CN114230429A - Method for synthesizing methyl cyclopentadiene from 3-hydroxymethyl cyclopentanone - Google Patents

Method for synthesizing methyl cyclopentadiene from 3-hydroxymethyl cyclopentanone Download PDF

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CN114230429A
CN114230429A CN202010943199.7A CN202010943199A CN114230429A CN 114230429 A CN114230429 A CN 114230429A CN 202010943199 A CN202010943199 A CN 202010943199A CN 114230429 A CN114230429 A CN 114230429A
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hydrogen
hydroxymethyl
cyclopentanone
catalyst
methyl cyclopentadiene
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CN114230429B (en
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李宁
佟国宾
李广亿
王爱琴
王晓东
丛昱
张涛
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a method for synthesizing methyl cyclopentadiene from 3-hydroxymethyl cyclopentanone. The method takes 3-hydroxymethyl cyclopentanone as a raw material, and directly synthesizes the methyl cyclopentadiene target product through one-step conversion in a fixed bed continuous reactor under the action of a supported A/X catalyst. The invention has simple process route and simple catalyst preparation, and provides an effective way for synthesizing the methylcyclopentadiene by taking 3-hydroxymethyl cyclopentanone as a raw material.

Description

Method for synthesizing methyl cyclopentadiene from 3-hydroxymethyl cyclopentanone
Technical Field
The invention belongs to the field of synthesis of fine chemical products, and particularly relates to a method for synthesizing methyl cyclopentadiene from 3-hydroxymethyl cyclopentanone.
Background
Methyl cyclopentadiene is an important chemical widely used and is a main raw material for producing curing agents, antiknock agents, metal derivatives and the like. Such as methylcyclopentadiene, can be used to prepare an epoxy resin curing agent-methylnadic anhydride (abbreviated as MNA); is also a key raw material for synthesizing gasoline antiknock agent-methyl cyclopentadienyl manganese tricarbonyl (MMT for short). In addition, the flame retardant is also commonly used for a series of products such as synthetic dye additives, high-grade essences and fragrances, reactive flame retardants, high-energy fuels RJ-4 and the like. Because methyl exists in the methyl cyclopentadiene molecule, the chemical product has more excellent properties than cyclopentadiene in certain performances, and the application range is still continuously expanded. However, because the direct source of the methyl cyclopentadiene is still limited, the research on the synthesis of the methyl cyclopentadiene has very important research value and practical significance.
Methyl cyclopentadiene is prepared mainly through cyclopentadiene methylation reaction and may be separated from ethylene cracking C9 fraction. CN101205168A discloses a method for preparing methyl cyclopentadiene, which comprises reacting cyclopentadiene with alkali including sodium, potassium or sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, etc. to generate sodium cyclopentadiene or potassium cyclopentadiene, and then carrying out methylation reaction with monochloro methane to prepare methyl cyclopentadiene. Although the reaction speed is high and the conversion rate is high, flammable metal sodium or potassium is used and flammable and explosive hydrogen is generated, so that the method has safety risk, the reaction condition is extremely strict and is not easy to control, the corrosion to equipment is high when strong alkali is used, the production cost is high, and the development and application of downstream products are restricted. And the fraction obtained by ethylene cracking C9 is depolymerized and rectified to obtain methyl cyclopentadiene, so that the problems are avoided, and CN102010285B discloses a method for extracting methyl cyclopentadiene from ethylene cracking carbon nine-heavy fraction, wherein firstly, a gas-phase material generated by depolymerizing the raw material C9 heavy fraction in a depolymerization reactor enters a first rectifying tower, a mixture of crude cyclopentadiene and crude methyl cyclopentadiene obtained from the top of the tower enters a second rectifying tower, the crude methyl cyclopentadiene obtained from the side line is dimerized, the obtained methyl cyclopentadiene dimers enter a third rectifying tower for reduced pressure rectification, and the high-purity methyl cyclopentadiene dimers are obtained from the side line. Although the purity of the target product is high, petroleum resources with limited reserves are used as raw materials, the ethylene cracking C9 fraction is very complex, the content requirements for directly decomposing the poly-p-methylcyclopentadiene dimer and the like are high, a large amount of polymers generated in the depolymerization process can only be used as low-added-value chemicals, so that the resource waste is caused, and meanwhile, the repeated depolymerization and rectification process causes complex process equipment and high energy consumption. Therefore, the search for green and renewable methyl cyclopentadiene synthesis process routes has become the direction of industry transformation.
