CN112239391B - Method for preparing 1,3-butadiene by butene dehydrogenation - Google Patents

Method for preparing 1,3-butadiene by butene dehydrogenation Download PDF

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CN112239391B
CN112239391B CN201910638288.8A CN201910638288A CN112239391B CN 112239391 B CN112239391 B CN 112239391B CN 201910638288 A CN201910638288 A CN 201910638288A CN 112239391 B CN112239391 B CN 112239391B
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butene
butadiene
catalyst
preparing
dehydrogenating
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CN112239391A (en
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缪长喜
危春玲
范玉桥
华伟明
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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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    • 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
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J35/394—
    • B01J35/615—
    • B01J35/635—

Abstract

The invention relates to a method for preparing 1,3-butadiene by butene dehydrogenation, which mainly solves the problem of lower yield of 1,3-butadiene in the prior art. Taking a mixed gas of 1-butene and carbon dioxide as a raw material, wherein the reaction temperature is 550-650 ℃, and the mass airspeed of 1-butene is 2-10 hours ‑1 The mol ratio of the raw material 1-butene to the carbon dioxide is 1 (2-10), and the raw material is contacted with a 1-butene dehydrogenation catalyst to react to obtain 1, 3-butadiene; the catalyst comprises a carrier and an active component, wherein the carrier comprises one selected from MCM-41, SBA-15, HMS, MCF or Silicalite-1 molecular sieve, the active component is selected from indium, the carrier contains abundant hole hydroxyl groups, the active component can interact with the carrier, the technical problem is well solved, and the catalyst can be used in industrial production for preparing 1,3-butadiene by dehydrogenation under the carbon dioxide atmosphere of 1-butene.

Description

Method for preparing 1,3-butadiene by butene dehydrogenation
Technical Field
The invention relates to a method for preparing 1,3-butadiene by dehydrogenating 1-butene.
Background
CO 2 Plays an important role in global warming. Annual CO 2 Is about 1.2 hundred million tons and is artificially CO 2 The total discharge amounts to about 24 billion tons. CO while controlling emissions levels 2 The utilization of (3) is also beneficial to our environment. Mukherjee et al published in 2016 a report on CO 2 Progress in dehydrogenation of lower alkanes and ethylbenzene as weak oxidants (CO 2 as a soft oxidant for oxidative dehydrogenation reaction:An eco benign process for industry,Journal of CO 2 Utilization, volume 16, pages 301-312, 2016). With other oxidants (e.g. O 2 、SO 2 And N 2 O) compared with CO 2 Has several advantages. CO 2 Ratio O 2 Mild, avoids the combustion of valuable hydrocarbons, and CO 2 Is less hazardous than N 2 O and SO 2 。CO 2 Selectivity can be enhanced by poisoning non-selective sites on the catalyst surface. CO 2 It is also possible to react (C+CO) by the Boudeouard reaction 2 2 CO) eliminates part of carbon deposition on the surface of the catalyst, and slows down the deactivation of the catalyst. In addition, CO 2 Is the largest of these gases, which reduces hot spots.
1,3-butadiene has a unique conjugated double bond structure, is widely used for industrial synthesis of chemical products such as styrene butadiene rubber, nitrile butadiene rubber, acrylonitrile-butadiene-styrene resin, nylon-66 and the like, and has important positions in petrochemical production. As represented by the vigorous demand of the synthetic rubber industry, the downstream demand of 1,3-butadiene is increasing, and the conventional method for preparing 1,3-butadiene by extracting the C4 by-product of ethylene cracking is greatly impacted by the light weight of the ethylene cracking raw material, so that the supply of 1,3-butadiene is becoming tight. Therefore, a route for producing 1,3-butadiene by oxidative dehydrogenation of butene has attracted attention. The preparation of butadiene by dehydrogenation of butylene under the carbon dioxide atmosphere is a novel green process with application prospect. The reported catalysts are Fe 2 O 3 /Al 2 O 3 System (Improving oxidative dehydrogenation of-Butene to 1,3-Butadiene on A) l2 O 3 by Fe 2 O 3 using CO 2 As Soft oxadan, applied Catalysis A: general, volume 508, pages 61-67, 2015) and Pt/Al 2 O 3 System (Effects of Pt) 0 -PtO x particle size on 1-butene oxidative dehydrogenation to 1,3-butadiene using CO 2 as soft oxidant,Journal of CO 2 Utilization, volume 2016, 15, pages 154-159), the highest yields of 1,3-butadiene were only 22%.
