CN113083358B - Magnesium compound modified Ti-HMS/nano carbon fiber composite catalyst, preparation and application - Google Patents

Magnesium compound modified Ti-HMS/nano carbon fiber composite catalyst, preparation and application Download PDF

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CN113083358B
CN113083358B CN201911335451.XA CN201911335451A CN113083358B CN 113083358 B CN113083358 B CN 113083358B CN 201911335451 A CN201911335451 A CN 201911335451A CN 113083358 B CN113083358 B CN 113083358B
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hms
carbon fiber
nano carbon
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CN113083358A (en
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翁羽飞
周飞
奚军
蒋方红
许艾娜
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China Petroleum and Chemical Corp
Sinopec Shanghai Petrochemical Co Ltd
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Sinopec Shanghai Petrochemical Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a magnesium compound modified Ti-HMS/carbon nanofiber composite catalyst, a preparation method and application. The invention introduces active magnesium-containing compound and nano carbon fiber into the catalyst to obtain a modified titanium silicalite molecular sieve catalyst; the modified titanium silicalite molecular sieve catalyst is used for synthesizing dicyclopentadiene dioxide by DCPD catalytic oxidation, and has high DCPD conversion rate and product selectivity; and the catalyst has long service life and can run for a long period.

Description

Magnesium compound modified Ti-HMS/nano carbon fiber composite catalyst, preparation and application
Technical Field
The invention belongs to the technical field of catalytic oxidation synthesis of organic epoxy compounds and catalytic oxidation of olefins, and particularly relates to a titanium-silicon molecular sieve catalyst which is based on carbon nanofibers as a carrier, is modified by a magnesium-containing compound and has mesoporous characteristics, and preparation and application.
Background
Dicyclopentadiene is an important component in petroleum cracking carbon five fractions and accounts for about 14% -19% of the carbon five fractions. Dicyclopentadiene, the epoxidation reaction product of dicyclopentadiene, is a cycloaliphatic epoxide with excellent properties. Compared with common epoxy resin, dicyclopentadiene dioxide has better performances in the aspects of high temperature resistance, heat resistance, weather resistance, ultraviolet resistance, electric insulation, high strength and the like. Based on the above properties, dicyclopentadiene dioxide is widely used in high temperature resistant castable, glass fiber reinforced plastic, adhesives, laminates, electronic device packaging and the like.
In the prior art, twoThe dicyclopentadiene is usually oxidized by the methods of peracetic acid method, chlorohydrin method, hydroperoxide catalytic epoxidation method and the like through epoxidation reaction, but the three methods have the defects of complex reaction process, serious equipment corrosion, easy generation of acid ring-opening of epoxide to generate byproducts, high discharge of three wastes and the like at present. In recent years, a green oxidation process using hydrogen peroxide as an oxygen source and a heteropolyacid compound as a catalyst has been widely paid attention. According to the catalytic mechanism, the catalyst can be divided into a homogeneous catalyst and a heterogeneous catalyst, the homogeneous catalytic reaction is to directly add heteropolyacid or salts thereof into a reaction system, the catalytic efficiency is high, the catalyst is not easy to recycle, the cost is high, and the three wastes are discharged more; the heterogeneous catalytic reaction realizes the recycling of the catalyst while maintaining relatively high catalytic efficiency, so that the heterogeneous catalytic reaction is widely focused and studied by scientific researchers at home and abroad. Ventullo et al report Na 2 WO 4 /H 3 PO 4 /H 