In recent years, with the increasingly prominent problems of greenhouse effect, environmental pollution and the like brought by large-scale development and utilization of fossil resources, people have attracted extensive attention to the synthesis of high-value-added chemicals by using renewable biomass energy sources with abundant reserves as raw materials. For example, CN109134223A discloses a method for preparing 3-hydroxymethylcyclopentanone from 5-hydroxymethylfurfural, wherein 3-hydroxymethylcyclopentanone can be obtained by performing a hydrogenation rearrangement reaction on 5-hydroxymethylfurfural obtained by hydrolysis and dehydration of cellulose as a raw material in an aqueous phase. According to the method, 3-hydroxymethyl cyclopentanone is used as a raw material, an organic reagent is used as a solvent, and the methyl cyclopentadiene chemical with a high additional value is directly synthesized by one-step conversion in a fixed bed continuous reactor. Up to now, no report is available on the direct one-step conversion synthesis of methylcyclopentadiene from 3-hydroxymethylcyclopentanone.
Disclosure of Invention
The invention aims to provide a method for synthesizing methyl cyclopentadiene by 3-hydroxymethyl cyclopentanone. In particular to a method for directly synthesizing a methyl cyclopentadiene target product by one-step conversion in a fixed bed continuous reactor under the action of a supported A/X catalyst by taking 3-hydroxymethyl cyclopentanone as a raw material.
The invention is realized by the following technical scheme:
a method for synthesizing methyl cyclopentadiene from 3-hydroxymethyl cyclopentanone comprises the steps of taking 3-hydroxymethyl cyclopentanone as a raw material, pumping 3-hydroxymethyl cyclopentanone solutions with different concentrations into a fixed bed continuous reactor at a certain speed by using a liquid chromatography pump under the action of a supported A/X catalyst at a reaction temperature of 200--1(preferably 0.02-80 h)-1More preferably 0.05 to 60 hours-1) Directly obtaining the methyl cyclopentadiene by one-step conversion.
The chemical structural formulas of the raw material 3-hydroxymethyl cyclopentanone and the target product methyl cyclopentadiene are shown in Table 1:
TABLE 1 structural formulas of the starting materials and products
Figure RE-GDA0002728546430000021
Based on the technical scheme, the reaction for synthesizing the methyl cyclopentadiene by using the 3-hydroxymethyl cyclopentanone can be carried out without using a solvent, and one or a mixture of two or more of the following organic solvents can be adopted: benzene, toluene, tetrahydrofuran, decalin, cyclohexane, cyclopentane, n-hexane, n-pentane, n-heptane.
Based on the technical scheme, the mass concentration of the raw material 3-hydroxymethyl cyclopentanone is 0.1-100%, preferably 0.5-80%, and more preferably 1-60%.
Based on the technical scheme, the supported A/X catalyst is prepared by an isometric impregnation method, wherein the supported metal A is one or two or more of Pt, Pd, Ru, Ir, La, Co, Ni and Cu, and the mass loading of the metal A in the supported catalyst is 0.1-50%, preferably 0.2-45%, and more preferably 0.5-40%; the carrier X in the load type A/X catalyst is one or two or more than two of alumina, copper zinc aluminum, zirconium phosphate, phosphorylated niobium oxide, phosphorylated zirconium oxide, Nafion resin, Amberlyst resin, H-ZSM-5, H-beta, H-Y, H-USY, H-MOR and La-Y.
The specific process for preparing the catalyst by the isometric impregnation method comprises the following steps: the carrier component X is pretreated for 1 to 30 hours (preferably 2 to 24 hours, more preferably 3 to 18 hours) at 100-800 ℃ (preferably 200-700 ℃, more preferably 300-600 ℃), the impregnation solution is an aqueous solution of soluble salt of the metal A, the impregnation solution is added dropwise in equal volume to the pretreated carrier X, stirring is carried out while dropwise adding, then the mixture is kept stand for 1 to 36 hours (preferably 2 to 30 hours, more preferably 3 to 24 hours), and the mixture is baked at 120 ℃ for 12 to 48 hours, and then the mixture is baked at 200-900 ℃ (preferably 250-800 ℃, more preferably 300-700 ℃) for 0.1 to 12 hours (preferably 0.2 to 10 hours, more preferably 0.5 to 8 hours). Thus obtaining the load type A/X catalyst.
