阅读说明：本技术 一种烯烃异构化的方法 (Olefin isomerization method ) 是由 白延锋 田虎 贺栋栋 张建强 薛伟 陈锦康 刘国杰 王鹏 于 2021-08-31 设计创作，主要内容包括：本发明提供了一种烯烃异构化的方法,属于有机合成技术领域。所述的方法为：将反应物通入管式反应炉中,在不加入溶剂的情况下,加入催化剂,得到异构化烯烃；所述的催化剂为氧化镁改性的ZSM-5分子筛,或由ZSM-5分子筛和碱金属组成的混合催化剂,所使用的催化剂,具有易于得到、廉价、易于分离、可套用等特点；本发明所述的反应在管式反应器内进行,反应时间缩短,反应的选择性和转化率提高,反应的收率提高；本发明公开反应的反应转化率高,收率50-70％,选择性为94-98％,反应时间为30-60分钟,且该方法,三废少,能耗低。(The invention provides an olefin isomerization method, and belongs to the technical field of organic synthesis. The method comprises the following steps: introducing the reactants into a tubular reaction furnace, and adding a catalyst under the condition of not adding a solvent to obtain isomerized olefin; the catalyst is a magnesium oxide modified ZSM-5 molecular sieve or a mixed catalyst consisting of the ZSM-5 molecular sieve and alkali metal, and the used catalyst has the characteristics of easy acquisition, low cost, easy separation, applicability and the like; the reaction is carried out in the tubular reactor, the reaction time is shortened, the selectivity and the conversion rate of the reaction are improved, and the yield of the reaction is improved; the reaction disclosed by the invention has the advantages of high reaction conversion rate, yield of 50-70%, selectivity of 94-98%, reaction time of 30-60 minutes, less three wastes and low energy consumption.)

1. A process for the isomerization of olefins characterized by: the method comprises the following steps: putting reactants into a reactor, and introducing a fixed bed containing a catalyst for reaction under the condition of not adding a solvent to obtain isomerized olefin, wherein the specific reaction formula is shown as a formula I;

the catalyst is a ZSM-5 molecular sieve modified by magnesium oxide or a mixed catalyst consisting of the ZSM-5 molecular sieve and alkali metal.

Wherein R1, R2, R3 and R4 are respectively and independently selected from: hydrogen or a branched alkyl group of C1-C6, a linear alkyl group of C1-C6, an aryl group or a hydroxymethyl group.

2. The method of claim 1, wherein: the alkali metal in the mixed catalyst is selected from one or more of lithium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, cesium carbonate and magnesium oxide.

3. The method of claim 2, wherein: the alkali metal in the mixed catalyst is selected from magnesium oxide.

4. The method of claim 1, wherein: the preparation method of the ZSM-5 molecular sieve comprises the following steps:

h is to be₂O、TPAOH、NaAlO₂According to the molar ratio 4015: 19: 1, uniformly mixing, dropwise adding TEOS under vigorous stirring, stirring for 1 hour, transferring into a high-pressure kettle, heating at 180 ℃ for 48 hours, cooling to room temperature, washing with absolute ethyl alcohol, drying for 12 hours, and calcining at 550 ℃ for 3-6 hours to prepare the ZSM-5 molecular sieve;

the addition amount of the TEOS is n (TEOS): n (NaAlO)₂)＝40：1。

5. The method of claim 1, wherein: the preparation method of the magnesium oxide modified ZSM-5 molecular sieve comprises the following steps:

mixing a ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

6. The method of claim 1, wherein: the dosage of the catalyst is 0.5-12% of the mass of the olefin.

7. The method of claim 1, wherein: the mixed catalyst consists of a ZSM-5 molecular sieve and alkali metal, wherein the mass ratio of the ZSM-5 molecular sieve to the alkali metal is 1: 0.5-2.

8. The method of claim 1, wherein: the reaction temperature is 30-100 ℃, the pressure is 0-4MPa, and the reaction is kept in the reactor for 20-60 minutes.

