CN113457724A - Bifunctional catalyst for preparing toluene and co-producing diphenylmethane by directly converting synthesis gas and benzene, and preparation method and application thereof - Google Patents

Bifunctional catalyst for preparing toluene and co-producing diphenylmethane by directly converting synthesis gas and benzene, and preparation method and application thereof Download PDF

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CN113457724A
CN113457724A CN202110670256.3A CN202110670256A CN113457724A CN 113457724 A CN113457724 A CN 113457724A CN 202110670256 A CN202110670256 A CN 202110670256A CN 113457724 A CN113457724 A CN 113457724A
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benzene
synthesis gas
catalyst
toluene
bifunctional catalyst
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CN113457724B (en
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常浩浩
王子剑
罗阿淋
刘永梅
曹勇
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Fudan University
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    • 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
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    • 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
    • B01J29/42—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 iron group metals, noble metals or copper
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    • B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
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    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
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Abstract

The invention discloses a bifunctional catalyst for directly preparing toluene and diphenylmethane by catalyzing synthesis gas and benzene, and a preparation method and application thereof, wherein the catalyst is formed by compounding a binary metal oxide and different molecular sieves by physical mixing or deposition-precipitation methods and the like, and the binary metal oxide Zn is used for preparing the toluene and diphenylmethane by catalyzing the synthesis gas and the benzenexByOzB = Ni, Mn, In, Cd, Ga, Zr, Zn/(Zn + B) molar ratio (0-1): 1, ZnxByOzThe amount of the catalyst is 30-90 wt% of the total amount of the catalyst. The invention can realize the high-selectivity co-production of toluene and diphenylmethane in the product and the regulation and control of the distribution of the corresponding product by modulating the composite mode of the binary oxide and the molecular sieve.

Description

Bifunctional catalyst for preparing toluene and co-producing diphenylmethane by directly converting synthesis gas and benzene, and preparation method and application thereof
Technical Field
The invention relates to a bifunctional catalyst and a preparation method and application thereof, in particular to a bifunctional catalyst for catalyzing direct conversion of synthesis gas and benzene to prepare toluene and diphenylmethane and a preparation method and application thereof, and belongs to the technical field of chemistry.
Background
Toluene is an important organic chemical raw material and is mainly prepared from crude oil through petroleum deterioration, cracking and other processes. Diphenylmethane, commonly known as artificial geranium oil, is an important intermediate of spices, dyes and medicines, and is an indispensable important intermediate raw material in pharmacy and fine chemical industry. The traditional diphenylmethane synthesis route adopts aluminum amalgam and AlCl which have serious environmental pollution3The catalyst or the reaction raw material containing halogen has high synthesis cost and serious environmental pollution and is eliminated by countries in the world.
The development of a new method and a new route for catalytic conversion of synthesis gas and coal has great theoretical and practical significance for realizing clean and high-value utilization of carbon resources. The synthesis gas has wide sources and can be directly obtained from coal, natural gas or biomass energy conversion seeds. However, the existing route for preparing aromatic hydrocarbon by coal chemical industry has the problems of more byproducts, low conversion rate and the like. Chinese patent CN111167507 adopts a method of mixing and tabletting bimetallic oxides and molecular sieves to prepare toluene and xylene under the high-temperature gas phase condition of 450 ℃ and 3MPa, but has the problems of high reaction temperature, long catalyst preparation period and the like. Aiming at the defects, the invention improves the traditional catalyst, reduces the reaction temperature, improves the space-time yield, is easy to separate the product and has more obvious economic value.
Take the example of the alkylation reaction of synthesis gas and benzene to produce toluene and diphenylmethane. The alkylation reaction of synthesis gas and benzene belongs to a series reaction, and the main route is as follows:
the synthesis gas is selectively synthesized into reaction intermediates, namely methanol and formaldehyde under the catalysis of a transition metal catalyst or a noble metal catalyst, and the synthesized reaction intermediates are subjected to alkylation reaction with benzene under the catalysis of a solid acid catalyst (molecular sieve) to generate toluene and diphenylmethane.
The traditional reaction for producing diphenylmethane by benzyl chloride has low utilization rate of benzene, the benzyl chloride has high price and toxicity such as strong carcinogenicity, and the like, so the invention provides the process for preparing the diphenylmethane and the toluene by using the synthesis gas.
