CN114057620A

CN114057620A - Method and system for preparing hydrogen peroxide cyclopentylbenzene by cyclopentene

Info

Publication number: CN114057620A
Application number: CN202010774059.1A
Authority: CN
Inventors: 李安; 夏金魁; 刘坤; 肖哲; 邱旭; 周从山
Original assignee: China Petroleum and Chemical Corp; Sinopec Baling Co
Current assignee: China Petroleum and Chemical Corp; Sinopec Baling Co
Priority date: 2020-08-04
Filing date: 2020-08-04
Publication date: 2022-02-18

Abstract

The invention relates to the field of chemical industry, and discloses a method and a system for preparing hydrogen peroxide cyclopentylbenzene by cyclopentene, wherein the method comprises the following steps: carrying out diolefin hydrotreating on an aromatic alkylation raw material, then carrying out aralkyl alkylation to obtain a material containing cyclopentylbenzene, removing impurities from the material containing cyclopentylbenzene, and then carrying out peroxidation to obtain hydrogen peroxide cyclopentylbenzene; wherein, the mode of edulcoration includes: and (3) carrying out at least one treatment of water washing, dehydration, desulfurization and dechlorination on the material containing the cyclopentylbenzene to obtain the material after impurity removal. The method can also improve the yield of the hydrogen peroxide cyclopentylbenzene.

Description

Method and system for preparing hydrogen peroxide cyclopentylbenzene by cyclopentene

Technical Field

The invention relates to the field of chemical industry, in particular to a method and a system for preparing hydrogen peroxide cyclopentylbenzene from cyclopentene.

Background

Phenol is an important compound in chemical industry, and can be used for preparing chemical products and intermediates such as phenolic resin, caprolactam, bisphenol A, salicylic acid, picric acid, pentachlorophenol, 2,4-D, adipic acid, phenolphthalein n-acetoacetoxy aniline and the like, and has important application in the industries such as chemical raw materials, alkylphenol, synthetic fibers, plastics, synthetic rubber, medicines, pesticides, spices, dyes, coatings, oil refining and the like. In addition, phenol can be used as a solvent, an experimental reagent and a disinfectant, and the protein on the chromosome in the plant cell can be separated from the DNA by the aqueous solution of the phenol, so that the DNA can be conveniently dyed. At present, the cumyl benzene method which is a common route for producing phenol is traditionally used, and cyclopentanone is also produced by adipic acid condensation or cyclopentene hydration. The methods can only produce phenol or cyclopentanone singly, and have the problems of low economic benefit of production, serious corrosion of acid used in the production process to equipment and the like. The high-value phenol and cyclopentanone can be simultaneously produced from the cyclopentylbenzene through the processes of peroxidation and acidolysis, the atom utilization rate reaches 100%, and the route has high economic value.

In the process of preparing cyclopentylbenzene hydroperoxide from cyclopentene, impurities present in the reaction mass may inhibit the generation of free radicals during the peroxidation process, ultimately affecting the conversion and selectivity of the target product. Therefore, it is of great significance to purify the reaction raw materials.

Disclosure of Invention

In order to solve the problem that the yield of the cyclopentylbenzene hydroperoxide is low due to impurities in reaction raw materials when the cyclopentene is used for preparing the cyclopentylbenzene hydroperoxide, the invention provides a method and a system for preparing the cyclopentylbenzene hydroperoxide from the cyclopentene, and the method can effectively improve the yield of the cyclopentylbenzene hydroperoxide.

In order to achieve the above object, a first aspect of the present invention provides a method for preparing cyclopentylbenzene hydroperoxide from cyclopentene, comprising: carrying out diolefin hydrotreating on an aromatic alkylation raw material, then carrying out aralkyl alkylation to obtain a material containing cyclopentylbenzene, removing impurities from the material containing cyclopentylbenzene, and then carrying out peroxidation to obtain hydrogen peroxide cyclopentylbenzene;

wherein, the mode of edulcoration includes: and (3) carrying out at least one treatment of water washing, dehydration, desulfurization and dechlorination on the material containing the cyclopentylbenzene to obtain the material after impurity removal.

The second aspect of the present invention provides a system for preparing cyclopentylbenzene hydroperoxide from cyclopentene, comprising:

the hydrogenation unit is used for carrying out diene hydrogenation treatment on the aromatic alkylation raw material to obtain a hydrogenated material;

an aralkylation unit for aralkylating cyclopentene to obtain a material containing cyclopentylbenzene;

the impurity removal unit is used for removing impurities from the raw material containing the cyclopentylbenzene to obtain a material after impurity removal;

the peroxidation unit is used for carrying out peroxidation on the cyclopentylbenzene to obtain hydrogen peroxide cyclopentylbenzene;

wherein, the edulcoration unit contains at least one of washing module, dehydration module, desulfurization module and dechlorination module.

The method can effectively reduce the content of various impurities in the reaction raw materials, improve the catalytic activity and the service cycle of the aralkyl catalyst, greatly reduce the production cost and improve the production efficiency.

The method can also improve the yield of the hydrogen peroxide cyclopentylbenzene prepared from the cyclopentene.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In the research process, the inventor of the invention finds that impurities in an aralkylation raw material obviously influence the subsequent process of preparing the cyclopentylbenzene hydroperoxide by peroxidation of the cyclopentylbenzene in the process of preparing the cyclopentylbenzene hydroperoxide by utilizing cyclopentene, and experiments prove that the yield of the cyclopentylbenzene hydroperoxide can be remarkably improved by directly hydrogenating and removing the impurities from the aralkylation raw material before the aralkylation, and then removing the impurities before the peroxidation.