9. The method of claim 8, wherein: the reaction temperature is 40-60 ℃, the pressure is 0.8-1.2MPa, and the reaction lasts for 30-50 minutes in the reactor.

10. The method of claim 1, wherein: the flow rate of the olefin entering the fixed bed is 15-30 g/min.

Technical Field

The invention belongs to the technical field of organic synthesis, and particularly relates to an olefin isomerization method.

Background

Olefins, as a basic unit of a class of organic compounds, have this important role in the field of organic synthesis. Meanwhile, olefins are also precursors of various functionalized complex frameworks and complex compounds, and play an important role in various fields such as materials, medicines, food additives, pesticides and the like. Through recent developments, the industry has developed a number of classical approaches to the construction of olefins, such as: wittig reaction, Julia reaction, Peterson alkenylation, HWE reaction, etc. However, these methods, while often not highly selective, can introduce significant amounts of by-products, such as: a large amount of triphenyl phosphine oxide by-products are brought about in the Wittig reaction, which brings inconvenience to the post-treatment.

Currently, scientists develop a new method for obtaining new olefins or highly selective olefins by using the isomerization reaction of olefins, i.e., by using the positional shift of carbon-carbon double bonds or cis-trans isomerization without changing the compound skeleton, which is definitely an environment-friendly and atom-economic new method. In recent years, the processes for effecting isomerization of olefins are mainly divided into four categories: transition metal catalysis, acid catalysis, base catalysis, and photocatalysis. Among them, although many types of studies have shown that transition metal catalysis has a very good catalytic effect on the isomerization reaction of olefins, for example: metals such as iron, cobalt, nickel, ruthenium, iridium (chem.rev.,2015,115,54625569; j.am.chem.soc.,2021,143, 2792-. Acid-catalyzed olefin isomerization often uses strong and medium acids of sulfuric acid and perchloric acid, but such acid catalysts are often highly corrosive and difficult to recover, and when lewis acid catalysts such as boron trifluoride or aluminum trichloride are used, olefin polymerization byproducts often occur. The olefin isomerization reaction catalyzed by the alkali adopts potassium tert-butoxide, but the alkali is strong in alkalinity and narrow in application range, and most of other alkali compounds have low catalytic activity or other byproducts. The visible light catalyzed olefin isomerization reaction has mild reaction conditions, but needs special equipment and is difficult to realize industrialization.

Because the method has a plurality of defects or inconveniences in the actual use process, Chinese patent application 201210065262.7 discloses a preparation method of a linear chain olefin skeletal isomerization catalyst, which comprises the specific steps of treating a synthesized rare earth ZSM-35 molecular sieve with an alkali solution at 30-90 ℃ for 0.5-10 hours; washing the obtained product to be neutral, extruding the product with a binder for forming, exchanging with an ammonium nitrate solution, filtering, washing with deionized water, drying and roasting; the obtained sample is treated by water vapor at 400-700 ℃ for 1-8 hours to prepare the isomerization catalyst. Compared with the untreated ZSM-35 molecular sieve catalyst, the alkaline water-treated and modified ZSM-35 molecular sieve catalyst prepared by the invention has the advantages that although the reaction stability is improved, the repeated utilization rate of the catalyst is not ideal.

Thus, there is still a need for further improvements or new developments of novel catalytic schemes.

Disclosure of Invention

Aiming at the defects of the method, the patent provides an efficient, stable and low-cost olefin isomerization process for the industrial production of olefin isomerization reaction. The process has the characteristics of high catalytic efficiency, mild reaction, high product purity, easy separation, reusable catalyst and the like, is an economic, environment-friendly and efficient process production scheme, and has wide application prospect.