Disclosure of Invention
One of the technical problems to be solved by the invention is the problem of lower yield of 1,3-butadiene in the prior art, and a novel method for preparing 1,3-butadiene is provided, and the method has the characteristic of 1,3-butadiene yield by adopting a novel catalyst for 1-butene dehydrogenation reaction.
The second technical problem to be solved by the invention is to provide a 1-butene dehydrogenation catalyst corresponding to one of the technical problems.
The invention provides a preparation method of a 1-butene dehydrogenation catalyst corresponding to one of the technical problems.
In order to solve one of the technical problems, the invention adopts the following technical scheme: a method for preparing 1,3-butadiene by dehydrogenating 1-butene uses the mixed gas of 1-butene and carbon dioxide as raw material, the reaction temperature is 550-650 ℃, and the mass airspeed of 1-butene is 2-10 hours -1 The mole ratio of the raw material 1-butene to the carbon dioxide is 1 (2-10), and the raw material is contacted and reacted with a 1-butene dehydrogenation catalyst to obtain the 1, 3-butadiene.
In the technical scheme, the reaction comprises the following steps: the catalyst is activated for 1-3 hours in the argon atmosphere at 550-650 ℃ before the reaction, and the mol ratio of the raw material 1-butene to the carbon dioxide is 1 (4-8).
In order to solve the second technical problem, the technical scheme adopted by the invention is as follows: a 1-butene dehydrogenation catalyst, the catalyst comprising a support and an active component, the support being selected from one of MCM-41, SBA-15, HMS, MCF or Silicalite-1 molecular sieves, preferably Silicalite-1 molecular sieves; the active component is selected from indium.
In the technical scheme, the carrier is preferably Silicalite-1 molecular sieve, and the specific surface area of the Silicalite-1 molecular sieve is 380-420 m 2 Per gram, the total pore volume is 0.49-0.55 cm 3 /g。
In the technical scheme, the active component indium accounts for the total mass percent of the catalyst, and the mass percent of the indium accounts for In 2 O 3 Accounting for 0.6 to 25 percent; preferably 3.5 to 15%.
In the technical scheme, the scanning electron microscope of the catalyst is approximately spherical in morphology, and the grain size of the particles is 70 nm-3 mu m.
In the technical scheme, in the aspect of improving the yield of the 1,3-butadiene, the active component indium and the carrier hydroxyl are acted and dispersed in the silicon hydroxyl holes, so that the active component indium has the effect of promoting the activity.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the preparation method of the 1-butene dehydrogenation catalyst comprises the following steps:
(1) The carrier is contacted with hydrogen peroxide to obtain a pretreated carrier;
(2) The active component is contacted with water at 60-90 ℃, then is contacted with the pretreated carrier in the step (1), and the pH value of the solution is controlled to 7.5-9, thus obtaining a solid catalyst;
(3) Preferably, the method further comprises the steps of filtering, washing, drying and roasting the solid obtained in the step (2) to obtain the 1-butene dehydrogenation catalyst.
In the above technical scheme, the active component is selected from In salt, and the raw material of the In salt is selected from In (NO) 3 ) 3 、InCl 3 Or In 2 (SO 4 ) 3 At least one of them is preferably In (NO 3 ) 3 。
In the above technical scheme, the concentration of the hydrogen peroxide solution in the step (1) is 2% -5%, preferably, the carrier contacts with hydrogen peroxide and further comprises the steps of soaking, washing with deionized water and drying; wherein the soaking time is 12-36 hours, and the drying condition is 80-120 ℃ for 12-36 hours.
In the technical scheme, the hydroxyl content of the pretreated carrier obtained in the step (1) is 0.4-0.6 mmol/g.
In the technical scheme, ammonia water is selected in the step (2) to control the pH value of the solution, wherein the concentration of the ammonia water is 5-7 mol/L, and the control range of the pH value is preferably 8-8.5.
In the technical scheme, the drying condition in the step (3) is 80-120 ℃ for 10-30 hours.
In the technical scheme, the roasting condition in the step (3) is roasting for 3-8 hours at 600-650 ℃ in air atmosphere.
The shape and size of the catalyst sample in the invention are tested on a Phenom G3 scanning electron microscope, and the voltage is 10kV.