Based on the technical scheme, the supported A/X catalyst needs to be subjected to in-situ reduction treatment in a hydrogen atmosphere before use, and the reduction conditions are as follows: hydrogen pressure of 0.001-3.0MPa (preferably 0.005-2.5MPa, more preferably 0.01-2MPa), and hydrogen space velocity of 10-10000h-1(preferably 50 to 9000 h)-1More preferably 100--1) The reduction temperature is 200 ℃ to 700 ℃ (preferably 250 ℃ to 650 ℃, more preferably 300 ℃ to 600 ℃), and the reduction time is 0.5 to 12 hours (preferably 1 to 10 hours, more preferably 1.5 to 8 hours).
The invention has the beneficial effects that: the method can convert 3-hydroxymethyl cyclopentanone into methyl cyclopentadiene in one step by utilizing the fixed bed continuous flow reactor under the action of the catalyst, has high reaction conversion rate, good selectivity, mild conditions and simple process route, the raw material can be prepared from reproducible lignocellulose platform compound-5-hydroxymethyl furfural, and the hydrodeoxygenation and isomerization reactions of the raw material adopt common catalysts, are cheap and easy to obtain and are simple to prepare. Therefore, the method of the invention is a practical and simple method for synthesizing the methylcyclopentadiene.
Drawings
FIG. 1 is a mass spectrum of the product.
Detailed Description
The invention will now be illustrated by means of specific examples, without restricting its scope to these examples.
Examples 1 to 25
The process for preparing the supported A/X catalyst by an isometric impregnation method comprises the following steps: one or two or more of soluble salt aqueous solutions of Pt, Pd, Ru, Ir, La, Co, Ni or Cu are immersed in one or two or more of pretreated carrier alumina, copper zinc aluminum, zirconium phosphate, phosphorylated niobium oxide, phosphorylated zirconium oxide, Nafion resin, Amberlyst resin, H-ZSM-5, H-beta, H-Y, H-USY, H-MOR and La-Y in equal volume, and the solution is left to stand for 12 hours, dried at 120 ℃ for 12 hours, then roasted at 500 ℃ for 4 hours, and then tabletted and molded (examples 1 to 25).
Investigation of the reactivity of different catalysts for synthesizing methyl cyclopentadiene from 3-hydroxymethyl cyclopentanone: 1 g of the prepared supported A/X catalyst is filled in a fixed bed continuous reactor, and then the hydrogen pressure is 0.3MPa, and the hydrogen airspeed is 600h-1Heating to 400 ℃ at the speed of 5 ℃/min, reducing for 3 hours at the temperature, then reducing the bed temperature of the fixed bed continuous reactor to 300 ℃, controlling the hydrogen pressure to be 0.03MPa, pumping the 30% concentration 3-hydroxymethyl cyclopentanone tetrahydrofuran solution into the fixed bed continuous reactor at a certain speed by using a liquid chromatography pump, wherein the molar ratio of hydrogen to 3-hydroxymethyl cyclopentanone is 100:1, and the mass space velocity of 3-hydroxymethyl cyclopentanoneIs 3.0h-1The results are shown in Table 2.
TABLE 2 reactivity of different catalysts for the synthesis of methylcyclopentadiene from 3-hydroxymethylcyclopentanone
Figure RE-GDA0002728546430000031
Figure RE-GDA0002728546430000041
As can be seen from the data in Table 2, the catalysts listed in the table all have good effects on the synthesis of methylcyclopentadiene from 3-hydroxymethylcyclopentanone. The active metal and carrier species have a large effect on both the feedstock conversion and product yield, while the active metal loading has no significant effect on the reaction. The 3-hydroxymethyl cyclopentanone can be completely converted under the action of the catalyst 5% Ru/H-USY, and the yield of the target product methyl cyclopentadiene can reach 87%.
Examples 26 to 42
1 g of the 5% Ru/H-USY catalyst prepared in example 24 was charged in a fixed-bed continuous reactor at a hydrogen pressure of 0.3MPa and a hydrogen space velocity of 600H-1Heating to 400 ℃ at the speed of 5 ℃/min, reducing for 3 hours at the temperature, then reducing the bed temperature of the fixed bed continuous reactor to 300 ℃, regulating the hydrogen pressure to a required value, pumping 3-hydroxymethyl cyclopentanone solutions with different concentrations into the fixed bed continuous reactor at a certain speed by using a liquid chromatography pump, wherein the molar ratio of hydrogen to 3-hydroxymethyl cyclopentanone is 100:1, and the mass space velocity of the 3-hydroxymethyl cyclopentanone is 3.0h-1The results are shown in Table 3 (examples 26 to 42).
TABLE 3 Effect of different concentrations, solvents and hydrogen pressures on the reactivity of 3-hydroxymethylcyclopentanone to methylcyclopentadiene
Figure RE-GDA0002728546430000051
It can be seen from the data results in table 3 that the solvents listed in the table all have good effects on the reaction of synthesizing methylcyclopentadiene from 3-hydroxymethylcyclopentanone, the hydrogen pressure has little effect on the reaction, the substrate concentration has no significant effect on the reaction, and even in the case of not using a solvent (i.e. the raw material concentration is 100%), methylcyclopentadiene with higher yield can be obtained.
Examples 43 to 55
1 g of the 5% Ru/H-USY catalyst prepared in example 24 was charged in a fixed-bed continuous reactor at a hydrogen pressure of 0.3MPa and a hydrogen space velocity of 600H-1The temperature is raised to 400 ℃ at the speed of 5 ℃/min, the reduction is carried out for 3 hours at the temperature, then the bed temperature of the fixed bed continuous reactor is lowered to the required reaction temperature, the hydrogen pressure is controlled to be 0.03MPa, a cyclohexane solution of 3-hydroxymethyl cyclopentanone with the concentration of 30% is pumped into the fixed bed continuous reactor at a certain speed by a liquid chromatography pump, the molar ratio of different hydrogen to 3-hydroxymethyl cyclopentanone and the mass space velocity of different 3-hydroxymethyl cyclopentanones are controlled, the influence of the reaction conditions on the reaction is examined, and the experimental results are shown in Table 4 (examples 43-55).
TABLE 4 influence of different reaction conditions on the reactivity of 3-hydroxymethylcyclopentanone to methylcyclopentadiene
Figure RE-GDA0002728546430000061
From the data in Table 4, it can be seen that the molar ratio of hydrogen to the starting material and the mass space velocity do not greatly affect the reaction of 3-hydroxymethylcyclopentanone to methylcyclopentadiene under the conditions we used. The reaction temperature has a great influence on the yield of the methyl cyclopentadiene, and when the temperature is lower than 200 ℃, the yield of the methyl cyclopentadiene is obviously reduced.
It can be seen from the above examples that under the action of cheap and readily available catalyst in a fixed bed continuous flow reactor, the high yield preparation of methylcyclopentadiene from 3-hydroxymethylcyclopentanone can be completely achieved, and the purity of the obtained methylcyclopentadiene is as high as 95%. The reaction process has mild conditions and simple process route, and is a practical and efficient method for synthesizing methyl cyclopentadiene.
Comparative examples 56 to 64
The specification with the Chinese patent application publication number of CN111217657A discloses a method for synthesizing methyl cyclopentadiene by 3-methyl-2-cyclopentene-1-ketone under a supported metal oxide catalyst, and the catalyst used in the invention is compared in an experiment in a system of the technical scheme of the invention.
1 g of the catalyst in the invention is taken and filled in a fixed bed continuous reactor, and then the hydrogen pressure is 0.3MPa, and the hydrogen airspeed is 600h-1Heating to 400 ℃ at the speed of 5 ℃/min, reducing for 3 hours at the temperature, then reducing the bed temperature of the fixed bed continuous reactor to 300 ℃, controlling the hydrogen pressure to be 0.03MPa, pumping the cyclohexane solution of 3-hydroxymethyl cyclopentanone with the concentration of 30% into the fixed bed continuous reactor at a certain speed by using a liquid chromatography pump, wherein the molar ratio of hydrogen to 3-hydroxymethyl cyclopentanone is 20:1, and the mass space velocity of 3-hydroxymethyl cyclopentanone is 10.0h-1The results are shown in Table 5 (comparative examples 56 to 64).