The invention provides a method for preparing hydrogen peroxide cyclopentylbenzene by cyclopentene, which comprises the following steps: carrying out diolefin hydrotreating on an aromatic alkylation raw material, then carrying out aralkyl alkylation to obtain a material containing cyclopentylbenzene, removing impurities from the material containing cyclopentylbenzene, and then carrying out peroxidation to obtain hydrogen peroxide cyclopentylbenzene;

In the present invention, the aralkylation starting material may be a cyclopentene-containing starting material, or a cyclopentene-and-benzene-containing starting material, and preferably a cyclopentene-containing starting material, and in the preferred case, the yield of cyclopentylbenzene hydroperoxide can be increased.

For example, when the aralkylation feed is a cyclopentene-containing feed, the cyclopentene-containing feed may be subjected to diolefin hydrogenation first, and then the hydrogenated material and benzene may be subjected to aralkylation. When the aralkylation feed is a feed containing cyclopentene and benzene, the feed containing cyclopentene and benzene may be subjected to diolefin hydrotreatment and aralkylation in this order.

In the present invention, the cyclopentene-containing raw material may contain at least one of cyclopentadiene, a sulfur-containing compound, a nitrogen-containing compound, a chlorine-containing compound, and an oxygen-containing compound in addition to cyclopentene.

Preferably, the content of impurities in the cyclopentene-containing raw material is 500ppm or more, and may be, for example, 500ppm or more, 1000ppm or more, 2000ppm or more, 3000ppm or more, 4000ppm or more, 5000ppm or more, 6000ppm or more, 7000ppm or more, 8000ppm or more, 9000ppm or more, 10000ppm or more, or the like.

Preferably, the content of the cyclopentadiene in the cyclopentene-containing raw material is 500-10000ppm, more preferably 500-5000 ppm.

In the present invention, the sulfur-containing compound may be a sulfur-containing compound that is conventional in the art, and may be, for example, mercaptan, thiophenol and hydrogen sulfide.

Preferably, the amount of the sulfur-containing compound in the cyclopentene-containing feedstock is 0 to 2000ppm, more preferably 0 to 1000 ppm.

In the present invention, the nitrogen-containing compound may be a nitrogen-containing compound conventional in the art, and may be, for example, pyridine, acridine, indole and carbazole.

Preferably, the content of the nitrogen-containing compound in the cyclopentene-containing raw material is 0 to 3000ppm, more preferably 0 to 2000 ppm.

In the present invention, the chlorine-containing compound may be a chlorine-containing compound conventional in the art, and may be, for example, hydrogen chloride, organochlorine, chlorocyclopentane, etc.

Preferably, the content of the chlorine-containing compound in the cyclopentene-containing raw material is 0 to 5000ppm, more preferably 0 to 2500 ppm.

In the present invention, the oxygen-containing compound may be an oxygen-containing compound which is conventional in the art, and may be, for example, organic acids, phenols and ketones.

Preferably, the amount of the oxygen-containing compound in the cyclopentene-containing feedstock is 0 to 3000ppm, more preferably 0 to 2000 ppm.

In the present invention, the content of cyclopentadiene is measured by mass spectrometry; the content of the nitrogen-containing compound is measured by mass spectrometry; the content of the oxygen-containing compound is measured by mass spectrometry; the content of the sulfur-containing compound is measured by mass spectrometry; the content of the chlorine-containing compound was determined by mass spectrometry.

In the present invention, the purpose of the diene hydrogenation is to convert cyclopentadiene to cyclopentene.

In the present invention, preferably, the diene hydrotreating mode includes: and contacting the aralkylation raw material with hydrogen in the presence of a diene selective hydrogenation catalyst to obtain a hydrogenated material.

Preferably, the cyclopentadiene content in the hydrogenated material is below 100ppm, more preferably below 50ppm, based on the total weight of the hydrogenated material. Within the preferred ranges, the selectivity and yield of the aromatic alkylation reaction can be effectively improved.

In the present invention, the diene selective hydrogenation catalyst may be a hydrogenation catalyst conventionally used in the art, and preferably, the diene selective hydrogenation catalyst comprises an active component palladium and a first carrier, wherein the active component palladium is contained in an amount of 0.1 to 3 wt% based on the total weight of the diene selective catalyst.

In the present invention, the first carrier may be a first carrier conventionally used in the art, and preferably, the first carrier is selected from at least one of calcium carbonate, activated carbon, barium sulfate, montmorillonite, zeolite, and sepiolite.

In the present invention, the diolefin selective hydrogenation catalyst can be obtained commercially or can be obtained by self-production. The preparation method of the diolefin selective hydrogenation catalyst can be a preparation method which is conventional in the field, and is not described in detail herein.

In the present invention, the hydrogenation conditions may be conditions conventionally used in the art, and preferably, the hydrogenation conditions include: the temperature is 50-90 deg.C, and the pressure is 0.2-2 MPa.

In the present invention, the amount of the hydrogen may be selected within a wide range, and preferably, the molar ratio of the cyclopentene to the hydrogen is 1:0.02 to 0.2 on a pure basis.

Preferably, the mass space velocity in the diene hydrotreating process is 0.5-10h^-1。

In the present invention, the mass space velocity is the mass space velocity of the raw materials fed to the reactor, and is not particularly limited, and it means the mass space velocity of the aralkylation raw material (which may be a cyclopentene raw material or a raw material of cyclopentene and benzene) and hydrogen.