The amount of hydroxyl groups in the carrier was measured by TG, a thermal analyzer of TA instruments company TA-4000 (TGA-2050). Sample 2-3 mg placed in 40 ml/min N 2 In the atmosphere, the temperature is increased to 800 ℃ from room temperature at a speed of 10 ℃/graduation, a catalyst weight loss curve is detected, the hydroxyl content of a sample is calculated from the weight loss of the sample above 200 ℃ (the hydroxyl groups are subjected to condensation dehydration, two hydroxyl groups are dehydrated to form a molecule of water), and the carrier is placed in a dryer containing saturated NaCl solution for 48 hours before measurement.
The diffuse reflection infrared spectrometry of the catalyst is carried out on a Nicolet 6700 type Fourier transform infrared spectrometer equipped with an in-situ accessory, a sample is firstly activated for 2 hours at 500 ℃ by using He gas with the flow rate of 20 milliliters/min, and the temperature is reduced to 300 ℃ for analysis.
By adopting the technical scheme of the invention, the catalyst prepared by the method has the advantages that the reaction temperature is 600 ℃, the catalyst dosage is 0.1 g, the total flow of reaction gas is 21ml/min, when the molar ratio of 1-butene to carbon dioxide is 1:6, the yield of 1,3-butadiene is 41.1% after 10 minutes of reaction, and the better technical effect is obtained.
The invention is further illustrated by the following examples.
Drawings
FIG. 1 shows 5% in 2 O 3 SEM photograph of Silicalite-1 catalyst.
FIG. 2 is a Silicalite-1 carrier and 5% in 2 O 3 Diffuse reflectance IR spectrum of Silicalite-1 catalyst.
As can be seen from FIG. 1, the catalyst is approximately spherical in particle size, with a grain size of about 300nm.
As can be seen from FIG. 2, 3520cm -1 The absorption peak at the position is the hydroxyl In the silicon hydroxyl hole, the hole hydroxyl of the Silicalite-1 carrier is rich, and a small amount of In is loaded 2 O 3 After that, the absorption peak intensity was significantly reduced, indicating In 2 O 3 Dispersed in the silicon hydroxyl cavities by interaction with this type of hydroxyl group.
Detailed Description
[ example 1 ]
Silicalite-1 molecular sieve (specific surface area 405m 2 Per gram, pore volume of 0.51cm 3 Pretreatment method of/g): molecular sieve at 3% H 2 O 2 Soaking in the solution for 24 hours, washing with deionized water, and drying at 100 ℃ for 24 hours, wherein the hydroxyl content of the molecular sieve before treatment is 0.38mmol/g, and the hydroxyl content of the molecular sieve after treatment is 0.51mmol/g. Will correspond to 0.5 g In at 70 DEG C 2 O 3 In (NO) 3 ) 3 Dissolving in 35mL of water, adding 9.5 g of pretreated Silicalite-1 molecular sieve into the water solution under stirring, continuously stirring and dropwise adding 6mol/L of ammonia water until the pH value of the final solution is 8, filtering, washing, drying the obtained solid at 100 ℃ for 24 hours, and roasting at 600 ℃ for 5 hours in an air atmosphere to obtain the required catalyst, wherein the composition and specific preparation parameters of the catalyst are shown in Table 1. SEM and diffuse reflection infrared spectra of the catalyst are shown in fig. 1 and 2.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: the catalyst is activated for 1 hour at 600 ℃ by introducing argon, the reaction temperature is 600 ℃, the catalyst dosage is 0.1 g, the total flow of reaction gas is 21ml/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 2.
[ comparative example 1 ]
Will correspond to 0.5 g In at 70 DEG C 2 O 3 In (NO) 3 ) 3 Dissolved in 35mL of water, 9.5 g of SiO was added to the aqueous solution with stirring 2 Stirring was continued until the water evaporated to dryness. The resulting solid was dried at 100℃for 24 hours and calcined at 600℃for 5 hours in an air atmosphere to give the desired catalyst, the composition of which and the specific preparation parameters are shown in Table 1.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: the catalyst is activated for 1 hour at 600 ℃ by introducing argon, the reaction temperature is 600 ℃, the catalyst dosage is 0.1 g, the total flow of reaction gas is 21ml/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 2.