2 O 2 In the two-phase catalytic epoxidation reaction system, the conversion rate of most of olefins such as cyclohexene, styrene and the like is 95 percent, and the selectivity of the epoxide compound is about 80 percent (J.Org.chem, 1983,48 (21): 3831-3833). Ishii et al report heteropolyacids H 3 PW 12 O 40 Or H 3 PMo 12 O 40 With cetyl pyridine chloride in the presence of a catalyst consisting of 35% H 2 O 2 The epoxidation reaction of various organic substrates can be effectively carried out in a homogeneous or two-phase system. However, when the catalyst system is used for synthesizing dicyclopentadiene dioxide, the defects of easy loss of heteropolyacid, high difficulty in separating and recycling the catalyst, low repeated use times and the like exist, and the catalyst system is difficult to be used in an industrial device (J.Org.chem, 1998, 53 (15): 3587-3593). Li Li et al report H 3 PW 12 O 40 Impregnating silica surfaces with H 2 O 2 As an oxidant, the catalyst has high initial activity when used for synthesizing dicyclopentadiene dioxide, but the heteropolyacid adsorbed on the surface of silicon dioxide is easy to run off in the reaction process, and the catalyst cannot be reused (heteropolyacidNew green synthesis process [ D ] for preparing dicyclopentadiene dioxide by catalyzing dicyclopentadiene][ Shuoshi paper ]]Jilin, university of northeast, 2007). Thus, the heteropolyacid is supported on the surface of the silica by an impregnation method or a sol-gel method, so that the problem of catalyst recovery can be solved, but the heteropolyacid is easy to fall off from the surface of the catalyst carrier in the reaction process, so that the service life of the catalyst is short, and the catalyst activity is obviously reduced after the catalyst is generally repeatedly used for 5 to 6 times, and the catalyst is not easy to be used in an industrial production device. In summary, the heterogeneous catalytic oxidation method is used for preparing the epoxy pentadiene dioxide, and the catalyst is recycled, but the problem that the heteropolyacid is easy to fall off and the service life of the catalyst is short exists.
Disclosure of Invention
In order to solve the problems of the dicyclopentadiene dioxide synthesis process defect, short catalyst life and the like, the inventor discovers that dicyclopentadiene can be effectively synthesized into dicyclopentadiene dioxide (DCPDDO) by adopting a titanium-silicon molecular sieve catalyst and using organic peroxide as an oxidant, and the reaction yield can reach 90-100%.
The existing Ti-HMS molecular sieve catalyst is used for synthesizing DCPD DO, has good initial activity, but the reaction activity is obviously reduced along with the increase of the using times. The important reason is that the excessive organic peroxide can introduce more water into the reaction system, and partial decomposition of the excessive organic peroxide can generate water and acid in the reaction process, so that the polymerization of reaction products is easy to cause the blocking of catalyst pore channels, the cracking of HMS skeleton and the loss of titanium, thereby inactivating the catalyst, and the Ti-HMS is limited to be used for dicyclopentadiene dioxide synthesis.
In order to solve the problem, the inventor improves the titanium-containing molecular sieve catalyst Ti-HMS with mesoporous characteristics, and introduces active magnesium-containing compounds and nano carbon fibers into the catalyst, so that the performance of the Ti-HMS is greatly improved.
The technical scheme of the invention is specifically introduced as follows.
The invention provides a Ti-HMS/nano carbon fiber composite catalyst modified by magnesium compound, which has mesoporous characteristics and is modifiedA catalyst comprising the components: 0.1 to 6 percent of Ti, 50 to 70 percent of nano carbon fiber and SiO 2 The mass fraction is 25-45%, the mass fraction of magnesium oxide is 0.01-2%, and the UV-vis spectrogram of the catalyst has a strong absorption peak at 220 nm.
The invention also provides a preparation method of the magnesium compound modified Ti-HMS/nano carbon fiber composite catalyst, which comprises the following steps:
a) Under inert atmosphere, dissolving a silicon source, a titanium source and a template agent in a mixed solvent of water and organic alcohol, stirring and crystallizing at room temperature for 0.5-10 hours, adding nano carbon fiber, continuously stirring for 10-72 hours, crystallizing at 150-200 ℃ for 1-7 days, and separating, washing and drying a crystallized product to obtain the Ti-HMS loaded by the nano carbon fiber;
b) Adding the Ti-HMS loaded by the carbon nanofiber into the catalyst containing Mg (OH) 2 、MgO、MgCO 3 、4MgCO 3 。Mg(OH) 2 .5H 2 O, dolomite (MgCO) 3 .CaCO 3 ) Stirring the mixture of any one or more of the above in water solution for 10 to 48 hours at room temperature, separating out solid, washing the liquid until the liquid is neutral, drying, and then roasting the liquid in inert atmosphere at 300 to 1000 ℃ for 2 to 20 hours to obtain a Ti-HMS catalyst matrix taking magnesium-containing compound modified nano carbon fiber as a carrier;
c) Treating Ti-HMS catalyst parent body with organosilicon solution at 25-300 deg.c for 0.5-100 hr; the usage amount of the organic silicon is 10% -70% of the weight of the Ti-HMS catalyst matrix; and then filtering and separating out a solid catalyst, washing the solid catalyst by using an inert solvent, and baking the solid catalyst for 10-24 hours in an environment with the pressure of 0.133-1.33 KPa and the temperature of 80-200 ℃ to prepare the magnesium compound modified Ti-HMS/nano carbon fiber composite catalyst.
Further, in step a), the silicon source is one or two of orthosilicate or hydrocarbyl silicate; the titanium source is titanate; the template agent is of the general formula RNH 2 R is a chain alkyl group of 6 to 18 carbon atoms; RNH (RNH) 2 And Si in the silicon source in a molar ratio of 0.01 to 0.3:1, the molar ratio of Si in the silicon source to Ti in the titanium source being 5: 1-200:1, water and siliconThe source molar ratio is 4-20:1, the volume ratio of the alcohol to the silicon source is 1-4:1, and the molar ratio of the carbon nanofiber to the silicon source is 5-20:1.
Further, the titanate used is selected from any one of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, and tetraisobutyl titanate.
Further, in step a), the carbon nanofibers used are produced from a carbon-containing gas source, preferably CO, CH 4 、C 2 H 6 、C 3 H 8 Any one of the elements in group VIII of the periodic table is selected as a reaction raw material, and more preferably any one single metal element or a plurality of element alloys in Fe, co and Ni is selected as a catalyst, and the carbon nanofiber is formed through catalytic pyrolysis reaction by a carbon-containing gas source, wherein the catalytic growth temperature of the carbon nanofiber is 550-650 ℃.
Further, in the step b), the volume ratio of the nano carbon fiber loaded Ti-HMS to the magnesium compound aqueous solution is 1:1 to 1:3, mgO, mg (OH) 2 、MgCO 3 、4MgCO 3 。Mg(OH) 2 ·5H 2 The mole ratio of any one or a mixture of more than one of O and dolomite to the silicon source used in the step a) is 0.01:100-3: 100; the roasting temperature is 400-800 ℃ and the roasting time is 3-8 hours.
Further, in step c), the organosilicon solution is used, and the organosilicon is selected from any one of halosilanes, silazanes or silylamines.
Further, in step c), the organic silicon is selected from any one of trimethylchlorosilane, triethylsilicon chloride, hexamethyldisilazane or N-trimethylsilylimidazole.
Further, in the step c), the organic silicon solution is used, and the solvent is selected from any one or a mixture of more than one of benzene, toluene, isopropylbenzene, ethylbenzene, cyclohexane, n-heptane, octane and dodecane.
Further, in step c), washing with an inert solvent, comprising: the solid catalyst is washed 3 times by toluene, benzene or alkane inert solvent, and the volume of the inert solvent used for each washing is 5-10 times of the volume of the solid catalyst.
The invention further provides an application of the titanium-silicon molecular sieve catalyst taking the carbon nanofiber as a carrier in the reaction of preparing dicyclopentadiene dioxide by catalytic oxidation of dicyclopentadiene DCPD.