Subjecting the hydrogenated feedstock to aralkylation, preferably in a manner comprising: the hydrogenated material is subjected to aralkylation in the presence of an aralkylation catalyst to obtain a cyclopentylbenzene-containing material.

In the present invention, the aralkylation catalyst may be an aralkylation catalyst conventionally used in the art, and preferably, the aralkylation catalyst is a solid acid catalyst and/or an ionic liquid catalyst.

In the present invention, the solid acid catalyst may be a solid acid catalyst conventionally used in the art, and preferably, the solid acid catalyst is selected from AlCl₃At least one of H beta molecular sieve, MCM-22 molecular sieve and HUSY molecular sieve.

In the present invention, the ionic liquid catalyst may be an ionic liquid catalyst conventionally used in the art, and preferably, the ionic liquid catalyst is at least one selected from the group consisting of 1-ethylpyridine aluminum trichloride ionic liquid, 1-methyl-3-alkylimidazole aluminum trichloride ionic liquid, and 1-butylpyridine aluminum trichloride ionic liquid.

In the present invention, preferably, the aralkylation catalyst is selected from AlCl₃At least one of H beta molecular sieve and 1-ethyl pyridine aluminum trichloride ionic liquid.

In the present invention, the aralkylation catalyst can be obtained commercially.

In the present invention, the mass space velocity of the total material can be selected in a wide range, and preferably, the mass space velocity is 0.05-3h^-1More preferably 0.1 to 2 hours^-1。

It is to be understood that the total feed herein is the sum of the cyclopentene feedstock (hydrotreated) and the benzene feedstock (with or without hydrotreating) passed to the aralkylation unit.

In the present invention, the molar ratio of benzene to cyclopentene can be selected from a wide range, and preferably is 2 to 10:1, for example, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, and any range between any two values, and more preferably 4 to 7: 1. It is understood that the theoretical values of benzene and cyclopentene are used here.

In the present invention, the conditions for the aralkylation may be conditions conventional in the art, and include: the temperature is 50-180 ℃, and more preferably 80-150 ℃; the pressure is 0.1 to 3MPa, more preferably 0.5 to 2 MPa.

In the present invention, the pressure refers to gauge pressure unless otherwise specified.

In the invention, the cyclopentyl benzene hydroperoxide is obtained by removing impurities from the material containing the cyclopentyl benzene and then carrying out peroxidation. Wherein, the mode of edulcoration includes: and (3) carrying out at least one treatment of water washing, dehydration, desulfurization and dechlorination on the material containing the cyclopentylbenzene to obtain the material after impurity removal.

Wherein the purpose of water washing is to remove oxygen-containing compounds and/or nitrogen-containing compounds which can be dissolved in water; the purpose of dehydration is to remove the water mixed in the water washing process; the purpose of desulfurization is to remove sulfur-containing compounds; the purpose of dechlorination is to remove chlorine-containing compounds.

In the present invention, the manner of the water washing treatment may be a manner conventionally used in the art, and preferably, the manner of the water washing treatment includes: the washing conditions are such that the nitrogen-containing compound content in the washed material is 100ppm or less, more preferably 50ppm or less, and may be, for example, 50ppm or less, 40ppm or less, 30ppm or less, 20ppm or less, 10ppm or less, and still more preferably 20ppm or less.

In the present invention, the washing conditions may be those conventional in the art, and preferably, the washing temperature is 20 to 50 ℃ and the volume ratio of the material to be washed and water is 1:5 to 15.

Preferably, the water washing is performed in a water washing column.

In the present invention, the conditions and manner of dehydration may be conventional in the art, and preferably, the manner of dehydration treatment includes: the dehydration is carried out in the presence of a dehydrating molecular sieve under conditions such that the water content of the dehydrated material is 600ppm or less, more preferably 200ppm or less, and for example, may be 200ppm or less, 100ppm or less, 80ppm or less, 60ppm or less, 40ppm or less, 20ppm or less, 10ppm or less, and more preferably 20ppm or less.

In the present invention, the water content may be measured by an electrometric method.

Preferably, the conditions for dehydration include: the temperature is 20-45 ℃, the pressure is 0.1-0.7MPa, and the mass space velocity is 5-20h^-1。

Preferably, the dehydration is carried out in a dehydration column.

Preferably, the dehydrated molecular sieve may be one conventionally used in the art, and preferably, the dehydrated molecular sieve is selected from at least one of 4A molecular sieve, 3A molecular sieve, and 5A molecular sieve; more preferably, the dehydrated molecular sieve is UOP4A molecular sieve.

The dehydrated molecular sieve is commercially available and will not be described in detail herein.

In the present invention, the desulfurization treatment may be performed in a manner conventionally used in the art, and preferably, the desulfurization treatment includes: the desulfurization is carried out in the presence of a desulfurization adsorbent, and the desulfurization condition ensures that the content of sulfur-containing compounds in the desulfurized material is below 100 ppm; more preferably 50ppm or less, for example, 50ppm or less, 40ppm or less, 30ppm or less, 20ppm or less, 10ppm or less, and still more preferably 10ppm or less.

Preferably, the desulfurization is carried out in a desulfurization tower.

In the present invention, the desulfurization adsorbent may be a desulfurization adsorbent conventionally used in the art, and preferably, the desulfurization adsorbent is selected from at least one of a beta-type molecular sieve, a Y-type molecular sieve, a USY-type molecular sieve, a ZSM-5 molecular sieve, mordenite, an MCM-41 molecular sieve, and an SBA-15 molecular sieve.

Preferably, the desulfurization adsorbent is a copper-loaded desulfurization adsorbent, and can be a Cu/beta type molecular sieve, a Cu/Y type molecular sieve, a Cu/USY type molecular sieve and the like.