TABLE 5 Effect of Supported Metal oxide catalyst systems on the reactivity of 3-hydroxymethylcyclopentanone to methylcyclopentadiene
Figure RE-GDA0002728546430000071
From the data results in table 5, it can be seen that the supported metal oxide catalyst used in the technical scheme of chinese patent application publication No. CN111217657A can also convert 3-hydroxymethylcyclopentanone into methylcyclopentadiene in the reaction system of the present invention, but the catalytic effect is generally low, the reaction stays in the intermediate process, intermediate products such as 3-hydroxymethylcyclopentanone and methylcyclopentenone are produced, and byproducts such as methylcyclopentene are produced, and the conversion rate of raw materials and the yield of products are far from the effects achieved by the supported a/X catalyst in the present invention.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or modifications of the invention described in the foregoing embodiments, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (8)

  1. The method for synthesizing the methyl cyclopentadiene by using the 3-hydroxymethyl cyclopentanone is characterized by comprising the following steps of: 3-hydroxymethyl cyclopentanone is taken as a raw material, in a fixed bed continuous reactor, under the action of a supported A/X catalyst, the reaction temperature is 200-600 ℃, the hydrogen pressure is 0.01-3MPa, the molar ratio of hydrogen to 3-hydroxymethyl cyclopentanone is 2-500:1, and the mass space velocity of 3-hydroxymethyl cyclopentanone is 0.01-100h-1Directly obtaining methyl cyclopentadiene through one-step conversion;
    the supported A/X catalyst is prepared by an isometric impregnation method; the supported metal A is one or two or more of Pt, Pd, Ru, Ir, La, Co, Ni and Cu, and the carrier X is one or two or more of alumina, copper-zinc-aluminum, zirconium phosphate, phosphorylated niobium oxide, phosphorylated zirconium oxide, Nafion resin, Amberlyst resin, H-ZSM-5, H-beta, H-Y, H-USY, H-MOR and La-Y; the mass loading of the metal A in the supported A/X catalyst is 0.1 to 50%, preferably 0.2 to 40%, more preferably 0.5 to 30%.
  2. 2. The method of claim 1, wherein: the reaction temperature is 260 ℃ and 550 ℃; the hydrogen pressure is 0.01-2 MPa; the molar ratio of the hydrogen to the 3-hydroxymethyl cyclopentanone is 5-400: 1; the mass space velocity of the 3-hydroxymethyl cyclopentanone is 0.02-80h-1。
  3. 3. The method of claim 1, wherein: the reaction temperature is 280-500 ℃; the hydrogen pressure is 0.01-1 MPa; the molar ratio of the hydrogen to the 3-hydroxymethyl cyclopentanone is 10-300: 1; the mass space velocity of the 3-hydroxymethyl cyclopentanone is 0.05-60h-1。
  4. 4. The method of claim 1, wherein: the reaction for synthesizing the methyl cyclopentadiene by using the 3-hydroxymethyl cyclopentanone does not add a solvent, or adopts one or two or more of the following organic solvents: benzene, toluene, tetrahydrofuran, decalin, cyclohexane, cyclopentane, n-hexane, n-pentane, n-heptane.
  5. 5. Method according to claims 1 and 2, characterized in that: the mass concentration of the 3-hydroxymethyl cyclopentanone is 0.1-100%, preferably 0.5-80%, more preferably 30-50%.
  6. 6. The method according to any one of claims 1 to 5, wherein: the method comprises the step of carrying out in-situ reduction pretreatment on the supported A/X catalyst in a hydrogen atmosphere, wherein the reduction conditions are as follows: the hydrogen pressure is 0.001-3.0MPa, and the hydrogen airspeed is 10-10000h-1The reduction temperature is 200 ℃ and 700 ℃, and the reduction time is 0.5-12 hours.
  7. 7. The method of claim 6, wherein: the hydrogen pressure is 0.005-2.5MPa, and the hydrogen airspeed is 50-9000h-1The reduction temperature is 250 ℃ to 650 ℃, and the reduction time is preferably 1-10 hours.
  8. 8. The method of claim 7, wherein: the hydrogen pressure is 0.01-2MPa, the hydrogen space velocity is 100--1The reduction temperature is preferably 300 ℃ and 600 ℃, and the reduction time is 1.5-8 hours.
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US5723708A (en) * 1994-09-29 1998-03-03 Nippon Petrochemicals Company, Limited Method for producing cyclopentadienes
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CN111217657A (en) * 2018-11-25 2020-06-02 中国科学院大连化学物理研究所 Method for synthesizing methyl cyclopentadiene from 3-methyl-2-cyclopentene-1-ketone
CN114315504A (en) * 2020-09-29 2022-04-12 中国科学院大连化学物理研究所 Method for preparing methyl cyclopentadiene by catalyzing AxByOz type composite metal oxide

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0899911A (en) * 1994-09-29 1996-04-16 Nippon Petrochem Co Ltd Production of cyclopentadienes
US5723708A (en) * 1994-09-29 1998-03-03 Nippon Petrochemicals Company, Limited Method for producing cyclopentadienes
CN103420776A (en) * 2012-05-22 2013-12-04 中国石油化工股份有限公司 Preparation method for methyl cyclopentene
CN106866331A (en) * 2015-12-12 2017-06-20 中国科学院大连化学物理研究所 A kind of method that cyclopentadiene or dicyclopentadiene are prepared by furfuryl alcohol
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