[ example 2 ]
Will correspond to 0.06 grams of In at 60℃ 2 O 3 In (NO) 3 ) 3 Dissolving in 35mL of water, adding 9.94 g of the pretreated Silicalite-1 molecular sieve obtained in example 1 into the aqueous solution under stirring, continuously stirring and dropwise adding 6mol/L of ammonia water until the pH value of the final solution is 8, filtering, washing, drying the obtained solid at 80 ℃ for 30 hours, and roasting at 600 ℃ for 4 hours in an air atmosphere to obtain the required catalyst, wherein the composition and specific preparation parameters of the catalyst are listed in Table 1.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: the catalyst is activated for 1 hour at 600 ℃ by introducing argon, the reaction temperature is 600 ℃, the catalyst dosage is 0.1 g, the total flow of reaction gas is 21ml/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 2.
[ example 3 ]
Will correspond to 0.12 g In at 65 DEG C 2 O 3 In (NO) 3 ) 3 Dissolving in 35mL of water, adding 9.88 g of the pretreated Silicalite-1 molecular sieve obtained in example 1 into the water solution under stirring, continuously stirring and dropwise adding 6mol/L of ammonia water until the pH value of the final solution is 8, filtering, washing, drying the obtained solid at 120 ℃ for 10 hours, and roasting at 650 ℃ for 4 hours in an air atmosphere to obtain the required catalyst, wherein the composition and specific preparation parameters of the catalyst are listed in Table 1.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: the catalyst is activated for 1 hour at 600 ℃ by introducing argon, the reaction temperature is 600 ℃, the catalyst dosage is 0.1 g, the total flow of reaction gas is 21ml/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 2.
[ example 4 ]
Phase at 70 DEG CWhen In at 0.36 g In 2 O 3 In (NO) 3 ) 3 Dissolving in 35mL of water, adding 9.64 g of the pretreated Silicalite-1 molecular sieve obtained in example 1 into the water solution under stirring, continuously stirring and dropwise adding 6mol/L of ammonia water until the pH value of the final solution is 8, filtering, washing, drying the obtained solid at 85 ℃ for 28 hours, and roasting at 600 ℃ for 6 hours in an air atmosphere to obtain the required catalyst, wherein the composition and specific preparation parameters of the catalyst are listed in Table 1.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: the catalyst is activated for 1h at 600 ℃ by introducing argon, the reaction temperature is 600 ℃, the catalyst dosage is 0.1 g, the total flow of reaction gas is 21mL/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 2.
[ example 5 ]
Will correspond to 0.85 g In at 90 DEG C 2 O 3 In (NO) 3 ) 3 Dissolving in 35mL of water, adding 9.15 g of the pretreated Silicalite-1 molecular sieve obtained in example 1 into the water solution under stirring, continuously stirring and dropwise adding 6mol/L of ammonia water until the pH value of the final solution is 8, filtering, washing, drying the obtained solid at 90 ℃ for 24 hours, and roasting at 625 ℃ for 5 hours in an air atmosphere to obtain the required catalyst, wherein the composition and specific preparation parameters of the catalyst are listed in Table 1.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: the catalyst is activated for 1 hour at 600 ℃ by introducing argon, the reaction temperature is 600 ℃, the catalyst dosage is 0.1 g, the total flow of reaction gas is 21ml/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 2.
[ example 6 ]
Will correspond to 1.21 grams of In at 85 DEG C 2 O 3 In (NO) 3 ) 3 In 35mL of water, 8.79 g of the pretreatment S obtained in example 1 was added to the aqueous solution with stirringThe ilialite-1 molecular sieve was continuously stirred and added dropwise with 6mol/L ammonia until the pH of the final solution was 8, the resulting solid was dried at 100℃for 24 hours after filtration and washing, and calcined at 600℃for 5 hours in an air atmosphere to give the desired catalyst, the composition of which and the specific preparation parameters are shown in Table 1.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: the catalyst is activated for 1 hour at 600 ℃ by introducing argon, the reaction temperature is 600 ℃, the catalyst dosage is 0.1 g, the total flow of reaction gas is 21ml/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 2.