Preferably, the loading of copper in the desulfurization adsorbent is 3 to 30 wt%.

The desulfurization adsorbent is commercially available and will not be described in detail herein.

In the present invention, the desulfurization conditions may be those conventional in the art, and preferably, the desulfurization conditions include: the temperature is 20-50 ℃, the pressure is 0.6-2MPa, and the mass space velocity is 0.25-4h^-1。

In the present invention, the dechlorination may be a method conventionally used in the art, and preferably, the dechlorination comprises: the dechlorination is carried out in the presence of a dechlorination adsorbent, and the dechlorination condition ensures that the content of chlorine-containing compounds in dechlorinated materials is below 70 ppm; more preferably 40ppm or less, for example, 40ppm or less, 30ppm or less, 20ppm or less, 10ppm or less, and still more preferably 10ppm or less.

Preferably, the dechlorination is carried out in a dechlorination column.

In the present invention, the dechlorination adsorbent may be a dechlorination adsorbent conventionally used in the art, and preferably, the dechlorination adsorbent is selected from at least one of an X-type molecular sieve, a Y-type molecular sieve, an MOR-type molecular sieve, activated carbon, and an MCM-41 molecular sieve.

Preferably, the dechlorination adsorbent is Na₂CO₃The supported dechlorination adsorbent may be, for example, Na₂CO₃Molecular sieve type/X, Na₂CO₃Y type molecular sieve, Na₂CO₃Molecular sieves of the/MOR type, etc.

Preferably, Na in the dechlorination adsorbent₂CO₃The amount of (B) is 5 to 25% by weight.

Preferably, the dechlorination adsorbent is an X-type molecular sieve modified by potassium carbonate.

The dechlorination adsorbent may be commercially available and will not be described in detail herein.

In the present invention, the dechlorination conditions may be conditions conventional in the art, and preferably, the dechlorination conditions include: the temperature is 20-50 deg.CThe pressure is 0.6-2MPa, and the mass space velocity is 0.25-5h^-1。

In a preferred embodiment of the present invention, the removing of the impurities comprises: and sequentially washing and dehydrating the material containing the cyclopentylbenzene to obtain a dehydrated material, desulfurizing the dehydrated material to obtain a desulfurized material, and dechlorinating the desulfurized material to obtain an impurity-removed material. The removal of impurities in the preferred manner can further increase the yield of cyclopentylbenzene hydroperoxide.

In the present invention, the peroxidation may be a conventional one used in the art, and preferably, the peroxidation includes: mixing a peroxidation catalyst, the materials after impurity removal and an optional initiator to obtain a homogeneous solution, introducing oxygen-containing gas into the homogeneous solution, and carrying out peroxidation at 50-130 ℃ to obtain the hydrogen peroxide cyclopentylbenzene.

In the present invention, the step of peroxidation is preferably a batch reaction.

In the present invention, the peroxidation of cyclopentylbenzene can be carried out at 50-130 deg.C, preferably 85-120 deg.C, such as 85, 90, 95, 100, 105, 110, 120 deg.C, and any range between any two values. Within the preferred ranges, higher cyclopentylbenzene conversion and cyclopentylbenzene hydroperoxide selectivity and yield can be achieved.

In the present invention, the time of the peroxidation may not be particularly limited, and preferably, the time of the peroxidation is 2 to 24 hours, more preferably 8 to 15 hours.

In the present invention, the peroxidation catalyst may be a peroxidation catalyst conventionally used in the art, and preferably, the peroxidation catalyst is selected from the group consisting of imine and N-OH-containing compounds.

Preferably, the peroxidation catalyst is selected from the group consisting of N-hydroxyphthalimide, 4-amino-N-hydroxyphthalimide, 3-amino-N-hydroxyphthalimide, tetrabromo-N-hydroxyphthalimide, tetrachloro-N-hydroxyphthalimide, N-hydroxychloroimides, N-hydroxycedrinimides, N-hydroxytricotriimides, N-hydroxyphenyl-1, 2, 4-trimethylimides, N '-dihydroxy (pyromellitimide), N' -dihydroxy (benzophenone-3, 3',4,4' -tetracarboxydiimides), N-hydroxymaleimide, pyridine-2, 3-dicarboximide, pyridine-3-dicarboximide, and mixtures thereof, N-hydroxysuccinimide, N-hydroxy (tartrimide), N-hydroxy-5-norbornene-2, 3-dicarboximide, exo-N-hydroxy-7-oxabicyclo [2.2.1] hept-5-ene-2, 3-dicarboximide, N-hydroxy-cis-cyclohexane-1, 2-dicarboximide, N-hydroxy-cis-4-cyclohexene-1, 2-dicarboximide, the sodium salt of N-hydroxynaphthalimide, N-hydroxy-o-benzenedisulfonimide, and at least one of N, N', N "-trihydroxyisocyanuric acid, more preferably N-hydroxyphthalimide (NHPI). Under the preferred conditions, the effect of peroxidation can be enhanced.

In the present invention, the amount of the peroxidation catalyst can be selected from a wide range, and preferably, the peroxidation catalyst is used in an amount of 0.01 to 10 wt%, based on the weight of the cyclopentylbenzene, such as 0.01, 0.02, 0.05, 0.08, 0.1, 0.2, 0.5, 0.8, 1,2, 5, 8, 10 wt% and any range between any two values, preferably 0.05 to 0.5 wt%.

For example, it may be a peroxide initiator or an azo initiator, preferably, the initiator is a peroxide initiator.