The specific application method is as follows: dicyclopentadiene DCPD is used as a reaction raw material, organic peroxide is used as an oxidant, a nonpolar compound inert to a reaction system is used as a solvent, and the DCPD undergoes catalytic oxidation reaction under the action of a Ti-HMS/nano carbon fiber composite catalyst modified by a magnesium-containing compound to generate dicyclopentadiene dioxide; wherein:
the oxidant is selected from any one of benzoyl peroxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide or cumene hydroperoxide; the inert solvent is selected from any one of benzene, toluene, ethylbenzene, cumene, acetone or petroleum ether; the catalytic oxidation reaction temperature is 50-150 ℃, the pressure (gauge pressure) is 0-10 MPa, the molar ratio of the organic peroxide to DCPD is 6:1-2:1, and the volume ratio of the inert solvent to the DCPD is 10:1-30:1.
Further, the catalytic oxidation reaction temperature is 60-100 ℃, the pressure (gauge pressure) is 0.3-2 MPa, and the molar ratio of the organic peroxide to DCPD is 3:1-2:1.
Furthermore, the catalytic oxidation reaction adopts an intermittent reaction process or a fixed bed continuous reaction process; the batch reaction process is adopted, and the mass ratio of the catalyst to DCPD is 0.01: 100-20: 100, the reaction time is 2-10 hours; adopting a fixed bed continuous reaction process, wherein the volume space velocity of the total material is 0.1-3 h -1 。
Further, the mass ratio of catalyst to DCPD was 0.5: 100-10: 100, the reaction time is 3-6 hours.
Compared with the prior art, the invention has the following advantages:
1. the catalyst is modified by nano carbon fiber, so that the hydrophobic property is improved, and the service life of the catalyst is greatly prolonged;
2. the active magnesium-containing compound is introduced into the catalyst carrier, so that the coking resistance of the catalyst is obviously enhanced, and the catalyst is not easy to deactivate.
3. The Ti-HMS catalyst provided by the invention is used for synthesizing dicyclopentadiene dioxide, not only has high DCPD conversion rate and product selectivity, but also can run for a long period.
4. The catalyst provided by the invention is also suitable for epoxidation reaction of cyclic mono-olefin and non-conjugated cyclic multi-olefin with 4-18 carbon atoms, such as cyclobutene, cyclopentene, cyclohexene, cyclooctene, cyclododecene, norbornene, alpha-pinene and the like, and can oxidize aliphatic olefin and aromatic olefin in the general formula (1) to generate compound in the general formula (2), wherein R in the general formula (1) and the general formula (2) 1 、R 2 、R 3 、R 4 Independently selected from any one of hydrogen, C1-C14 linear alkyl, branched alkyl, cycloalkyl and aryl.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention is further illustrated by the following examples, but the present invention is not limited to the examples. Product yield definition in this patent specification:
dcpdpo yield = moles of dcpdpo in the reaction product/moles of DCPD starting material participating in the reaction ×100%
Example 1
Under the condition of stirring at room temperature, adding 23 g of hexadecylamine into 112ml of water and 110 ml of ethanol in sequence in a reactor, and stirring; 65 g of ethyl orthosilicate and 10 g of ethyl titanate dissolved in 30 ml of ethanol are added into the solution, stirred for 30 minutes, crystallized for 12 hours, added with 74.9 g of nano carbon fiber, stirred for 10 to 72 hours continuously, the temperature of the reactor is raised, the reaction material is crystallized for 1 day at 200 ℃, the solid is obtained by filtering, the template agent in the catalyst is extracted by ethanol, and then the solution is washed by pure water until the eluent is neutral. And drying the washed solid at 110 ℃ for 12 hours to obtain the Ti-HMS taking the carbon nanofiber as the carrier.
Adding 3 times of pure water and 0.54 g of Mg (OH) into the Ti-HMS solid taking the carbon nanofiber as a carrier 2 Stirring at room temperature for 48 hr, separating solid, washing with pure water until the water washing solution is neutral, and washing with 8Drying at 0 ℃ for 20 hours, and then roasting at 400 ℃ in helium atmosphere for 20 hours to obtain Ti-HMS taking the magnesium compound modified nano carbon fiber as a carrier;
the prepared powder catalyst sample is pressed into tablets, crushed and screened, 50 g of particles with 20-50 meshes are taken and put into a reactor, then 35 g of trimethylchlorosilane and 200 ml of toluene are added into the reactor, the mixture is stirred, the reaction temperature is 120 ℃ for silanization for 10 hours, the reaction is stopped, the solid catalyst is taken out, the toluene is leached, and the solid catalyst is dried for 30 hours in a vacuum system with the temperature of 80 ℃ and the system pressure of 0.133 KPa.
Example 2
15 g of dodecylamine are added into a reactor in turn under the condition of stirring at room temperature, and added into 80ml of water and 40 ml of ethanol, and stirred; 65 g of ethyl orthosilicate and 14 g of butyl titanate dissolved in 30 ml of ethanol are added into the solution, the mixture is stirred for 30 minutes, the crystallization is carried out for 6 hours, 37.4 g of nano carbon fiber is added, the mixture is continuously stirred for 60 hours, the temperature is raised, the materials in the reactor are crystallized for 7 days at 150 ℃, the solid is obtained by filtering, the template agent in the catalyst is removed by ethanol extraction, and then the washing is carried out by pure water until the eluent is neutral. And drying the washed solid at 110 ℃ for 10 hours to obtain the Ti-HMS taking the carbon nanofiber as the carrier.
Adding pure water with 3 times of the volume of a solid catalyst into Ti-HMS solid taking the carbon nanofiber as a carrier, and adding 0.6 g of MgCO 3 0.1 g MgO, stirring for 48 hours at room temperature, separating out solid, washing with pure water until the water washing liquid is neutral, drying at 80 ℃ for 20 hours, and roasting at 500 ℃ in helium atmosphere for 24 hours to obtain Ti-HMS taking magnesium-containing compound modified nano carbon fiber as a carrier;
the prepared powder catalyst sample is pressed into tablets, crushed and screened, 50 g of particles with 20-50 meshes are taken and put into a reactor, then 20 g of triethylchlorosilane and 200 ml of toluene are added into the reactor, the mixture is stirred, the reaction temperature is 180 ℃ for silanization for 6 hours, the reaction is stopped, the solid catalyst is taken out, the cyclohexane is leached to remove the alkyl silicon, and the mixture is dried for 10 hours in a vacuum system with the temperature of 220 ℃ and the system pressure of 0.133 KPa.
Example 3
Under the condition of stirring at room temperature, adding 0.7 g of tetradecylamine into 22ml of water and 60 ml of ethanol in sequence in the reaction, and stirring; 65 g of ethyl orthosilicate and 5 g of ethyl titanate dissolved in 30 ml of ethanol are added into the solution, stirred for 30 minutes, crystallized for 6 to 12 hours, added with 18.7 g of nano carbon fiber, continuously stirred for 10 to 72 hours, heated, crystallized for 1 day at 150 ℃, filtered to obtain solid, and the template agent in the catalyst is removed by ethanol extraction. Then washing with pure water until the eluent is neutral. And drying the washed solid at 110 ℃ to obtain the Ti-HMS taking the carbon nanofiber as the carrier. Adding pure water with the same volume as that of solid catalyst into Ti-HMS solid with the carbon nanofiber as a carrier, and adding 0.02 g basic magnesium carbonate (4 MgCO 3 。Mg(OH) 2 .5H 2 O) at room temperature, stirring for 48 hours, separating out solid, washing with pure water until the water washing liquid is neutral, drying at 80 ℃ for 20 hours, and then roasting at 500 ℃ in helium atmosphere for 20 hours to obtain Ti-HMS with metal oxide modified and nano carbon fiber as a carrier;
after the prepared powder catalyst sample is pressed into tablets, crushing and screening are carried out, 50 g of particles with 20-50 meshes are taken and put into a reactor, then 5 g of hexamethyldisilazane and 200 ml of toluene are added into the reactor, the mixture is stirred, the reaction temperature is 200 ℃ for silanization for 6 hours, the reaction is stopped, the solid catalyst is taken out, the cyclohexane is leached to remove the silylation agent, and then the mixture is dried for 30 hours in a vacuum system with the temperature of 105 ℃ and the system pressure of 1.33 KPa.
Example 4
Under the condition of room temperature and stirring, sequentially adding 10 g of hexylamine and 5 g of dodecylamine into 80ml of water and 60 ml of ethanol into a reactor, and stirring; 65 g of ethyl orthosilicate and 0.5 g of ethyl titanate dissolved in 30 ml of ethanol are added into the solution, stirred for 30 minutes, crystallized for 24 hours, added with 30 g of nano carbon fiber, continuously stirred for 10 to 72 hours, heated, crystallized for 7 days at 150 ℃ in a reactor, filtered to obtain solid, template agent in the catalyst is extracted by ethanol, and then washed by pure water until the eluent is neutral. The washed solid was dried at 110℃for 12 hours and then calcined at 600℃in helium atmosphere for 4 hours to obtain Ti-HMS having hexagonal mesopores.
Adding pure water into the Ti-HMS solid taking the carbon nanofiber as a carrier, wherein the volume ratio of the pure water to the solid catalyst is 2:1, 1.5 g of dolomite (MgCO 3 .CaCO 3 ) Stirring at room temperature for 48 hours, separating out solid, washing with pure water until the water washing liquid is neutral, drying at 80 ℃ for 20 hours, and then roasting at 800 ℃ with helium for 20 hours to obtain the Ti-HMS with the active magnesium-containing compound modified and the nano carbon fiber as the carrier
After the prepared powder catalyst sample is pressed into tablets, crushing and screening are carried out, 50 g of particles with 20-50 meshes are taken and put into a reactor, then 20 g of N-trimethylsilylimidazole and 200 ml of toluene are added into the reactor, the mixture is stirred, the reaction temperature is 200 ℃ for silanization for 6 hours, the reaction is stopped, the solid catalyst is taken out, cyclohexane is leached to remove the silylation agent, and then the mixture is dried for 10 hours in a vacuum system with the temperature of 200 ℃ and the system pressure of 0.133 KPa.
Examples 5 to 14
The catalysts prepared in examples 1-4 were used in a 100 ml stainless steel stirred reactor to synthesize dicyclopentadiene dioxide, and the batch reaction process examined the effects of temperature, pressure, material ratio, catalyst amount, reaction time and solvent on the product, and the results are shown in Table 1.
Wherein the catalysts used in examples 5 to 7 were provided in example 1, the catalysts used in examples 8 to 10 were provided in example 2, the catalysts used in examples 11 to 12 were provided in example 3, and the catalysts used in examples 13 to 14 were provided in example 4.
TABLE 1
Examples 15 to 21
DCPD is used as a raw material, a 100 ml fixed bed reactor is used for synthesizing DCPDO through continuous reaction, the influence of catalysts prepared in examples 1-4 on synthesizing the DCPDO at different temperatures, pressures, material ratios and airspeeds is examined, and the results are shown in Table 2.
Wherein the catalysts used in examples 15 to 17 were provided in example 1, the catalysts used in examples 18 to 19 were provided in example 2, and the catalysts used in examples 20 to 21 were provided in example 3, the experimental results are shown in Table 2.
TABLE 2
Examples 22 to 28
Propylene, butylene, n-pentene, cyclopentene, hexene, cyclohexene and styrene are used as raw materials to replace DCPD, and the volume ratio of olefin to solvent is 1:20, the kettle-type reactor is subjected to epoxidation reaction to obtain alkylene oxide corresponding to the reaction raw material olefin, and the product yield is shown in table 3. Examples 22 to 24 used the catalyst provided in example 1, examples 25 to 26 used the catalyst provided in example 2, examples 27 to 28 used the catalyst provided in example 3, and the experimental results are shown in Table 3.
TABLE 3 Table 3
According to the preparation method of the catalyst provided by the invention, the nano carbon fiber is used as a carrier, so that the catalytic water resistance is greatly improved, and the example 29 and the example 30 are further compared and illustrated.
Example 29
In a 500 ml autoclave, 20 g of the catalyst provided in example 4 of the present invention was fixed on a cooling coil in the autoclave in a stainless steel wire basket manner, 300 ml of cumene, 60 g of 80% CHP,15 g of DCPD were charged, the reaction temperature was 80 to 90, the reaction pressure was 1MPa, the stirring speed was 600r/min, the reaction time was 3 hours, the reaction was terminated, the material was cooled to room temperature, and the material was discharged. According to the feeding proportion of the first batch, a second batch of reverse raw materials is put into the autoclave, the second batch of reaction is started, and the reaction of the subsequent batch is sequentially carried out. The effect of the number of catalyst uses on the reaction was examined. The water content in the reaction raw material was 1000ppm, and the results are shown in Table 4.
TABLE 4 Table 4
Number of catalyst reuse times DCPDPO reaction yield/%
1 100.0
10 99.6
20 99.2
Example 30
Mesoporous titanium silicalite catalyst Ti-HMS was prepared according to published literature (see CN 106279069A) as a comparative example, the experimental method was the same as example 29, the mass fraction of water in the reaction raw material was 1000ppm, and the influence of catalyst reuse on the reaction was examined, and the results are shown in Table 5.
TABLE 5
Number of catalyst reuse times DCPDPO reaction yield/%
1 90.1
2 89.5
3 88.3
4 87.2
5 82.3
While the preferred embodiments of the present invention have been illustrated and described, the present invention is not limited to the embodiments, and various equivalent modifications and substitutions can be made by one skilled in the art without departing from the spirit of the present invention, and these equivalent modifications and substitutions are intended to be included in the scope of the present invention as defined in the appended claims.

Claims (9)

1. A Ti-HMS/nano carbon fiber composite catalyst modified by magnesium compound is characterized in that: the Ti-HMS/nano carbon fiber composite catalyst has mesoporous characteristics, and comprises the following components: 0.1 to 6 percent of Ti, 50 to 70 percent of nano carbon fiber and SiO 2 25-45% of magnesium oxide and 0.01-2% of magnesium oxide;
the composite catalyst is prepared by the following steps:
a) Under inert atmosphere, dissolving a silicon source, a titanium source and a template agent in a mixed solvent of water and organic alcohol, stirring and crystallizing at room temperature for 0.5-10 hours, adding nano carbon fiber, continuously stirring for 10-72 hours, crystallizing at 150-200 ℃ for 1-7 days, and separating, washing and drying a crystallized product to obtain the Ti-HMS loaded by the nano carbon fiber;
b) Adding the Ti-HMS loaded by the carbon nanofiber into the catalyst containing Mg (OH) 2 、MgO、MgCO 3 、4MgCO 3 .Mg(OH) 2 .5H 2 In O, dolomiteStirring the mixture of any one or more of the above materials in water solution for 10 to 48 hours at room temperature, separating out solid, washing the liquid until the liquid is neutral, drying, and roasting the liquid in inert atmosphere at 300 to 1000 ℃ for 2 to 20 hours to obtain a Ti-HMS catalyst matrix taking magnesium-containing compound modified nano carbon fiber as a carrier;
c) Treating Ti-HMS catalyst parent body with organosilicon solution at 25-300 deg.c for 0.5-100 hr; the usage amount of the organic silicon is 10% -70% of the weight of the Ti-HMS catalyst matrix; and then filtering and separating out a solid catalyst, washing the solid catalyst by using an inert solvent, and baking the solid catalyst for 10-24 hours in an environment with the pressure of 0.133-1.33 KPa and the temperature of 80-200 ℃ to prepare the magnesium compound modified Ti-HMS/nano carbon fiber composite catalyst.
2. The composite catalyst according to claim 1, wherein: in the step a), the silicon source is one or two of orthosilicate or alkyl silicate; the titanium source is titanate; the template agent is of the general formula RNH 2 R is a chain alkyl group of 6 to 18 carbon atoms; RNH (RNH) 2 And Si in the silicon source in a molar ratio of 0.01 to 0.3:1, the molar ratio of Si in the silicon source to Ti in the titanium source being 5: 1-200:1, wherein the molar ratio of water to silicon source is 4-20:1, the volume ratio of alcohol to silicon source is 1-4:1, and the molar ratio of nano carbon fiber to silicon source is 5-20:1.
3. The composite catalyst according to claim 1, wherein: in step a), the carbon nanofibers are produced from carbon-containing gas sources CO, CH 4 、C 2 H 6 、C 3 H 8 Any one of the elements is used as a reaction raw material, any one of single metal elements or a plurality of element alloys in Fe, co and Ni of the VIII group of the periodic table is used as a catalyst, the carbon-containing gas source is used for catalytic cracking reaction to form the nano carbon fiber, and the catalytic growth temperature of the nano carbon fiber is 550-650 ℃.
4. The composite catalyst according to claim 1, wherein: in step b), the Ti-HMS loaded by the nano carbon fiber and the magnesium-containing compound are dissolved in waterThe volume ratio of the liquid is 1:1 to 1:3, mgO, mg (OH) 2 、MgCO 3 、4MgCO 3 ·Mg(OH) 2 ·5H 2 The mole ratio of any one or a mixture of more than one of O and dolomite to the silicon source used in the step a) is 0.01:100-3: 100; the roasting temperature is 400-800 ℃ and the roasting time is 3-8 hours.
5. The composite catalyst according to claim 1, wherein: in step c), the organosilicon solution is used, and the organosilicon is selected from any one of halosilanes, silazanes or silylamines.
6. The application of the magnesium compound modified Ti-HMS/nano carbon fiber composite catalyst in the reaction of preparing dicyclopentadiene dioxide by catalytic oxidation of dicyclopentadiene DCPD according to claim 1.
7. The use according to claim 6, characterized in that: the application method comprises the following steps: dicyclopentadiene DCPD is used as a reaction raw material, organic peroxide is used as an oxidant, a nonpolar compound inert to a reaction system is used as a solvent, and the DCPD undergoes catalytic oxidation reaction under the action of a Ti-HMS/nano carbon fiber composite catalyst modified by a magnesium-containing compound to generate dicyclopentadiene dioxide; wherein:
the oxidant is selected from any one of benzoyl peroxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide or cumene hydroperoxide; the inert solvent is selected from any one of benzene, toluene, ethylbenzene, cumene, acetone or petroleum ether; the catalytic oxidation reaction temperature is 50-150 ℃, the pressure gauge pressure is 0-10 MPa, the molar ratio of the organic peroxide to DCPD is 6:1-2:1, and the volume ratio of the inert solvent to the DCPD is 10:1-30:1.
8. The use according to claim 6, characterized in that: the catalytic oxidation reaction temperature is 60-100 ℃, the pressure gauge pressure is 0.3-2 MPa, and the molar ratio of the organic peroxide to DCPD is 3:1-2:1.
9. According toThe use according to claim 6, characterized in that: the catalytic oxidation reaction adopts an intermittent reaction process or a fixed bed continuous reaction process; the batch reaction process is adopted, and the mass ratio of the catalyst to DCPD is 0.01: 100-20: 100, the reaction time is 2-10 hours; adopting a fixed bed continuous reaction process, wherein the volume space velocity of the total material is 0.1-3 h -1 。
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