[ example 7 ]
Will correspond to 1.5 grams of In at 80 DEG C 2 O 3 In (NO) 3 ) 3 Dissolving in 35mL of water, adding 8.5 g of the pretreated Silicalite-1 molecular sieve obtained in example 1 into the water solution under stirring, continuously stirring and dropwise adding 6mol/L of ammonia water until the pH value of the final solution is 8, filtering, washing, drying the obtained solid at 95 ℃ for 24 hours, and roasting at 625 ℃ for 6 hours in an air atmosphere to obtain the required catalyst, wherein the composition and specific preparation parameters of the catalyst are listed in Table 1.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: the catalyst is activated for 1h at 600 ℃ by introducing argon, the reaction temperature is 600 ℃, the catalyst dosage is 0.1 g, the total flow of the reaction gas is 21ml/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 2.
[ example 8 ]
Will correspond to 1.8 grams of In at 75℃ 2 O 3 In (NO) 3 ) 3 Dissolving in 35mL water, adding 8.2 g of the pretreated Silicalite-1 molecular sieve obtained in example 1 into the water solution under stirring, continuously stirring and dropwise adding 6mol/L ammonia water until the pH value of the final solution is 8, filtering, washing, drying the obtained solid at 110deg.C for 20 hours, and concentrating the filtrateCalcination was carried out in an air atmosphere at 650℃for 4 hours to obtain the desired catalyst, the composition of which and the specific preparation parameters are shown in Table 1.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: the catalyst is activated for 1 hour at 600 ℃ by introducing argon, the reaction temperature is 600 ℃, the catalyst dosage is 0.1 g, the total flow of reaction gas is 21ml/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 2.
[ example 9 ]
Will correspond to 2.0 grams of In at 80℃ 2 O 3 In (NO) 3 ) 3 Dissolving in 35mL of water, adding 8.0 g of the pretreated Silicalite-1 molecular sieve obtained in example 1 into the water solution under stirring, continuously stirring and dropwise adding 6mol/L of ammonia water until the pH value of the final solution is 8, filtering, washing, drying the obtained solid at 115 ℃ for 12 hours, and roasting at 600 ℃ for 7 hours in an air atmosphere to obtain the required catalyst, wherein the composition and specific preparation parameters of the catalyst are listed in Table 1.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: the catalyst is activated for 1 hour at 600 ℃ by introducing argon, the reaction temperature is 600 ℃, the catalyst dosage is 0.1 g, the total flow of reaction gas is 21ml/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 2.
[ example 10 ]
Will correspond to 2.5 grams of In at 70 DEG C 2 O 3 In (NO) 3 ) 3 Dissolving in 35mL of water, adding 7.5 g of the pretreated Silicalite-1 molecular sieve obtained in example 1 into the water solution under stirring, continuously stirring and dropwise adding 6mol/L of ammonia water until the pH value of the final solution is 8, filtering, washing, drying the obtained solid at 100 ℃ for 24 hours, and roasting at 600 ℃ for 5 hours in an air atmosphere to obtain the required catalyst, wherein the composition and specific preparation parameters of the catalyst are listed in Table 1.
The catalyst evaluation conditions in the isothermal fixed bed reactor were as follows: the catalyst is activated for 1h at 600 ℃ by introducing argon, the reaction temperature is 600 ℃, the catalyst dosage is 0.1 g, the total flow of the reaction gas is 21ml/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 2.
TABLE 1
TABLE 2
[ example 11 ]
The catalyst prepared in example 1 was taken and evaluated in an isothermal fixed bed reactor as follows: the catalyst is activated for 1 hour at 600 ℃ by introducing argon, the reaction temperature is 600 ℃, the catalyst dosage is 0.05 g, the total flow of the reaction gas is 21ml/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 3.
[ example 12 ]
The catalyst prepared in example 1 was taken and evaluated in an isothermal fixed bed reactor as follows: the catalyst is activated for 1 hour at 600 ℃ by introducing argon, the reaction temperature is 600 ℃, the catalyst dosage is 0.2 g, the total flow of reaction gas is 21ml/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 3.
[ example 13 ]
The catalyst prepared in example 1 was taken and evaluated in an isothermal fixed bed reactor as follows: the catalyst is activated for 1 hour at 550 ℃ by introducing argon, the reaction temperature is 550 ℃, the catalyst dosage is 0.1 g, the total flow of the reaction gas is 21ml/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 3.