In the present invention, the peroxide initiator may be a peroxide initiator conventionally used in the art, and is preferably at least one selected from the group consisting of a hydroperoxy type initiator, a diacyl peroxide type initiator, a dialkyl peroxide type initiator, a diester peroxide type initiator, and a peroxy organic acid/ketone initiator, and more preferably a hydroperoxy type initiator.

In the present invention, the hydroperoxy initiator is preferably at least one selected from the group consisting of cyclopentylbenzene hydroperoxide, tert-butyl hydroperoxide, cyclopentyl-1-phenyl-1-hydroperoxide, cyclohexyl-1-phenyl-1-hydroperoxide, pinane hydroperoxide, 1,3, 3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide.

In the present invention, it is preferable that the diacyl peroxide initiator is at least one selected from the group consisting of dibenzoyl peroxide, di-4-chlorobenzoyl peroxide, di-2, 4-dichlorobenzoyl peroxide, dibenzoyl peroxide and di-4-chlorobenzoyl peroxide.

In the present invention, preferably, the dialkyl peroxide initiator is selected from the group consisting of 1, 1-bis- (t-butylperoxy) cyclohexane, 1-bis- (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 2-dihydroperoxy propane, 2, 5-dimethyl-2, 5-bis- (benzoylperoxy) hexane, 3,6,6,9, 9-hexamethyl-1, 2,4, 5-tetraoxacyclononane, 1-bis- (t-amylperoxy) cyclohexane, 2-bis- (t-butylperoxy) butane, 1-bis- (t-butylperoxy) cyclohexane, 1-bis- (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 1,3, 5-dimethylcyclohexane, and mixtures thereof, 1, 1-bis- (tert-butylperoxy) cyclohexane, 2-bis- (tert-butylperoxy) propane, 1-bis- (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-bis- (tert-butylperoxy) hexane, at least one of 2, 5-dimethyl-2, 5-bis- (3,3, 5-trimethylhexanoylperoxy) hexane, 3,6,6,9, 9-hexamethyl-1, 2,4, 5-tetraoxacyclononane, 3,6, 9-triethyl-3, 6, 9-trimethyl-1, 4, 7-triperoxyloxane, di- (2-tert-butylperoxyisopropyl) benzene and tert-butylcumyl peroxide.

In the present invention, it is preferred that the peroxydiester initiator is selected from the group consisting of t-amyl peroxy-3, 5, 5-trimethylhexanoate, t-butyl peroxyacetate, t-butyl monoperoxymaleate, t-butyl monoperoxyphthalate, t-amyl peroxybenzoate, n-butyl 4, 4-bis- (t-butylperoxy) valerate, t-butyl monoperoxymaleate, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-butyl peroxyisopropylcarbonate, t-butyl peroxy-2-methylbenzoate, ethyl 3, 3-bis- (t-butylperoxy) butyrate, di-t-butyl peroxyazelate, di- (t-butylperoxy) phthalate, ethyl 3, 3-bis- (t-amylperoxy) butyrate, ethyl 3, 3-bis- (t-butylperoxy) butyrate and 1, at least one of 1,3, 3-tetramethyl butyl peroxyneodecanoate.

In the present invention, preferably, the peroxy organic acid/ketone initiator is selected from at least one of peracetic acid, 3-chloroperoxybenzoic acid, disuccinic acid peroxide, diperoxydodecanedioic acid, methyl ethyl ketone peroxide, methyl ethyl (meth) ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide and cyclohexanone peroxide.

In the present invention, the azo initiator may be an azo initiator conventionally used in the art, and preferably, it is perazodiisobutyronitrile and/or perazodiisoheptonitrile.

In the present invention, most preferably, the initiator is cyclopentylbenzene hydroperoxide. The use of cyclopentylbenzene hydroperoxide as an initiator can increase the selectivity of cyclopentylbenzene hydroperoxide compared to other initiators.

In the present invention, the amount of the initiator can be selected within a wide range, and preferably, the amount of the initiator is 0 to 10% by weight, based on the weight of cyclopentylbenzene, such as 0, 0.01, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1,2, 3, 4,5, 6, 7, 8, 9, 10% by weight and any range between any two values, preferably 0.01 to 5% by weight. Within the above preferred range, the effect of peroxidation can be enhanced.

In the present invention, the weight of cyclopentylbenzene is theoretical.

In the present invention, the oxygen-containing gas used may be a gas containing oxygen as is conventional in the art, such as air, pure oxygen, or a mixture of oxygen and other gases, and the kind thereof is not particularly limited. Preferably, the concentration of oxygen in the oxygen-containing gas is from 20 to 100% by volume.

In the present invention, the amount of the oxygen-containing gas to be used may be selected from a wide range, and preferably, the volume of the oxygen-containing gas introduced per mole of cyclopentylbenzene is 0.2 to 8L/(min. mol), for example, 0.2, 0.4, 0.6, 0.8, 1,2, 3, 4,5, 6, 7, 8L/(min. mol), and any range consisting of any two values. Within the preferred ranges, higher cyclopentylbenzene conversion and cyclopentylbenzene hydroperoxide selectivity and yield can be achieved.

In the invention, the hydrogenation and impurity removal method can also be used for the hydrogenation and impurity removal process of other materials containing the impurities. It is understood that cyclopentadiene can be other kinds of diene compounds in the case of different raw materials.

The operation manner and conditions of the system have been described in detail in the first aspect, and are not described herein again.