In order to achieve the purpose, the invention adopts the following technical scheme:

in one aspect, the present invention provides a process for isomerization of olefins, the process comprising: putting reactants into a reactor, introducing a fixed bed containing a catalyst for reaction under the condition of not adding a solvent, and obtaining isomerized olefin after a period of time, wherein the specific reaction formula is shown as a formula I;

r1, R2, R3 and R4 are respectively and independently selected from: hydrogen or a branched alkyl group of C1-C6, a linear alkyl group of C1-C6, an aryl group or a hydroxymethyl group.

The reactor described in the above process is a tubular reactor.

The catalyst in the method is a ZSM-5 molecular sieve modified by magnesium oxide or a mixed catalyst consisting of the ZSM-5 molecular sieve and alkali metal;

the alkali metal in the mixed catalyst is selected from one or more of lithium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, cesium carbonate and magnesium oxide;

preferably, the alkali metal in the mixed catalyst is selected from magnesium oxide.

In some preferred embodiments, the olefin isomerization process is: placing the reactants in a tubular reactor, introducing a fixed bed containing a magnesium oxide modified ZSM-5 molecular sieve for reaction under the condition of not adding a solvent, and obtaining isomerized olefin after a period of time;

in other preferred embodiments, the olefin isomerization process is: placing the reactants in a tubular reactor, introducing a fixed bed containing a mixed catalyst consisting of a ZSM-5 molecular sieve and alkali metal to react under the condition of not adding a solvent, and obtaining isomerized olefin after a period of time;

the preparation method of the ZSM-5 molecular sieve comprises the following steps:

h is to be₂O、TPAOH、NaAlO₂According to the molar ratio 4015: 19: 1, uniformly mixing, dropwise adding TEOS under vigorous stirring, stirring for 1 hour, transferring into a high-pressure kettle, heating at 180 ℃ for 48 hours, cooling to room temperature, washing with absolute ethyl alcohol, drying for 12 hours, and calcining at 550 ℃ for 3-6 hours to prepare the ZSM-5 molecular sieve;

the addition amount of the TEOS is n (TEOS): n (NaAlO)₂)＝40：1。

The preparation method of the magnesium oxide modified ZSM-5 molecular sieve comprises the following steps:

mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The dosage of the catalyst in the method is 0.5 to 12 percent of the olefin mass, and preferably 2.5 to 5 percent

The catalyst in the reaction system provided by the invention can ensure that the catalytic isomerization effect is better and the dosage is lower within the preferable dosage range.

The mixed catalyst consists of a ZSM-5 molecular sieve and alkali metal, wherein the mass ratio of the ZSM-5 molecular sieve to the alkali metal is 1: 0.5-2, preferably 1: 1.0-1.5.

The reaction temperature in the method is 30-100 ℃, the pressure is 0-4MPa, and the reaction is kept in the reactor for 20-60 minutes.

Preferably, the reaction temperature is 40-60 ℃, the pressure is 0.8-1.2MPa, and the reaction is kept in the reactor for 30-50 minutes.

The flow rate of the mixed solution of olefin and catalyst in the above method is 15-30g/min, preferably 20-25 g/min.

The mixed solution of the olefin and the catalyst does not need to be added with any solvent, wherein the water content of the olefin is less than 5 percent, and is preferably less than 1 percent.

Compared with the prior art, the invention has the beneficial effects that:

1. the magnesium oxide modified ZSM-5 molecular sieve or the mixed catalyst consisting of the ZSM-5 molecular sieve and the alkali metal, which is disclosed by the invention, has the characteristics of easy obtaining, low price, easy separation, applicability and the like;

2. the reaction is carried out in the tubular reactor, the reaction time is shortened, the selectivity and the conversion rate of the reaction are improved, and the yield of the reaction is improved; the reaction disclosed by the invention has high conversion rate, the yield is 50-70%, the selectivity is 94-98%, and the reaction time is 30-60 minutes;

3. according to the method, when the isomerized olefin with the product purity of more than 98% is obtained, unreacted raw materials can be recycled, and the yield after recycling can reach more than 95%;

4. the method of the invention has the advantages of less three wastes and low energy consumption.

Detailed Description

The following examples further illustrate the invention but are not intended to limit the invention thereto.

Basic embodiment

The preparation method of the ZSM-5 molecular sieve comprises the following steps:

h is to be₂O、TPAOH、NaAlO₂According to the molar ratio 4015: 19: 1, uniformly mixing, dropwise adding TEOS under vigorous stirring, stirring for 1 hour, transferring into a high-pressure kettle, heating at 180 ℃ for 48 hours, cooling to room temperature, washing with absolute ethyl alcohol, drying for 12 hours, and calcining at 550 ℃ for 3-6 hours to prepare the ZSM-5 molecular sieve;

the addition amount of the TEOS is n (TEOS): n (NaAlO)₂)＝40：1。

Example 1

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

And (3) filling the ZSM-5 molecular sieve modified by magnesium oxide into a fixed bed column, wherein the dosage of the catalyst is 5% of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 62%, and the selectivity is calculated to be 98%.

Example 2

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The ZSM-5 molecular sieve modified by magnesium oxide is filled into a fixed bed column, and the dosage of the catalyst is 2.5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 60% and the selectivity is calculated to be 98%.

Example 3

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

And (3) filling the ZSM-5 molecular sieve modified by magnesium oxide into a fixed bed column, wherein the dosage of the catalyst is 12 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is 63 percent and the selectivity is 98 percent.

Example 4

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The ZSM-5 molecular sieve modified by magnesium oxide is filled into a fixed bed column, and the dosage of the catalyst is 0.5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is 57 percent and the selectivity is 98 percent.

Example 5

ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 55% and the selectivity is calculated to be 67%.

Example 6

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1.5, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 61%, and the selectivity is calculated to be 98%.

Example 7

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:0.5, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 53% and the selectivity is calculated to be 83%.

Example 8

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:2, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 62%, and the selectivity is calculated to be 98%.

Example 9

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to be 60 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 64% and the selectivity is calculated to be 98%.

Example 10

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to be 30 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 58% and the selectivity is calculated to be 98%.

Example 11

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 20min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 38% and the selectivity is calculated to be 98%.

Example 12

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 64% and the selectivity is calculated to be 98%.

Example 13

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 0 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time to be 45min, and after the reaction is finished, rectifying and separating reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 48%, and the selectivity is calculated to be 98%.

Example 14

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1.2 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 61%, and the selectivity is calculated to be 98%.

Example 15

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 4 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 61%, and the selectivity is calculated to be 98%.

Example 16

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 15g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 60% and the selectivity is calculated to be 98%.

Example 17

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 30g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 62%, and the selectivity is calculated to be 98%.

Example 18

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 15g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time to be 45min, after the reaction is finished, rectifying and separating reaction liquid to obtain crude 1-propenyl benzene, recycling unreacted allyl benzene and a catalyst for 5 times, finally rectifying and separating, and combining to obtain the crude 1-propenyl benzene, thereby calculating the reaction yield to be 75% and the selectivity to be 98%.

Example 19

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

And (3) filling the recovered magnesium oxide modified ZSM-5 molecular sieve into a fixed bed column, wherein the dosage of the catalyst is 5% of the mass of the allylbenzene. Pumping allyl benzene into a preheater for preheating at a constant rate of 15g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 67%, and the selectivity is calculated to be 98%. The catalyst is recovered, and experiments show that the reaction yield and the selectivity are not greatly changed when the catalyst is used for 10 times.

Example 20

Uniformly mixing a ZSM-5 molecular sieve and magnesium oxide, and filling the mixture into a fixed bed column, wherein the dosage of a catalyst is 5% of the mass of allyl benzene, and the mass ratio of ZSM-5 to magnesium oxide is 1:1. pumping allyl benzene into a preheater for preheating at a constant rate of 15g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 62%, and the selectivity is calculated to be 98%.

Example 21

Uniformly mixing a ZSM-5 molecular sieve and sodium hydroxide, and filling the mixture into a fixed bed column, wherein the dosage of a catalyst is 5% of the mass of allyl benzene, and the mass ratio of the ZSM-5 to the sodium hydroxide is 1:1. pumping allyl benzene into a preheater for preheating at a constant rate of 15g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is 45% and the selectivity is 95% by calculation.

Example 22

Uniformly mixing a ZSM-5 molecular sieve and sodium carbonate, and filling the mixture into a fixed bed column, wherein the dosage of a catalyst is 5% of the mass of allyl benzene, and the mass ratio of the ZSM-5 to the sodium carbonate is 1:1. pumping allyl benzene into a preheater for preheating at a constant rate of 15g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 52% and the selectivity is calculated to be 92%.

Example 23

Uniformly mixing a ZSM-5 molecular sieve and lithium carbonate, and filling the mixture into a fixed bed column, wherein the using amount of a catalyst is 5% of the mass of allyl benzene, and the mass ratio of the ZSM-5 to the lithium carbonate is 1:1. pumping allyl benzene into a preheater for preheating at a constant rate of 15g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 50% and the selectivity is calculated to be 88%.

Example 24

Uniformly mixing a ZSM-5 molecular sieve and potassium carbonate, and filling the mixture into a fixed bed column, wherein the dosage of a catalyst is 5% of the mass of allyl benzene, and the mass ratio of ZSM-5 to potassium carbonate is 1:1. pumping allyl benzene into a preheater for preheating at a constant rate of 15g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 1-propenyl benzene, wherein the reaction yield is calculated to be 56% and the selectivity is calculated to be 90%.

Example 25

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the 3-methyl-2-butene-1-ol. Pumping 3-methyl-2-buten-1-ol into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of the 3-methyl-2-butenol, wherein the reaction yield is calculated to be 62%, and the selectivity is calculated to be 98%.

Example 26

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The ZSM-5 molecular sieve modified by magnesium oxide is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the allyl phenyl ether. Pumping allyl phenyl ether into a preheater for preheating at a constant rate of 25g/min using a high pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of the 1-propenyl phenyl ether, wherein the reaction yield is calculated to be 61%, and the selectivity is calculated to be 98%.

Example 27

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The ZSM-5 molecular sieve modified by magnesium oxide is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the 2-methyl-1-pentene. Pumping 2-methyl-1-pentene into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 2-methyl-2-pentene, wherein the reaction yield is 63 percent and the selectivity is 98 percent.

Example 28

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The ZSM-5 molecular sieve modified by magnesium oxide is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the 2-methyl-1-hexene. 2-methyl-1-hexene is pumped into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating the reaction liquid to obtain a crude product of 2-methyl-2-hexene, wherein the reaction yield is 63 percent and the selectivity is 98 percent.

Example 29

Mixing the prepared ZSM-5 molecular sieve and mesoporous MgO according to the mass ratio of 1:1, stirring for 1 hour at 50 ℃, slowly adding hydrazine hydrate to adjust the pH value to 10, continuously stirring for 1 hour, aging for 6 hours at 50 ℃, washing, drying for 24 hours at 110 ℃, and calcining for 3 hours at 500 ℃ to obtain the magnesium oxide modified ZSM-5 molecular sieve.

The magnesium oxide modified ZSM-5 molecular sieve is filled into a fixed bed column, and the dosage of the catalyst is 5 percent of the mass of the 3-methyl-3-butene-1-ol. Pumping 3-methyl-3-buten-1-ol into a preheater for preheating at a constant rate of 25g/min by using a high-pressure metering pump; setting the temperature of the tubular reactor to 40 ℃, adjusting a reverse pressure controller after the temperature of the tubular reactor is stable, controlling the pressure to be 1 +/-0.01 MPa, continuously feeding and discharging materials, keeping the reaction residence time for 45min, and after the reaction is finished, rectifying and separating reaction liquid to obtain a crude product of prenol, wherein the reaction yield is calculated to be 70%, and the selectivity is calculated to be 98%.