[ example 14 ]
The catalyst prepared in example 1 was taken and evaluated in an isothermal fixed bed reactor as follows: the catalyst is activated for 1 hour at 650 ℃ by introducing argon, the reaction temperature is 650 ℃, the catalyst dosage is 0.1 g, the total flow of reaction gas is 21ml/min, and the molar ratio of 1-butene to carbon dioxide is 1:6. The 1-butene conversion, 1,3-butadiene selectivity and 1,3-butadiene yield after 10 minutes and 4 hours of reaction are shown in Table 3.
TABLE 3 Table 3

Claims (14)

1. A method for preparing 1,3-butadiene by 1-butene dehydrogenation, which takes a mixed gas of 1-butene and carbon dioxide as raw materials, contacts a 1-butene dehydrogenation catalyst, and ensures that the mass space velocity of 1-butene is 2-10 hours at the reaction temperature of 550-650 DEG C -1 The molar ratio of the raw material 1-butene to the carbon dioxide is 1 (2-10), and 1,3-butadiene is obtained under the condition; the carrier of the catalyst is selected from Silicalite-1 molecular sieves; the carrier of the catalyst is contacted with hydrogen peroxide to obtain a pretreatment carrier, wherein the hydroxyl content of the pretreatment carrier is 0.4-0.6 mmol/g; the active component In the catalyst is selected from In 2 O 3 。
2. The method for preparing 1,3-butadiene by dehydrogenating 1-butene according to claim 1, wherein the catalyst is activated for 1-3 hours in an argon atmosphere at 550-650 ℃ before the reaction, and the molar ratio of raw material 1-butene to carbon dioxide is 1 (4-8).
3. The method for preparing 1,3-butadiene by dehydrogenating 1-butene according to claim 1, wherein the specific surface area of the Silicalite-1 molecular sieve is 380-420 m 2 Per gram, the total pore volume is 0.49-0.55 cm 3 /g。
4. The process for preparing 1,3-butadiene by dehydrogenating 1-butene according to claim 1, wherein the mass percentage of indium is In based on the total mass percentage of the catalyst 2 O 3 0.6-25%.
5. The process for preparing 1,3-butadiene by dehydrogenating 1-butene according to claim 4, wherein the mass percentage of indium is In based on the total mass percentage of the catalyst 2 O 3 3.5-15%.
6. The method for preparing 1,3-butadiene by dehydrogenating 1-butene according to claim 1, wherein the morphology of the scanning electron microscope of the catalyst is approximately spherical particles, and the grains of the particles are 70 nm-3 mm.
7. The method for preparing 1,3-butadiene by dehydrogenating 1-butene according to any of claims 1 to 6, the preparation method of the catalyst comprising the steps of:
(1) The carrier is contacted with hydrogen peroxide to obtain a pretreated carrier;
(2) In (NO) 3 ) 3 Contacting with water at 60-90 ℃, then contacting with the pretreated carrier in the step (1), and controlling the pH value of the solution to 7.5-9 to obtain a solid catalyst;
(3) The obtained solid catalyst is subjected to the steps of filtering, washing, drying and roasting to obtain the 1-butene dehydrogenation catalyst.
8. The method for preparing 1,3-butadiene by dehydrogenating 1-butene according to claim 7, wherein the concentration of the hydrogen peroxide solution in the step (1) is 2% -5%.
9. The method for preparing 1,3-butadiene by dehydrogenating 1-butene according to claim 7, wherein the step (1) further comprises the steps of soaking, washing with deionized water and drying after the carrier is contacted with hydrogen peroxide; wherein the soaking time is 12-36 hours, and the drying condition is 80-120 ℃ for 12-36 hours.
10. The method for preparing 1,3-butadiene by dehydrogenating 1-butene according to claim 7, wherein the hydroxyl group content of the pretreated carrier obtained in the step (1) is 0.4-0.6 mmol/g.
11. The method for preparing 1,3-butadiene by dehydrogenating 1-butene according to claim 7, wherein ammonia water is selected in the step (2) to control the pH value of the solution, wherein the concentration of the ammonia water is 5-7 mol/L.
12. The method for preparing 1,3-butadiene by dehydrogenating 1-butene according to claim 11, wherein the control range of the pH value is 8-8.5.
13. The method for preparing 1,3-butadiene by dehydrogenating 1-butene according to claim 7, wherein the drying condition is 80-120 ℃ for 10-30 hours.
14. The method for preparing 1,3-butadiene by dehydrogenating 1-butene according to claim 7, wherein the roasting condition is roasting for 3-8 hours at 600-650 ℃ in an air atmosphere.
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