It should be understood that the temperature and pressure involved in the present invention may fluctuate in temperature or pressure during actual operation, for example, the temperature may fluctuate by 3 ℃ or higher and the pressure may fluctuate by 0.1MPa or higher.

The present invention will be described in detail below by way of examples.

In the following examples, the water content was measured by electrometric method;

the content of cyclopentadiene is measured by mass spectrometry;

the content of the nitrogen-containing compound is measured by mass spectrometry;

the content of the oxygen-containing compound is measured by mass spectrometry;

the content of the sulfur-containing compound is measured by mass spectrometry;

the content of the chlorine-containing compound is measured by mass spectrometry;

the contents of cyclopentylbenzene and cyclopentylbenzene hydroperoxide were determined by gas chromatography analysis.

Each reagent and material is commercially available without specific mention.

In the following examples, the cyclopentene starting material contained 3000ppm of cyclopentadiene, 1200ppm of an oxygen-containing compound, 1100ppm of a nitrogen-containing compound, 1400ppm of water, 800ppm of a sulfur-containing compound and 2100ppm of a chlorine-containing compound, with the balance being cyclopentene. It is understood that the impurity level in the cyclopentene starting material may fluctuate, but may fluctuate within a range of up to and down 100ppm, and may fluctuate within a range of up to and down 50ppm for the sulfur-containing compound content.

In the following examples, the molecular sieves used were purchased from the institute of petrochemical science, of the company, limited, petrochemical industries, China.

Preparation example

Adding appropriate amount of Na₂PdCl₄Dissolving in water to form a homogeneous solution; then adding calcium carbonate with the weight 3 times that of water into the solution at room temperature, stirring for 12 hours at room temperature, washing, drying, and roasting for 5 hours at 400 ℃; and finally, treating for 4 hours at 400 ℃ in a hydrogen atmosphere to obtain the diolefin selective hydrogenation catalyst. Adjusting Na₂PdCl₄The dosage of the catalyst is that the content of Pd in the diolefin selective hydrogenation catalyst is respectively 0.5 weight percent and 1.0 weight percent, and 0.5 weight percent Pd/CaCO is respectively obtained₃Catalyst and 1 wt% Pd/CaCO₃A catalyst.

Example 1

This example illustrates the preparation of cyclopentylbenzene hydroperoxide from cyclopentene

(1) Hydrogenation of

The cyclopentene raw material is preheated by a preheater after being matched with hydrogen, and then is sent to a selective hydrogenation reactor at 0.5 wt% Pd/CaCO₃Hydrotreating is carried out in the presence of a catalyst. Wherein the mol ratio of cyclopentene to hydrogen is 1: 0.1, the hydrogenation temperature is 75 ℃, the hydrogen pressure is maintained at 0.3MPa, and the mass space velocity is 3h^-1。

The cyclopentadiene content of the hydrotreated material was determined, and the specific results are shown in table 1.

(2) Aralkylation

Taking the hydrogenated material obtained in the step (1) and benzene as reaction raw materials, and adding AlCl₃And (3) carrying out an aromatic alkylation reaction in the presence of the benzene to obtain a material containing cyclopentyl benzene. Wherein the molar ratio of benzene to cyclopentene is 6:1, the temperature of the reaction is 120 ℃; the reaction pressure is 0.5 MPa; the mass space velocity is 0.5h^-1。

The cyclopentene conversion and the cyclopentylbenzene yield of the material obtained by the reaction were measured and calculated, and the specific results are shown in table 2.

(3) Removing impurities

Feeding the material containing the cyclopentylbenzene into a water washing tower, wherein the water washing temperature is 40 ℃, and the material/water volume ratio is 1: 10; the material from the water washing tower is sent into a dehydration tower to contact with a 4A molecular sieve, the dehydration temperature is 30 ℃, the pressure is 0.5MPa, and the mass space velocity is 10h^-1。

The material from the dehydration tower is sent into a desulfurization tower to contact with a Cu/beta type molecular sieve, wherein the desulfurization temperature is 20 ℃, the pressure is 0.6MPa, and the mass space velocity is 0.25h^-1. Wherein the loading of copper in the Cu/beta type molecular sieve is 20 weight percent.

The material discharged from the desulfurizing tower is sent into a dechlorinating tower and Na₂CO₃Contacting with/X type molecular sieve, dechlorinating to obtain material with impurity removed, wherein the dechlorinated compound temperature is 20 deg.C, pressure is 0.7MPa, and mass space velocity is 0.3h^-1. Wherein, Na₂CO₃Na in/X type molecular sieve₂CO₃The loading of (b) was 15 wt%.

The impurity content of the material after impurity removal is measured, and the specific results are shown in table 1.

(4) Peroxidation of

Uniformly mixing the impurity-removed material obtained in the step (2) with cumene hydroperoxide, wherein the dosage of the cumene hydroperoxide is 1.0 percent of the weight of the impurity-removed material; then heating the mixture to react at 120 ℃; simultaneously blowing air into the reaction solution; the volume of oxygen-containing gas introduced per mole of cyclopentylbenzene per minute was 4L/(min. mol), and the reaction was continued for 8 hours.

The conversion of cyclopentylbenzene in the reaction mass and the yield of cyclopentylbenzene hydroperoxide were determined and calculated, and the specific results are shown in Table 3.

