the valence state of each element in the catalyst.
In the above technical solution, the component B is preferably at least one selected from Zn or Mg; the component C is preferably at least one selected from La, Ce or Nd; the preferable range of the value of a is 0.1-0.5; the preferable range of the value of b is 0.05-0.5; the preferable range of the value of c is 0-0.2.
The invention relates to a catalyst for preparing butadiene by oxidative dehydrogenation of butylene under the condition of low water ratio, which can be prepared by the following steps:
a) Preparing a mixed solution containing a catalyst auxiliary component and fully stirring;
b) Co-precipitating the mixed solution with an alkaline solution at a suitable pH value;
c) And mixing, drying, roasting and molding the main active component and the auxiliary agent component.
In the above technical scheme, the precursor of the auxiliary component can be selected from one of chloride or nitrate; the pH value in the precipitation process is 6-12, the washing temperature is 10-80 ℃, the drying temperature is 90-150 ℃, the drying time is 1-24 hours, the roasting temperature is 400-650 ℃, and the roasting time is 1-24 hours; the alkaline solution is selected from one of ammonia water, sodium hydroxide or potassium hydroxide, wherein the ammonia water is the best, and the concentration of the ammonia water is preferably 10-30%.
The application of the catalyst in the preparation of butadiene by oxidative dehydrogenation of butylene under the condition of low water ratio can adopt the following process steps:
The method comprises the steps of taking mixed gas of butylene, air or oxygen and water vapor as raw materials, enabling the temperature of a reaction inlet to be 300-500 ℃, enabling the mass space velocity of butylene to be 1.0-6.0 h -1, and enabling the raw materials to be in contact reaction with a catalyst to obtain butadiene.
Butene in the reactants: oxygen: the volume ratio of water vapor is 1: (0.5-4): (1-10), preheating water into steam before entering the reactor, and fully mixing the steam with the raw material gas.
In the above technical scheme, butene: the volume ratio of the water vapor is preferably 1: (2-6), and the more preferable scheme is 1: (2-5).
the catalyst can be shaped in different modes and is used in a fixed bed or a fluidized bed reactor.
Compared with the prior art, the invention has obvious advantages and outstanding effects.
The invention adopts BiPO 4 as a main active component, BiPO 4 has better oxygen activation capacity and reaction activity, meanwhile, the hydrophilicity is stronger, the reaction activity of the catalyst can be improved through stronger hydration, the utilization efficiency of water vapor is improved, and the consumption of the water vapor is reduced, thereby achieving the purposes of energy saving and emission reduction.
The butylene oxidative dehydrogenation reaction is carried out on a micro catalytic reaction device of a continuous flow quartz tube reactor. Analysis of products the contents of alkane, alkene, butadiene, etc. in the dehydrogenated product were analyzed on-line using HP-5890 gas chromatograph (HP-AL/S capillary column, 50 m.times.0.53 mm.times.15 μm; FID detector) and the conversion of the reaction and the product selectivity were calculated. The catalyst prepared by the method provided by the invention is used for the oxidative dehydrogenation of butylene, wherein the weight ratio of butylene: the molar ratio of water vapor is only 1: and (2) the catalyst can keep high performance under the condition of low water-olefin ratio, the conversion rate of butene reaches 70%, the selectivity of butadiene is higher than 90%, the catalyst has good performance and high stability, and a good technical effect is obtained.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
121.2g of iron nitrate (Fe (NO 3) 3 & 9H 2 O), 40g of chromium nitrate (Cr (NO 3) 3 & 9H 2 O), 29.6g of zinc nitrate (Zn (NO 3) 2 & 6H 2 O) and 21.7g of cerium nitrate (Ce (NO 3) 3 & 6H 2 O) were weighed and dissolved in 1L of deionized water, and stirred uniformly to form a solution, then the solution was coprecipitated with a 20% aqueous ammonia solution, the pH value of the precipitate was maintained at 9.5, the precipitation temperature was room temperature, then a solid sample in the precipitated product was separated by a centrifugal separator, washed with 1L of deionized water, the obtained solid was mixed uniformly with 304g of bismuth phosphate (BiPO 4), dried in an oven at 110 ℃ for 4 hours, the dried sample was further calcined in a muffle furnace at 600 ℃ for 4 hours to obtain catalyst A, and ground into particles of 40-60 mesh for catalyst evaluation, the molar ratio of the elemental composition of the catalyst A was BiPO 583948 Cr 0.1 Ce 0.1.