Disclosure of Invention
The invention aims to provide a bifunctional catalyst for preparing toluene and diphenylmethane by directly and efficiently directionally converting catalytic synthesis gas and benzene, and a preparation method and application thereof. The invention solves the problems of complex production process, low atom utilization rate, serious environmental pollution and the like of the existing toluene and diphenylmethane, and provides a new technology for directly co-producing toluene and diphenylmethane by catalyzing synthesis gas and benzene.
The invention provides a new technology for producing toluene and diphenylmethane by the reaction of catalytic synthesis gas and benzene, the reaction is carried out in an intermittent reaction kettle under the condition of benzene heat, the method is green and environment-friendly, the catalyst is easy to separate, the catalysis is efficient, the atom economy is realized, the reusability is good, and the production cost is reduced.
The invention provides a bifunctional catalyst for catalyzing direct coproduction of toluene and diphenylmethane from synthesis gas and benzene, wherein: the active component of the bifunctional catalyst is ZnxByOzThe carrier is any one of HZSM-5, HBETA or HY molecular sieve; active component ZnxByOzAccounts for 30-90 of the total amount of the bifunctional catalystwt％。
In the present invention, the active component ZnxByOzWherein the molar ratio of Zn/(Zn + B) is (0-1): 1, B is any one of Ni, Mn, In, Cd, Ga or Zr.
The invention provides a preparation method of a bifunctional catalyst for producing toluene and xylene by coupling catalytic synthesis gas and benzene, which comprises the following specific steps:
(1) and (2) adding metal salt with the total amount of two metal cations being 0.015mol according to the weight ratio of (0-1): 1 weighing and dissolving in ethanol, adding a carrier, and stirring at 400-800 rpm for 1.8-2.2 hours;
(2) weighing oxalic acid or ammonium oxalate with the total amount of metal cations being 1-1.2 times of that of the metal cations, and dissolving the oxalic acid or ammonium oxalate in ethanol;
(3) dropwise adding the solution obtained in the step (2) into the solution obtained in the step (1) at a constant speed under the condition of stirring, continuously stirring for 1.8-2.2 hours, performing suction filtration, and washing for multiple times;
(4) drying the solid matter obtained in the step (3) at 110 ℃ overnight, roasting the obtained product for 4 hours at 400 ℃ in nitrogen or argon, and roasting at 400-800 ℃ for 3-6 hours in air or oxygen to obtain an active component ZnxByOz；
(5) The active component Zn obtained in the step (4) isxByOzMechanically mixed with the support, impregnated or deposited-precipitated on the support, wherein: active component ZnxByOzAccounting for 30-90 wt% of the total catalyst.
The invention provides an application of a bifunctional catalyst for catalyzing the coupling of synthesis gas and benzene to produce toluene and xylene.
In the invention, the reaction temperature in the batch type reaction kettle is 270-380 ℃, and the reaction pressure is 4 MPa.
The invention has the advantages that:
(1) due to the oxide pair H of B2Has low activation capability and can only be used for activating CO to form formate, while ZnO can effectively dissociate H2H dissociated for hydrogenation2The formate on the B oxide can be hydrogenated to methanol or methoxy, so that the binary metal oxide Zn can be adjustedxByOzThe metal proportion of the benzene intermediate is adjusted, and the conversion rate of benzene can be effectively improved by proper amount of the intermediate;
(2) the silicon-aluminum ratio of the HZSM-5 molecular sieve is adjusted, namely the acid sites on the HZSM-5 molecular sieve are adjusted, and the proper acid amount is beneficial to alkylation reaction, so that the selectivity of diphenylmethane can be effectively improved and the conversion rate of benzene can be further improved by adjusting the silicon-aluminum ratio of the HZSM-5 molecular sieve;
(3) binary metal oxide ZnxByOzNon-noble metal components are selected, so that the cost is low and the method is suitable for mass production;
(4) binary metal oxide ZnxByOzThe colloidal coprecipitation method is adopted for synthesis, so that the repeatability is strong, the yield is high, and the large-scale preparation is facilitated.
Detailed Description
The invention is further illustrated by the following specific examples.