Example 2

(1) Hydrogenation of

Mixing cyclopentene raw material and benzene (the molar ratio of benzene to cyclopentene is 6: 1) with hydrogen, preheating by preheater, and feeding into selective hydrogenation reactor at 1 wt% Pd/CaCO₃Hydrotreating is carried out in the presence of a catalyst. Wherein the mol ratio of cyclopentene to hydrogen is 1: 0.05, the hydrogenation temperature is 55 ℃, the hydrogen pressure is maintained to be 0.8MPa, and the mass space velocity is 8h^-1。

(2) Aralkylation

And (2) taking the hydrogenated material obtained in the step (1) as a reaction raw material, and carrying out an aromatic alkylation reaction in the presence of an H beta molecular sieve to obtain a material containing cyclopentylbenzene. Wherein the reaction temperature is 150 ℃; the reaction pressure is 0.5 MPa; the mass space velocity is 1.2h^-1。

(3) Removing impurities

Feeding the material containing the cyclopentylbenzene into a water washing tower, wherein the water washing temperature is 20 ℃, and the material/water volume ratio is 1: 5; the material from the water washing tower is sent into a dehydration tower to contact with a 3A molecular sieve, the dehydration temperature is 35 ℃, the pressure is 0.4MPa, and the mass space velocity is 20h^-1。

Feeding the material from the dehydrating tower into a desulfurizing tower to contact with a Cu/Y type molecular sieve, wherein the desulfurizing temperature is 20 ℃, the pressure is 1.8MPa, and the mass space velocity is 0.25h^-1. Wherein the loading amount of copper in the Cu/Y type molecular sieve is 15 weight percent.

The material discharged from the desulfurizing tower is sent into a dechlorinating tower and Na₂CO₃Contacting with/X type molecular sieve, dechlorinating to obtain material with impurity removed, wherein the dechlorinated compound temperature is 20 deg.C, pressure is 0.8MPa, and mass space velocity is 0.3h^-1. Wherein, Na₂CO₃Type X isNa in the sub-sieve₂CO₃The loading of (b) was 20 wt%.

(4) Peroxidation of

Peroxidation was carried out as described in step (4) of example 1.

Example 3

(1) Hydrogenation of

Hydrogenation was carried out as described in step (1) of example 2, except that the molar ratio of benzene to cyclopentene was 8: 1. the cyclopentadiene content of the hydrotreated material was determined, and the specific results are shown in table 1.

(2) Aralkylation

The aralkylation was carried out as described in step (1) of example 2 to give a cyclopentylbenzene-containing material. The cyclopentene conversion and the cyclopentylbenzene yield of the material obtained by the reaction were measured and calculated, and the specific results are shown in table 2.

(3) Removing impurities

Feeding the material containing the cyclopentylbenzene into a water washing tower, wherein the water washing temperature is 50 ℃, and the material/water volume ratio is 1: 15; the material from the water washing tower is sent into a dehydration tower to contact with a 5A molecular sieve, the dehydration temperature is 32 ℃, the pressure is 0.35MPa, and the mass space velocity is 5h^-1。

Feeding the material from the dehydration tower into a desulfurization tower to contact with a Cu/USY type molecular sieve, wherein the desulfurization temperature is 30 ℃, the pressure is 0.8MPa, and the mass space velocity is 4h^-1. Wherein the loading of copper in the Cu/USY type molecular sieve is 25 weight percent.

The material discharged from the desulfurizing tower is sent into a dechlorinating tower and Na₂CO₃The MOR type molecular sieve is contacted and dechlorinated to obtain a material after impurity removal, wherein the dechlorinated compound temperature is 20 ℃, the pressure is 0.7MPa, and the mass space velocity is 0.3h^-1. Wherein, Na₂CO₃Na in/MOR type molecular sieve₂CO₃The loading of (b) was 10 wt%.

(4) Peroxidation of

Peroxidation was carried out as described in step (4) of example 1.

Example 4

The procedure was followed as described in example 1, except that the washing with water and the dehydration treatment were not carried out.

Example 5

The procedure was followed as in example 3, except that the desulfurization treatment was not carried out.

Example 6

The procedure is as in example 3, except that dechlorination is not carried out.

Comparative example 1

This comparative example illustrates the preparation of cyclopentylbenzene hydroperoxide from a reference cyclopentene

Cyclopentylbenzene hydroperoxide was prepared as described in example 1, except that neither the alkylation feed nor the cyclopentylbenzene-containing feed was hydrotreated or decontaminated.

Comparative example 2

The procedure was followed as in example 1 except that step (3) was carried out before step (2), i.e., the cyclopentene-containing feedstock was subjected to aralkylation after hydrogenation and impurity removal in this order, and then the cyclopentylbenzene-containing feedstock was subjected to peroxidation to obtain cyclopentylbenzene peroxide.

The cyclopentene conversion and the cyclopentylbenzene yield of the material obtained by the reaction were measured and calculated, and the specific results are shown in table 2. The impurity content of the material containing cyclopentylbenzene was determined and the specific results are shown in table 1. The conversion of cyclopentylbenzene in the reaction mass and the yield of cyclopentylbenzene hydroperoxide were determined and calculated, and the specific results are shown in Table 3.