[ example 2 ]
20.2g of iron nitrate (Fe (NO 3) 3 & 9H 2 O), 20g of chromium nitrate (Cr (NO 3) 3 & 9H 2 O), 14.8g of zinc nitrate (Zn (NO 3) 2 & 6H 2 O) and 8.7g of cerium nitrate (Ce (NO 3) 3 & 6H 2 O) were weighed and dissolved in 1L of deionized water, and stirred uniformly to form a solution, then the solution was coprecipitated with a 10% aqueous ammonia solution, the pH value of the precipitate was maintained at 6.0 and the precipitation temperature was 10 ℃, then a solid sample in the precipitated product was separated by a centrifugal separator, washed with 1L of deionized water, the obtained solid was mixed uniformly with 304g of bismuth phosphate (BiPO 4), dried in an oven at 110 ℃ for 4 hours, the dried sample was further calcined in a muffle furnace at 400 ℃ for 24 hours to obtain catalyst B, and the catalyst B was ground into particles of 40-60 mesh for catalyst evaluation.
[ example 3 ]
161.6g of iron nitrate (Fe (NO 3) 3 & 9H 2 O), 40g of chromium nitrate (Cr (NO 3) 3 & 9H 2 O), 59.2g of zinc nitrate (Zn (NO 3) 2 & 6H 2 O) and 86.8g of cerium nitrate (Ce (NO 3) 3 & 6H 2 O) were dissolved in 1L of deionized water and stirred uniformly to form a solution, then the solution was coprecipitated with a 30% aqueous ammonia solution, the precipitation pH was maintained at 12 and the precipitation temperature was 80 ℃, then a solid sample in the precipitated product was separated out with a centrifugal separator, washed with 1L of deionized water, the resulting solid was mixed uniformly with 304g of bismuth phosphate (BiPO 4), dried in an oven at 110 ℃ for 4 hours, the dried sample was again calcined in a muffle furnace at 650 ℃ for 1 hour to obtain catalyst C, and ground into particles of 40-60 mesh for catalyst evaluation, the molar ratio of elemental composition of the catalyst C was BiZn 0.1 Cr 5838 Ce.
[ example 4 ]
4.04g of iron nitrate (Fe (NO 3) 3.9H 2 O), 4.0g of chromium nitrate (Cr (NO 3) 3.9H 2 O), 2.96g of zinc nitrate (Zn (NO 3) 2.6H 2 O) and 4.34g of cerium nitrate (Ce (NO 3) 3.6H 2 O) were weighed and dissolved in 100mL of deionized water, and stirred uniformly to form a solution, then the catalyst precursor solution was coprecipitated with 15% aqueous ammonia solution, the precipitation pH was maintained at 8.0, the precipitation temperature was 40 ℃, then a solid sample in the precipitated product was separated by a centrifugal separator, washed with 100mL of deionized water, the obtained solid was mixed uniformly with 304g of bismuth phosphate (BiPO 4), dried in an oven at 110 ℃ for 4 hours, the dried sample was calcined in a muffle furnace at 600 ℃ for 4 hours to obtain catalyst D, which was ground into particles of 40-60 mesh for evaluation of catalyst D element composition, and the molar ratio of PFe 395838 Ce to 0.01.
[ example 5 ]
323.2g of iron nitrate (Fe (NO 3) 3 & 9H 2 O), 80g of chromium nitrate (Cr (NO 3) 3 & 9H 2 O), 148g of zinc nitrate (Zn (NO 3) 2 & 6H 2 O) and 217g of cerium nitrate (Ce (NO 3) 3 & 6H 2 O) were dissolved in 2L of deionized water and stirred uniformly to form a solution, then the catalyst precursor solution was coprecipitated with a 25% aqueous ammonia solution, the precipitation pH was maintained at 10.0 and the precipitation temperature was 60 ℃, then a solid sample in the precipitated product was separated out with a centrifugal separator, washed with 2L of deionized water, the obtained solid was mixed uniformly with 304g of bismuth phosphate (BiPO 4), dried in an oven at 110 ℃ for 4 hours, the dried sample was further calcined in a muffle furnace at 600 ℃ for 4 hours to obtain catalyst E, which was ground into 40-60 mesh particles for catalyst evaluation, the elemental composition of PFBie 638 Zn 638 Ce 0.5 O.
[ example 6 ]
161.6g of iron nitrate (Fe (NO 3) 3.9H 2 O), 25.6g of magnesium nitrate (Mg (NO 3) 2.6H 2 O) and 21.7g of cerium nitrate (Ce (NO 3) 3.6H 2 O) are weighed and dissolved in 1L of deionized water, and stirred uniformly to form a solution, then the solution and 2M NaOH are subjected to coprecipitation, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate product is separated by a centrifugal separator, the solid sample is washed by 1L of deionized water, the obtained solid and 304g of bismuth phosphate (BiPO 4) are mixed uniformly, the dried sample is dried in an oven at 110 ℃ for 4 hours, then the dried sample is calcined in a muffle furnace at 600 ℃ for 4 hours to obtain catalyst F, and the catalyst F is ground into particles of 40-60 meshes for catalyst evaluation, and the molar ratio of the element composition of the catalyst F is BiPFe 0.4 Mg 0.1 0.05 O x.
[ example 7 ]
161.6G of iron nitrate (Fe (NO 3) 3.9H 2 O), 25.6G of magnesium nitrate (Mg (NO 3) 2.6H 2 O) and 21.7G of lanthanum nitrate (La (NO 3) 3.6H 2 O) were weighed and dissolved in 1L of deionized water, and stirred uniformly to form a solution, then the above solution was coprecipitated with 2M KOH solution, the precipitation pH was maintained at 9.5, the precipitation temperature was room temperature, then a solid sample in the precipitated product was separated with a centrifugal separator, washed with 1L of deionized water, the obtained solid was mixed uniformly with 304G of bismuth phosphate (BiPO 4), dried in an oven at 110 ℃ for 4 hours, the dried sample was further calcined in a muffle furnace at 600 ℃ for 4 hours to obtain catalyst G, and ground into 40-60 mesh particles for catalyst evaluation, the molar ratio of the element composition of catalyst G was Bie 0.4 Mg 46 0.05 O x.
[ example 8 ]
161.6g of iron nitrate (Fe (NO 3) 3.9H 2 O), 25.6g of magnesium nitrate (Mg (NO 3) 2.6H 2 O) and 21.8g of neodymium nitrate (Nd (NO 3) 3.6H 2 O) were weighed and dissolved in 1L of deionized water, and stirred uniformly to form a solution, then the above solution was coprecipitated with 3M KOH solution, the precipitation pH was maintained at 9.5, the precipitation temperature was room temperature, then a solid sample in the precipitated product was separated with a centrifugal separator, washed with 1L of deionized water, the obtained solid was mixed uniformly with 304g of bismuth phosphate (BiPO 4), dried in an oven at 110 ℃ for 4 hours, the dried sample was further calcined in a muffle furnace at 600 ℃ for 4 hours to obtain catalyst H, and ground into 40-60 mesh particles for catalyst evaluation, the molar ratio of the element composition of the catalyst H was BiPFe 0.4 Mg 46637 Nd 68562O x.
[ example 9 ]
160g of chromium nitrate (Cr (NO 3) 3.9H 2 O), 25.6g of magnesium nitrate (Mg (NO 3) 2.6H 2 O) and 21.7g of cerium nitrate (Ce (NO 3) 3.6H 2 O) are weighed and dissolved in 1L of deionized water, the mixture is stirred uniformly to form a solution, then the solution and 20% ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate product is separated by a centrifugal separator, the precipitate product is washed by 1L of deionized water, the obtained solid and 304g of bismuth phosphate (BiPO 4) are mixed uniformly, the precipitate is dried in an oven at 110 ℃ for 4 hours, the dried sample is calcined in a muffle furnace at 600 ℃ for 4 hours to obtain catalyst I, and the catalyst I is ground into particles of 40-60 meshes for catalyst evaluation, and the molar ratio of the element composition of the catalyst I is BiPCr 0.4 Mg 0.1 Ce 0.05 O x.
[ example 10 ]
160g of chromium nitrate (Cr (NO 3) 3.9H 2 O), 29.6g of zinc nitrate (Zn (NO 3) 2.6H 2 O) and 21.7g of lanthanum nitrate (La (NO 3) 3.6H 2 O) are weighed and stirred uniformly in 1L of deionized water to form a solution, then the solution is coprecipitated with 20% ammonia water solution, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate product is separated by a centrifugal separator, the precipitate product is washed by 1L of deionized water, the obtained solid and 304g of bismuth phosphate (BiPO 4) are mixed uniformly, the dried sample is dried in an oven at 110 ℃ for 4 hours, the dried sample is calcined in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst J, and the catalyst J is ground into particles of 40-60 meshes for catalyst evaluation, and the molar ratio of the element composition of the catalyst J is BiPCr 0.4 Zn 0.1 La 0.05 O x.
[ example 11 ]
121.2g of iron nitrate (Fe (NO 3) 3.9H 2 O), 40g of chromium nitrate (Cr (NO 3) 3.9H 2 O), 14.8g of zinc nitrate (Zn (NO 3) 2.6H 2 O), 12.8g of magnesium nitrate (Mg (NO 3) 2.6H 2 O), 17.4g of cerium nitrate (Ce (NO 3) 3.6H 2 O) and 4.3g of lanthanum nitrate (La (NO 3) 3.6H 2 O) were weighed out and dissolved in 1L of deionized water, stirred to form a solution, and then the solution was coprecipitated with 20% aqueous ammonia solution, the precipitation pH was maintained at 9.5, the precipitation temperature was room temperature, then a solid sample in the precipitated product was separated with a centrifugal separator, washed with 1L of deionized water, the resulting solid was mixed with 304g of bismuth phosphate (BiPO 4), dried in a PFF 4 hours at 110 ℃ for 4 hours, and then ground to obtain a catalyst particle composition of BiPO 0.05 K 0.05 Mg, 0.05 K 0.05, and finally the catalyst was calcined at 0.05 mol ratio of 0.05 K 0.05.
[ example 12 ]
161.6g of ferric nitrate (Fe (NO 3) 3.9H 2 O) and 25.6g of magnesium nitrate (Mg (NO 3) 2.6H 2 O) are weighed and dissolved in 1L of deionized water, the mixture is uniformly stirred to form a solution, then the solution and 20% ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 9.5, the precipitation temperature is room temperature, then a solid sample in the precipitate product is separated by a centrifugal separator, the precipitate product is washed by 1L of deionized water, the obtained solid and 304g of bismuth phosphate (BiPO 4) are uniformly mixed, the mixture is dried in an oven at 110 ℃ for 4 hours, the dried sample is roasted in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst L, the catalyst L is ground into particles of 40-60 meshes and used for evaluating the catalyst, and the molar ratio of the element composition of the catalyst L is PFBie 0.4 Mg 0.1 O x.
Comparative example 1
304g of bismuth phosphate (BiPO 4) is weighed and roasted in a muffle furnace for 4 hours at 600 ℃ to obtain a catalyst M, and the catalyst M is ground into particles of 40-60 meshes for catalyst evaluation, wherein the molar ratio of the element composition of the catalyst M is BiPO 4.
Comparative example 2
161.6g of ferric nitrate (Fe (NO 3) 3.9H 2 O) is weighed and dissolved in 1L of deionized water, the mixture and 20% of ammonia water solution are subjected to coprecipitation, the pH value of the precipitate is kept at 9.5, then a solid sample in the precipitate product is separated by a centrifugal separator, the obtained solid and 304g of bismuth phosphate (BiPO 4) are uniformly mixed, the mixture is dried in an oven at 110 ℃ for 4 hours, the dried sample is roasted in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst N, and the catalyst N is ground into particles of 40-60 meshes for catalyst evaluation, wherein the element composition molar ratio of the catalyst N is BiPFe 0.4 O x.
comparative example 3
weighing a proper amount of ferric nitrate (Fe (NO 3) 3 & 9H 2 O) and zinc nitrate (Zn (NO 3) 2 & 6H 2 O) and dissolving the mixture in 1L of distilled water, uniformly stirring to form a solution, then carrying out coprecipitation on the solution and a 20% ammonia water solution, keeping the pH value of the precipitate at 9.5 and the precipitation temperature at room temperature, then separating a solid sample in the precipitate product by using a centrifugal separator, washing the solid sample by using 1L of distilled water, drying the obtained solid in an oven at 110 ℃ for 4 hours, roasting the dried sample in a muffle furnace at 600 ℃ for 4 hours to obtain a catalyst O, grinding the catalyst O into particles of 40-60 meshes for catalyst evaluation, wherein the element composition molar ratio of the catalyst O is ZnFe 2 O 4.
Comparative example 4
A proper amount of Bi 2 MoO 6 is weighed and ground into particles of 40-60 meshes for catalyst evaluation, and the element composition molar ratio of the catalyst P is Bi 2 MoO 6.
Comparative example 5
1212g of iron nitrate (Fe (NO 3) 3 & 9H 2 O), 40g of chromium nitrate (Cr (NO 3) 3 & 9H 2 O), 444g of zinc nitrate (Zn (NO 3) 2 & 6H 2 O) and 21.7g of cerium nitrate (Ce (NO 3) 3 & 6H 2 O) were weighed and dissolved in 1L of deionized water, and stirred uniformly to form a solution, then the solution was coprecipitated with 20% aqueous ammonia solution, the pH value of the precipitate was maintained at 9.5, the precipitation temperature was room temperature, then a solid sample in the precipitated product was separated out by a centrifugal separator, washed with 1L of deionized water, the obtained solid was mixed uniformly with 304g of bismuth phosphate (BiPO 4), dried in an oven at 110 ℃ for 4 hours, the dried sample was further calcined in a muffle furnace at 600 ℃ for 4 hours to obtain catalyst Q, which was ground into particles of 40-60 mesh for catalyst evaluation, and the elemental composition of catalyst Q was PFBie 0.1 Cr 1.5 Ce.
[ example 13 ]
0.5g of catalysts A to Q are taken for butylene oxidative dehydrogenation evaluation, feed gas is a mixture of butylene, oxygen and water vapor, wherein the molar ratio of butylene, oxygen and water is 1: 0.75: 3, raw material gases are fully mixed and then introduced into a reactor for oxidative dehydrogenation reaction, the inlet temperature of the reactor is 340 ℃, the reaction pressure is normal pressure, the mass space velocity of butylene is 4.0h -1, catalytic reaction is carried out under the conditions, reaction products are analyzed by gas chromatography, and the reaction results are listed in Table 1.
TABLE 1
| catalyst and process for preparing same | butene conversion (%) | Butadiene selectivity (%) |
| A | 71.0 | 94.2 |
| B | 69.3 | 92.5 |
| C | 70.1 | 93.6 |
| D | 67.8 | 90.0 |
| E | 72.4 | 92.1 |
| F | 70.1 | 93.9 |
| G | 69.2 | 93.7 |
| H | 69.5 | 92.3 |
| I | 72.2 | 91.6 |
| J | 71.4 | 90.3 |
| K | 70.7 | 93.8 |
| L | 70.5 | 89.5 |
| comparative example M | 40.2 | 82.1 |
| Comparative example N | 48.9 | 81.5 |
| Comparative example O | 45.1 | 84.0 |
| Comparative example P | 63.4 | 80.9 |
| Comparative example Q | 64.1 | 82.8 |
Butene conversion and butadiene selectivity over 10 hours of reaction
[ example 14 ]
0.5g of catalyst A, M is taken for butylene oxidative dehydrogenation evaluation, a feed gas is a mixture of butylene, oxygen and steam, wherein the molar ratio of butylene, oxygen and water is 1: 0.75: 3, raw material gases are fully mixed and then introduced into a reactor for oxidative dehydrogenation reaction, the inlet temperature of the reactor is 340 ℃, the reaction pressure is normal pressure, the mass space velocity of butylene is 4.0h -1, the catalytic reaction is carried out under the conditions, reaction products are analyzed by gas chromatography, and the reaction results are listed in Table 2.
TABLE 2
[ example 15 ]
0.5g of catalyst A is taken for butylene oxidative dehydrogenation evaluation, a feed gas is a mixture of butylene, oxygen and steam, wherein the molar ratio of butylene to oxygen is 1: 0.75, the molar ratio of water to butylene is listed in Table 3, raw material gases are fully mixed and then introduced into a reactor for oxidative dehydrogenation reaction, the inlet temperature of the reactor is 340 ℃, the reaction pressure is normal pressure, the mass space velocity of butylene is 4.0h -1, the catalytic reaction is carried out under the conditions, reaction products are analyzed by gas chromatography, and the reaction results are listed in Table 3.
TABLE 3
| Water to olefin ratio (mol) | Butene conversion (%) | Butadiene selectivity (%) |
| 1 | 55.4 | 83.8 |
| 2 | 65.1 | 89.1 |
| 3 | 71.0 | 94.2 |
| 4 | 72.2 | 94.5 |
| 5 | 73.0 | 94.7 |
| 6 | 73.3 | 94.8 |
| 10 | 70.1 | 94.7 |
Claims (9)
1. A catalyst for preparing butadiene by oxidative dehydrogenation of butylene under the condition of low water ratio comprises the following components:
a) BiPO 4 is used as a main active component;
b) An oxide of A, B, C component is taken as an auxiliary agent, and the auxiliary agent and BiPO 4 are calculated by molar ratio to form a composition with a chemical formula of BiPA a B b C c O x, wherein:
A is selected from at least one of Fe or Cr;
B is selected from at least one of Zn, Mg or Co;
C is selected from at least one of La, Ce or Nd;
the value range of a is 0.01-1;
The value range of b is 0.01-1;
The value range of c is 0-0.5;
x is the total number of oxygen atoms required to satisfy the valence state of each element in the catalyst.
2. The catalyst for preparing butadiene by oxidative dehydrogenation of butene under the condition of low water ratio according to claim 1, wherein the value range of a is 0.1-0.5.
3. The catalyst for preparing butadiene by oxidative dehydrogenation of butene under the condition of low water ratio according to claim 1, wherein the value of b ranges from 0.05 to 0.5.
4. the catalyst for preparing butadiene by oxidative dehydrogenation of butene under the condition of low water ratio according to claim 1, wherein the value range of c is 0-0.2.
5. The catalyst for the oxidative dehydrogenation of butene to butadiene under low water ratio conditions according to claim 1, wherein the preparation method of the catalyst comprises the following steps:
a) Preparing a mixed solution containing a catalyst auxiliary component and fully stirring;
b) Co-precipitating the mixed solution and an alkaline solution at a proper pH value, and then washing;
c) And mixing, drying, roasting and molding the main active component and the auxiliary agent component.
6. the catalyst for preparing butadiene by oxidative dehydrogenation of butene under the condition of low water ratio according to claim 5, wherein the pH value in the precipitation process is 6-12, the washing temperature is 10-80 ℃, the drying temperature is 90-150 ℃, the drying time is 1-24 hours, the roasting temperature is 400-650 ℃, and the roasting time is 1-24 hours.
7. The application of the catalyst for preparing butadiene by oxidative dehydrogenation of butylene under the condition of low water ratio is characterized in that mixed gas of butylene, oxygen-containing gas and steam is used as raw materials, the temperature of a reaction inlet is 300-500 ℃, the mass space velocity of butylene is 1.0-6.0 h -1, and butadiene is obtained after the raw materials are in contact reaction with the catalyst of any one of claims 1-6.
8. The use according to claim 7 of a catalyst for the oxidative dehydrogenation of butenes to butadiene under low water ratio conditions, wherein the molar ratio of butenes: oxygen-containing gas: the volume ratio of water vapor is 1: (0.5-4): (1-10).
9. Use of a catalyst according to claim 7 or 8 for the oxidative dehydrogenation of butenes to butadiene under low water ratio conditions, with the molar ratio of butenes: the volume ratio of water vapor is 1: (2-6).
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| CN111054353A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene |
| CN111054354A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene and preparation method thereof |
| CN112569973A (en) * | 2019-09-27 | 2021-03-30 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butene, preparation method and application thereof |
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