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. While the examples only show some of the conditions for achieving the production of diphenylmethane, they do not mean that these conditions must be met to achieve this.
The raw materials used in the examples were all purchased commercially unless otherwise specified.
Figure BDA0003118424270000031
Figure BDA0003118424270000032
Example 1
(1) According to the molar ratio of Zn/(Zn + Zr) of (0-1): 1 weighing Zn (NO)3)2.6H2O and Zr (NO)3)4·5H2O, then dissolving the two in an ethanol solution; adding a certain mass of HZSM-5 into the solution, wherein the percentage content of the HZSM-5 is 10-70%;
(2) weighing oxalic acid with the total amount of metal cations being 1-1.2 times of that of the metal cations, dissolving the oxalic acid in ethanol, dropwise adding the oxalic acid solution into the salt solution obtained in the step (1) under continuous stirring, and continuously stirring for 2 hours after dropwise adding; filtering, washing, drying at 110 ℃ overnight, sequentially roasting in Ar at 400 ℃ for 4h, and roasting in air at 500 ℃ for 8 h;
(3)ZnZrOXadding a molecular sieve into a 100mL reaction kettle, adding 16mL of benzene, replacing air in the reaction kettle with synthesis gas for three times, adjusting the pressure to 4MPa, heating to 330 ℃, reacting for 3 hours, and performing gas chromatography analysis, wherein the results are shown in Table 1:
TABLE 1
Figure BDA0003118424270000041
Reaction conditions are as follows:
in the present embodiment, with Si: molecular sieve loading of Al 15 produced 5 parts ZrO with different Zr/(Zn + Zr) molar ratios (i.e. metal ratios)2-ZnO bimetallic catalyst, in particular as follows:
TABLE 2
Figure BDA0003118424270000042
Figure BDA0003118424270000051
As is clear from the results in Table 1, ZnO or ZrO was found to be a single component2The catalytic activity for the reaction is low, the benzene conversion rate is only 4.2 percent and 4.4 percent respectively, the catalytic activity of the reaction is obviously improved after the binary composite oxide is formed by a coprecipitation method, when the molar ratio of Zn to Zr is 20:80, the benzene conversion rate is up to 13.2 percent, the selectivity of diphenylmethane is 42.5 percent, the selectivity of toluene is 46 percent,the space-time yield of the diphenylmethane is up to 2661mgDPMgox -1h-1。
From the results in table 2, it is understood that the conversion of benzene is first increased with the increase of the ZnO content in the binary metal oxide, and when the molar ratio of Zn to Zr is 20: at 80 deg.c, the conversion rate of benzene is up to 13.2%, the selectivity of diphenylmethane is up to 42.5%, and the selectivity of toluene is up to 46%. Then, as the zinc content continues to increase, the benzene conversion begins to decrease.
Example 2
(1) According to the molar ratio of Zn/(Zn + Zr) of 0.2: 1 weighing Zn (NO)3)2.6H2O and Zr (NO)3)4·5H2O, then dissolving the two in an ethanol solution; adding certain mass of HZSM-5 with different silica-alumina ratios into the solution;
(2) weighing oxalic acid with the total amount of metal cations being 1-1.2 times of that of the metal cations, dissolving the oxalic acid in ethanol, dropwise adding the oxalic acid solution into the salt solution under continuous stirring, and continuously stirring for 2 hours after dropwise adding; filtering, washing, drying at 110 ℃ overnight, then sequentially roasting in Ar gas at 400 ℃ for 4h, and then roasting in air at 500 ℃ for 8 h;
(3)ZnZrOXand HZSM-5 with different silica-alumina ratios is added into a 100mL reaction kettle, 16mL benzene is added, air in the reaction kettle is replaced by synthesis gas for three times, the pressure is adjusted to 4MPa, the temperature is raised to 330 ℃, the reaction is carried out for 3h, and the results are shown in Table 3 after gas chromatography analysis:
evaluation conditions were as follows: 50 wt% of HZSM-5 molecular sieve with different silica-alumina ratios and 50 wt% of 20Zn80Zr, roasting the catalyst at 330 ℃ and 4MPa by a two-step method;
the evaluation results (the following results are an average of 3 h) were as follows:
TABLE 3
Figure BDA0003118424270000052
Figure BDA0003118424270000061
As can be seen from table 3, the influence of the silica-alumina ratio of the HZSM-5 molecular sieve on the catalytic effect is: with the increase of the silicon-aluminum ratio of the HZSM-5 molecular sieve, the selectivity of the diphenylmethane is increased and then reduced, wherein when the silicon-aluminum ratio of the HZSM-5 molecular sieve is 15, the selectivity of the diphenylmethane reaches 42.5 percent, the selectivity of the toluene reaches 46 percent, the conversion rate of the benzene reaches more than 13.2 percent, and the optimal silicon-aluminum ratio of the HZSM-5 molecular sieve is 15.
Example 3:
(1) according to the molar ratio of Zn/(B + Zr) of 0.2: 1 weighing nitrate of B and Zr (NO)3)4·5H2O, then dissolving the two in an ethanol solution; adding HZSM-5 with a certain mass of Si/Al 15 into the solution;
(2) weighing oxalic acid with the total amount of metal cations being 1-1.2 times of that of the metal cations, dissolving the oxalic acid in ethanol, dropwise adding the oxalic acid solution into the salt solution under continuous stirring, and continuously stirring for 2 hours after dropwise adding; filtering, washing, drying at 110 ℃ overnight, sequentially roasting at Ar-400 ℃ for 4h, and roasting at air-500 ℃ for 8 h;
(3)ZnxByOzHZSM-5 with a silica-alumina ratio of 15 is added into a 100mL reaction kettle, 16mL benzene is added, air in the reaction kettle is replaced by synthesis gas three times, the pressure is adjusted to 4MPa, the temperature is raised to 330 ℃, the reaction is carried out for 3h, and the results of gas chromatographic analysis are shown in Table 4:
evaluation conditions were as follows: roasting an HZSM-5 molecular sieve with the silicon-aluminum ratio of 15 of 50 wt% and 20Zn80B of 50 wt% at 330 ℃ and 4MPa by a two-step method;
the evaluation results (the following results are an average of 3 h) were as follows:
TABLE 4
Figure BDA0003118424270000062
Figure BDA0003118424270000071
Example 4: catalysts prepared at different calcination temperatures
(1) According to the molar ratio of Zn/(Zn + Zr) of 0.2: 1 weighing Zn (NO)3)2.6H2O and Zr (NO)3)4·5H2O, then dissolving the two in an ethanol solution; adding a certain mass of HZSM-5 into the solution;
(2) weighing oxalic acid with the total amount of metal cations being 1-1.2 times of that of the metal cations, dissolving the oxalic acid in ethanol, dropwise adding the oxalic acid solution into the salt solution under continuous stirring, and continuously stirring for 2 hours after dropwise adding; filtering, washing, drying at 110 ℃ overnight, sequentially roasting at Ar-400 ℃ for 4h, and roasting at air-500 ℃ for 8 h;
(3) the 20Zn80Zr calcined at different temperatures and HZSM-5 with a silica-alumina ratio of 15 are added into a 100mL reaction kettle, 16mL benzene is added, air in the synthesis gas replacement kettle is replaced three times, the pressure is adjusted to be 4MPa, the temperature is raised to 330 ℃, the reaction is carried out for 3h, and the results are shown in Table 5:
evaluation conditions were as follows: 50 wt% of HZSM-5 molecular sieve with the silica-alumina ratio of 15 and 50 wt% of 20Zn80Zr, the temperature is 330 ℃, the pressure is 5MPa, and the catalyst is roasted by a two-step method.
The evaluation results (as an average of 3h results) were as follows:
TABLE 5
Figure BDA0003118424270000072
Example 5: catalysts prepared under different calcination atmospheres
Evaluation conditions were as follows: HZSM-5 molecular sieve with the silicon-aluminum ratio of 15 of 50 wt% and 20Zn80Zr of 50 wt% at 330 ℃ and 5MPa, and roasting the catalyst by a two-step method
The evaluation results (as an average of 3h results) were as follows:
TABLE 6
Figure BDA0003118424270000073
Figure BDA0003118424270000081
Example 6: catalyst prepared by sectional roasting and one-step roasting
Evaluation conditions were as follows: HZSM-5 molecular sieve with the silicon-aluminum ratio of 15 of 50wt percent and 20Zn80Zr of 50wt percent at 330 ℃ and 5MPa
The evaluation results (as an average of 3h results) were as follows:
TABLE 7
Figure BDA0003118424270000082
It should be noted that the above-mentioned embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the protection scope of the present invention.
Example 7: different kinds of molecular sieves loaded with binary metal oxides
(1) According to the molar ratio of Zn/(Zn + Zr) of (0-1): 1 weighing Zn (NO)3)2.6H2O and Zr (NO)3)4·5H2O, then dissolving the two in an ethanol solution; to the above solution was added different molecular sieves of mass Si/Al 15.
(2) Weighing oxalic acid with the total amount of metal cations being 1-1.2 times of that of the metal cations, dissolving the oxalic acid in ethanol, dropwise adding the oxalic acid solution into the salt solution under continuous stirring, and continuously stirring for 2 hours after dropwise adding; filtering, washing, drying at 110 ℃ overnight, sequentially roasting at Ar-400 ℃ for 4h, and roasting at air-500 ℃ for 8 h;
(3) adding 20% of ZnZr (20 mol% of Zn) and different molecular sieves into a 100mL reaction kettle, adding 16mL of benzene, replacing air in the kettle with synthesis gas for three times, adjusting the pressure to 4MPa, heating to 330 ℃, reacting for 3h, and carrying out gas chromatography analysis, wherein the results are shown in Table 8:
evaluation conditions were as follows: roasting 50 wt% of molecular sieve and 50 wt% of 20Zn80Zr at 330 ℃ and 4MPa by a two-step method;
the evaluation results (as an average of 3h results) were as follows:
TABLE 8
Figure BDA0003118424270000091

Claims (5)

1. A dual-function catalyst for catalyzing direct coproduction of toluene and diphenylmethane of synthesis gas and benzene is characterized in that: the active component of the bifunctional catalyst is ZnxByOzThe carrier is any one of HZSM-5, HBETA or HY molecular sieve; active component ZnxByOzAccounting for 30-90 wt% of the total amount of the bifunctional catalyst.
2. Bifunctional catalyst according to claim 1, characterized in that: active component ZnxByOzWherein the molar ratio of Zn/(Zn + B) is (0-1): 1, B is any one of Ni, Mn, In, Cd, Ga or Zr.
3. A method for preparing the bifunctional catalyst for catalyzing the coupling of synthesis gas and benzene to produce toluene and xylene according to claim 1, wherein the method comprises the following steps: the method comprises the following specific steps:
(1) and (2) adding metal salt with the total amount of two metal cations being 0.015mol according to the weight ratio of (0-1): 1 weighing and dissolving in ethanol, adding a carrier, and stirring at 400-800 rpm for 1.8-2.2 hours;
(2) weighing oxalic acid or ammonium oxalate with the total amount of metal cations being 1-1.2 times of that of the metal cations, and dissolving the oxalic acid or ammonium oxalate in ethanol;
(3) dropwise adding the solution obtained in the step (2) into the solution obtained in the step (1) at a constant speed under the condition of stirring, continuously stirring for 1.8-2.2 hours, performing suction filtration, and washing for multiple times;
(4) drying the solid matter obtained in the step (3) at 110 ℃ overnight, roasting the obtained product for 4 hours at 400 ℃ in nitrogen or argon, and roasting at 400-800 ℃ for 3-6 hours in air or oxygen to obtain an active component ZnxByOz；
(5) The active component Zn obtained in the step (4) isxByOzMechanical mixing with the carrier, impregnation or deposition-precipitation processesSupported on a carrier, wherein: active component ZnxByOzAccounting for 30-90 wt% of the total catalyst.
4. The application of the bifunctional catalyst for catalyzing the coupling of synthesis gas and benzene to produce toluene and xylene according to claim 1, wherein the bifunctional catalyst is used for directly co-producing toluene and xylene by adding benzene and synthesis gas into a batch reactor.
5. The application of the method as claimed in claim 1, wherein the reaction temperature in the batch type reaction kettle is 270-380 ℃ and the reaction pressure is 4 MPa.
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