TABLE 1

TABLE 2

Numbering	Conversion of cyclopentene/%)	Cyclopentylbenzene selectivity/%)	Cyclopentyl benzene yield/%)
				Example 1	99.8	99.6	99.4
Example 2	99.8	99.5	99.3
				Example 3	99.6	99.3	98.9
Example 4	99.2	99.0	98.2
				Example 5	99.1	98.5	97.6
Example 6	98.9	98.3	97.2
				Comparative example 1	98.3	97.8	96.1
Comparative example 2	99.9	99.7	99.6

TABLE 3

Numbering	Conversion of cyclopentylbenzene/%)	Cyclopentylbenzene hydroperoxide selectivity/%)	Cyclopentylbenzene hydroperoxide yield/%)
				Example 1	29.6	99.1	29.3
Example 2	29.3	98.8	28.9
				Example 3	28.9	98.5	28.5
Example 4	27.3	96.3	26.3
				Example 5	27.4	96.9	26.6
Example 6	27.5	96.2	26.5
				Comparative example 1	26.6	93.6	24.9
Comparative example 2	27.2	94.8	25.8

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A method for preparing hydrogen peroxide cyclopentylbenzene from cyclopentene is characterized by comprising the following steps: carrying out diolefin hydrotreating on an aromatic alkylation raw material, then carrying out aralkyl alkylation to obtain a material containing cyclopentylbenzene, removing impurities from the material containing cyclopentylbenzene, and then carrying out peroxidation to obtain hydrogen peroxide cyclopentylbenzene;

2. The process of claim 1, wherein the diolefin is hydrotreated in a manner comprising: contacting the aralkylation raw material with hydrogen in the presence of a diene selective hydrogenation catalyst to obtain a hydrogenated material;

preferably, the hydrogenation conditions include: the temperature is 50-90 ℃, and the pressure is 0.2-2 MPa;

preferably, the cyclopentadiene content in the hydrogenated material is less than 100ppm based on the total weight of the hydrogenated material.

3. The process according to claim 2, wherein the diolefin selective hydrogenation catalyst comprises the active components palladium and a first support,

wherein, the content of the active component palladium is 0.1-3 wt% based on the total weight of the dialkene selective catalyst;

preferably, the first carrier is selected from at least one of calcium carbonate, activated carbon, barium sulfate, montmorillonite, zeolite, and sepiolite.

4. The method of any one of claims 1-3, wherein the manner of aralkylation comprises: in the presence of an aralkylation catalyst, performing aralkylation on the hydrogenated material to obtain a material containing cyclopentylbenzene;

preferably, the aralkylation catalyst is a solid acid catalyst and/or an ionic liquid catalyst.

5. The process of any one of claims 1-4, wherein the conditions for aralkylation comprise: the temperature is 50-180 ℃, and more preferably 80-150 ℃; the pressure is 0.1-3MPa, more preferably 0.5-2 MPa; the mass space velocity is 0.05-3h^-1More preferably 0.1 to 2 hours^-1。

6. The method according to any one of claims 1 to 5, wherein the water washing conditions are such that the content of nitrogen-containing compounds in the water-washed material is 100ppm or less and the content of oxygen-containing compounds is 100ppm or less;

preferably, the conditions of the water washing include: the temperature is 20-50 ℃, and the volume ratio of the material to be washed and water is 1: 5-15.

7. The process of any one of claims 1 to 6, wherein the dehydration is carried out in the presence of a dehydrating molecular sieve under conditions such that the water content of the dehydrated material is below 600 ppm;

preferably, the conditions for dehydration include: the temperature is 20-45 ℃, the pressure is 0.1-0.7MPa, and the mass space velocity is 5-20h^-1；

Preferably, the dehydrated molecular sieve is selected from at least one of 4A molecular sieve, 3A molecular sieve and 5A molecular sieve.

8. The method according to any one of claims 1 to 7, wherein the desulfurization is carried out in the presence of a desulfurization adsorbent under conditions such that the content of sulfur-containing compounds in the desulfurized material is 100ppm or less;

preferably, the desulfurization adsorbent is selected from at least one of Cu/beta type molecular sieve, Cu/Y type molecular sieve, Cu/USY type molecular sieve, ZSM-5 molecular sieve, mordenite, MCM-41 molecular sieve and SBA-15 molecular sieve;

preferably, the desulfurization conditions include: the temperature is 20-50 ℃, the pressure is 0.6-2MPa, and the mass space velocity is 0.25-4h^-1。

9. The process of any of claims 1-8, wherein the dechlorination is carried out in the presence of a dechlorination adsorbent under conditions such that the content of chlorine-containing compounds in the dechlorinated material is below 70 ppm;

preferably, the dechlorination adsorbent is selected from Na₂CO₃Molecular sieve type/X, Na₂CO₃Y type molecular sieve, Na₂CO₃At least one of/MOR type molecular sieve, activated carbon and MCM-41 molecular sieve;

preferably, the dechlorination conditions include: the temperature is 20-50 ℃, the pressure is 0.3-1.5MPa, and the mass space velocity is 0.25-5h^-1。

10. The method according to any one of claims 1 to 9, wherein the removing comprises: and sequentially washing and dehydrating the material containing the cyclopentylbenzene to obtain a dehydrated material, desulfurizing the dehydrated material to obtain a desulfurized material, and dechlorinating the desulfurized material to obtain an impurity-removed material.

11. The method of any one of claims 1-10, wherein the peroxidation comprises: mixing a peroxidation catalyst, the materials after impurity removal and an optional initiator to obtain a homogeneous solution, introducing oxygen-containing gas into the homogeneous solution, and carrying out peroxidation at 50-130 ℃ to obtain cyclopentylbenzene hydroperoxide;

preferably, the time of peroxidation is from 2 to 24h, more preferably from 8 to 15 h.

12. The process of claim 11 wherein the peroxidation catalyst is selected from the group consisting of imines or N-OH containing compounds; and/or

The initiator is a peroxide, preferably an organic peroxide;

preferably, the peroxidation catalyst is used in an amount of 0.01 to 10 wt% and the initiator is used in an amount of 0 to 10 wt%, based on the weight of cyclopentylbenzene.

13. A system for preparing cyclopentylbenzene hydroperoxide from cyclopentene, comprising: