Process and system for the preparation of hydroperoxycyclopentylbenzene from cyclopentene

Abstract

The application relates to the chemical industry field and discloses a method and system for preparing hydrogen peroxide cyclopentyl benzene from cyclopentene, which comprises the following steps: obtaining a material containing cyclopentyl benzene by carrying out diene hydrogenation treatment on aralkylation raw materials and then aralkylating; removing impurities from the material containing cyclopentyl benzene; and obtaining hydrogen peroxide cyclopentyl benzene by peroxidation; wherein the impurity removal mode comprises at least one of the following treatments: water washing, dehydration, desulfurization and dechlorination of the material containing cyclopentyl benzene, so as to obtain a material after impurity removal. The method can also improve the yield of hydrogen peroxide cyclopentyl benzene.

Description

TECHNICAL FIELD

[0001] The present application relates to the chemical industry, in particular to a method and system for preparing hydrogen peroxide cyclopentyl benzene from cyclopentene. BACKGROUND

[0002] Phenol is an important chemical compound in the chemical industry. It can be used to produce phenolic resin, caprolactam, bisphenol A, salicylic acid, picric acid, pentachlorophenol, 2,4-D, adipic acid, phenolphthalein n-acetyl ethoxy aniline and other chemical products and intermediates, which have important uses in chemical raw materials, alkylphenol, synthetic fibers, plastics, synthetic rubber, medicine, pesticide, spice, dye, paint and oil refining industries. In addition, phenol can also be used as a solvent, experimental reagent and disinfectant. The aqueous solution of phenol can separate the protein on the chromosome in plant cells from DNA, making it easy to stain DNA. The traditional production route of phenol is cumene method, and cyclopentanone is also produced by condensation of adipic acid or hydration of cyclopentene. These methods can only produce phenol or cyclopentanone, and the economic benefits of simultaneous production are low. There are problems such as serious corrosion of equipment by acid used in the production process. Cyclopentyl benzene can produce high value phenol and cyclopentanone through peroxidation and acidolysis process, and the atomic utilization rate reaches 100%. This route has high economic value.

[0003] In the process of preparing hydrogen peroxide cyclopentyl benzene from cyclopentene, impurities present in the reaction material can inhibit the generation of free radicals in the peroxidation process, ultimately affecting the conversion rate and selectivity of the target product. Therefore, it is of great significance to refine the reaction raw material. SUMMARY

[0004] In order to solve the problem of low yield of hydrogen peroxide cyclopentyl benzene caused by impurities in the reaction raw material in the preparation of hydrogen peroxide cyclopentyl benzene from cyclopentene, the present application provides a method and system for preparing hydrogen peroxide cyclopentyl benzene from cyclopentene, which can effectively improve the yield of hydrogen peroxide cyclopentyl benzene.

[0005] In order to achieve the above purpose, the first aspect of the present application provides a method for preparing hydrogen peroxide cyclopentyl benzene from cyclopentene, which comprises: treating the aralkylation raw material by diene hydrogenation to obtain a material containing cyclopentyl benzene, removing impurities from the material containing cyclopentyl benzene, and then peroxidizing to obtain hydrogen peroxide cyclopentyl benzene.

[0006] Among them, the way of removing impurities includes at least one of water washing, dehydration, desulfurization and dechlorination of the material containing cyclopentyl benzene to obtain the impurity-removed material.

[0007] The second aspect of the present application provides a system for preparing hydrogen peroxide cyclopentyl benzene from cyclopentene, which comprises:

[0008] The hydrogenation unit is used to hydrogenate the aralkylated feedstock into a diene to obtain the hydrogenated material.

[0009] Arylalkylation unit, used to arylalkylate cyclopentene to obtain a material containing cyclopentylbenzene;

[0010] The impurity removal unit is used to remove impurities from the raw material containing cyclopentylbenzene to obtain the impurity-removed material;

[0011] The peroxidation unit is used to peroxidize cyclopentylbenzene to obtain cyclopentylbenzene hydrogen peroxide;

[0012] The impurity removal unit includes at least one of a water washing module, a dehydration module, a desulfurization module, and a dechlorination module.

[0013] The method described in this invention can effectively reduce the content of various impurities in the reaction raw materials, improve the catalytic activity and service life of the arylalkylation catalyst, greatly reduce production costs, and improve production efficiency.

[0014] The method described in this invention can also improve the yield of cyclopentene to prepare hydrogen peroxide cyclopentylbenzene. Detailed Implementation

[0015] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0016] During their research, the inventors of this invention discovered that impurities in the aralkylation feedstock significantly affect the subsequent peroxidation of cyclopentylbenzene to cyclopentylbenzene hydrogen peroxide during the preparation of cyclopentylbenzene hydrogen peroxide from cyclopentene. Although theoretically, direct hydrogenation and impurity removal of the aralkylation feedstock could also improve the yield of cyclopentylbenzene hydrogen peroxide, experiments have shown that hydrogenating the aralkylation feedstock with a diene before aralkylation and then removing impurities before the peroxidation reaction can more significantly improve the yield of cyclopentylbenzene hydrogen peroxide.

[0017] The first aspect of the present invention provides a method for preparing cyclopentyl hydroperoxide from cyclopentene, the method comprising: subjecting an aralkylation feedstock to diene hydrogenation treatment, followed by aralkylation to obtain a cyclopentylbenzene-containing material, removing impurities from the cyclopentylbenzene-containing material, and then peroxidizing it to obtain cyclopentyl hydroperoxide;

[0018] The impurities in the cyclopentyl benzene-containing material are removed by at least one of water washing, dehydration, desulfurization and dechlorination to obtain a material with impurities removed.

[0019] In the present application, the aralkylation raw material can be a cyclopentene-containing raw material or a raw material containing cyclopentene and benzene, and is preferably a cyclopentene-containing raw material, which can improve the yield of cyclopentyl benzene hydrogen peroxide in the preferred case.

[0020] For example, when the aralkylation raw material is a cyclopentene-containing raw material, the cyclopentene-containing raw material can be subjected to diene hydrogenation treatment first, and then the hydrogenated material and benzene are subjected to aralkylation. When the aralkylation raw material is a raw material containing cyclopentene and benzene, the cyclopentene and benzene-containing raw material can be subjected to diene hydrogenation treatment and aralkylation in sequence.

[0021] In the present application, the cyclopentene-containing raw material can contain at least one of cyclopentadiene, sulfur-containing compounds, nitrogen-containing compounds, chlorine-containing compounds and oxygen-containing compounds in addition to cyclopentene.

[0022] Preferably, the content of impurities in the cyclopentene-containing raw material is 500 ppm or more, such as 500 ppm or more, 1000 ppm or more, 2000 ppm or more, 3000 ppm or more, 4000 ppm or more, 5000 ppm or more, 6000 ppm or more, 7000 ppm or more, 8000 ppm or more, 9000 ppm or more, and 10000 ppm or more.

[0023] Preferably, the content of cyclopentadiene in the cyclopentene-containing raw material is 500-10000 ppm, and more preferably 500-5000 ppm.

[0024] In the present application, the sulfur-containing compounds can be conventional sulfur-containing compounds in the art, such as mercaptans, thiophenols and hydrogen sulfide.

[0025] Preferably, the content of sulfur-containing compounds in the cyclopentene-containing raw material is 0-2000 ppm, and more preferably 0-1000 ppm.

[0026] In the present application, the nitrogen-containing compounds can be conventional nitrogen-containing compounds in the art, such as pyridine, acridine, indole and carbazole.

[0027] Preferably, the content of nitrogen-containing compounds in the cyclopentene-containing raw material is 0-3000 ppm, and more preferably 0-2000 ppm.

[0028] In the present application, the chlorine-containing compounds can be conventional chlorine-containing compounds in the art, such as hydrogen chloride, organic chlorides, chlorinated cyclopentane, etc.

[0029] Preferably, the content of the chlorine-containing compound in the cyclopentene-containing raw material is 0-5000 ppm, more preferably 0-2500 ppm.

[0030] In the present application, the oxygen-containing compound can be a conventional oxygen-containing compound in the art, which can be an organic acid, a phenol, and a ketone compound.

[0031] Preferably, the content of the oxygen-containing compound in the cyclopentene-containing raw material is 0-3000 ppm, more preferably 0-2000 ppm.

[0032] In the present application, the content of the 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; and the content of the chlorine-containing compound is measured by mass spectrometry.

[0033] In the present application, the purpose of the diene hydrogenation is to convert the cyclopentadiene into cyclopentene.

[0034] In the present application, preferably, the diene hydrogenation treatment includes contacting the aralkylation raw material with hydrogen in the presence of a diene selective hydrogenation catalyst to obtain a hydrogenated material.

[0035] Preferably, the content of the cyclopentadiene in the hydrogenated material is less than 100 ppm, more preferably less than 50 ppm, based on the total weight of the hydrogenated material. Within the preferred range, the selectivity and yield of the aralkylation reaction can be effectively improved.

[0036] In the present application, the diene selective hydrogenation catalyst can be a conventional hydrogenation catalyst used in the art, preferably, the diene selective hydrogenation catalyst comprises a first carrier and an active component of palladium, wherein the content of the active component of palladium is 0.1-3 wt.%, based on the total weight of the diene selective hydrogenation catalyst.

[0037] In the present application, the first carrier can be a conventional first carrier used in the art, preferably, the first carrier is selected from at least one of calcium carbonate, activated carbon, barium sulfate, montmorillonite, zeolite, and sepiolite.

[0038] In the present application, the diene selective hydrogenation catalyst can be obtained by commercial purchase or self-preparation. The preparation method of the diene selective hydrogenation catalyst can be a conventional preparation method in the art, which is not described herein.

[0039] In the present application, the hydrogenation conditions can be the conditions conventionally used in the art, and preferably, the hydrogenation conditions include a temperature of 50-90°C and a pressure of 0.2-2 MPa.

[0040] In the present application, the amount of hydrogen can be selected within a wide range, and preferably, the molar ratio of the cyclopentene to the hydrogen is 1:0.02-0.2 in terms of pure substances.

[0041] Preferably, in the diene hydroprocessing, the mass space velocity is 0.5-10 h -1 .

[0042] In the present application, unless otherwise specified, the mass space velocity refers to the mass space velocity of the raw material input into the reactor, which refers to the mass space velocity of the aralkylation raw material (which can be a cyclopentene raw material or a raw material of cyclopentene and benzene) and hydrogen.

[0043] The hydrogenated material is subjected to aralkylation, and preferably, the aralkylation method includes aralkylating the hydrogenated material in the presence of an aralkylation catalyst to obtain a cyclopentylbenzene-containing material.

[0044] In the present application, the aralkylation catalyst can 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.

[0045] In the present application, the solid acid catalyst can be a solid acid catalyst conventionally used in the art, and preferably, the solid acid catalyst is selected from at least one of AlCl3, Hβ molecular sieve, MCM-22 molecular sieve, and HUSY molecular sieve.

[0046] In the present application, the ionic liquid catalyst can be an ionic liquid catalyst conventionally used in the art, and preferably, the ionic liquid catalyst is selected from at least one of 1-ethylpyridine aluminum trichloride ionic liquid, 1-methyl-3-alkyl imidazole aluminum trichloride ionic liquid, and 1-butylpyridine aluminum trichloride ionic liquid.

[0047] In the present application, preferably, the aralkylation catalyst is selected from at least one of AlCl3, Hβ molecular sieve, and 1-ethylpyridine aluminum trichloride ionic liquid.

[0048] In the present application, the aralkylation catalyst can be obtained by commercial purchase.

[0049] In the present application, the mass space velocity of the total material can be selected within a wide range, and preferably, the mass space velocity is 0.05-3 h -1 , and more preferably 0.1-2 h -1 .

[0050] It should be understood that the total material here is the sum of the cyclopentene raw material (hydroprocessed) and the benzene raw material (hydroprocessed or not) that is fed into the aralkylation device.

[0051] In the present application, the molar ratio of benzene to cyclopentene can be selected in a wide range, preferably, the molar ratio of benzene to cyclopentene is 2-10:1, such as can be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1 and any range consisting of any two values, more preferably 4-7:1. It should be understood that here is based on the theoretical value of benzene and cyclopentene.

[0052] In the present application, the conditions of the aralkylation can be conventional conditions in the art, including: the temperature is 50-180℃, more preferably 80-150℃; the pressure is 0.1-3MPa, more preferably 0.5-2MPa.

[0053] In the present application, the pressure refers to the gauge pressure unless otherwise specified.

[0054] In the present application, the cyclopentyl benzene-containing material is subjected to impurity removal and then peroxidation to obtain hydroperoxy cyclopentyl benzene. Among them, the impurity removal method includes at least one of water washing, dehydration, desulfurization and dechlorination of the cyclopentyl benzene-containing material to obtain the impurity-removed material.

[0055] Among them, the purpose of water washing is to remove oxygen-containing compounds and / or nitrogen-containing compounds that can be dissolved in water; the purpose of dehydration is to remove water mixed in the water washing process; the purpose of desulfurization is to remove sulfur-containing compounds; and the purpose of dechlorination is to remove chlorine-containing compounds.

[0056] In the present application, the water washing method can be a method commonly used in the art, preferably, the water washing method includes: the water washing conditions are such that the nitrogen-containing compound content in the water-washed material is below 100ppm, more preferably below 50ppm, such as can be below 50ppm, below 40ppm, below 30ppm, below 20ppm, below 10ppm, further preferably below 20ppm.

[0057] In the present application, the water washing conditions can be conventional conditions in the art, preferably, the water washing temperature is 20-50℃, and the volume ratio of the material to be water washed to water is 1:5-15.

[0058] Preferably, the water washing is carried out in a water washing tower.

[0059] In the present application, the dehydration conditions and mode can be conventional conditions and mode in the art, preferably, the dehydration mode comprises: the dehydration is carried out in the presence of a dehydration molecular sieve, and the dehydration conditions are such that the water content in the dehydrated material is below 600 ppm, more preferably below 200 ppm, such as below 200 ppm, below 100 ppm, below 80 ppm, below 60 ppm, below 40 ppm, below 20 ppm, below 10 ppm, further preferably below 20 ppm.

[0060] In the present application, the water content can be measured by coulometric method.

[0061] Preferably, the dehydration conditions comprise: the temperature is 20-45℃, the pressure is 0.1-0.7 MPa, and the mass space velocity is 5-20 h -1 .

[0062] Preferably, the dehydration is carried out in a dehydration tower.

[0063] Preferably, the dehydration molecular sieve can be a dehydration molecular sieve conventionally used in the art, preferably, the dehydration molecular sieve is selected from at least one of 4A molecular sieve, 3A molecular sieve and 5A molecular sieve; more preferably, the dehydration molecular sieve is UOP 4A molecular sieve.

[0064] The dehydration molecular sieve can be commercially available, which is not described here again.

[0065] In the present application, the desulfurization mode can be a mode conventionally used in the art, preferably, the desulfurization mode comprises: the desulfurization is carried out in the presence of a desulfurization adsorbent, and the desulfurization conditions are such that the sulfur compound content in the desulfurized material is below 100 ppm; more preferably below 50 ppm, such as below 50 ppm, below 40 ppm, below 30 ppm, below 20 ppm, below 10 ppm, further preferably below 10 ppm.

[0066] Preferably, the desulfurization is carried out in a desulfurization tower.

[0067] In the present application, the desulfurization adsorbent can be a desulfurization adsorbent conventionally used in the art, preferably, the desulfurization adsorbent is selected from at least one of β-type molecular sieve, Y-type molecular sieve, USY-type molecular sieve, ZSM-5 molecular sieve, mordenite, MCM-41 molecular sieve and SBA-15 molecular sieve.

[0068] Preferably, the desulfurization adsorbent is a copper-loaded desulfurization adsorbent, such as Cu / β-type molecular sieve, Cu / Y-type molecular sieve and Cu / USY-type molecular sieve, etc.

[0069] Preferably, the loading amount of copper in the desulfurization adsorbent is 3-30 wt%.

[0070] The desulfurization adsorbent can be commercially available, which will not be described here.

[0071] In the present application, the desulfurization conditions can be conventional conditions in the art, preferably, the desulfurization conditions include: temperature is 20-50℃, pressure is 0.6-2 MPa, mass space velocity is 0.25-4 h -1 .

[0072] In the present application, the dechlorination treatment mode can be a mode conventionally used in the art, preferably, the dechlorination treatment mode includes: the dechlorination is carried out in the presence of a dechlorination adsorbent, and the dechlorination conditions are such that the content of chlorinated compounds in the dechlorinated material is below 70 ppm; more preferably below 40 ppm, such as can be below 40 ppm, below 30 ppm, below 20 ppm, below 10 ppm, further preferably below 10 ppm.

[0073] Preferably, the dechlorination is carried out in a dechlorination tower.

[0074] In the present application, the dechlorination adsorbent can be a dechlorination adsorbent conventionally used in the art, preferably, the dechlorination adsorbent is selected from at least one of X-type molecular sieve, Y-type molecular sieve, MOR-type molecular sieve, activated carbon and MCM-41 molecular sieve.

[0075] Preferably, the dechlorination adsorbent is a Na2CO3-loaded dechlorination adsorbent, such as Na2CO3 / X-type molecular sieve, Na2CO3 / Y-type molecular sieve, Na2CO3 / MOR-type molecular sieve, etc.

[0076] Preferably, the loading amount of Na2CO3 in the dechlorination adsorbent is 5-25 wt%.

[0077] Preferably, the dechlorination adsorbent is a potassium carbonate-modified X-type molecular sieve.

[0078] The dechlorination adsorbent can be commercially available, which will not be described here.

[0079] In the present application, the dechlorination conditions can be conventional conditions in the art, preferably, the dechlorination conditions include: temperature is 20-50℃, pressure is 0.6-2 MPa, mass space velocity is 0.25-5 h -1 .

[0080] In a preferred embodiment of the present application, the impurity removal method comprises: sequentially subjecting the cyclopentyl benzene-containing material to water washing and dehydration treatment to obtain a dehydrated material, subjecting the dehydrated material to desulfurization treatment to obtain a desulfurized material, subjecting the desulfurized material to dechlorination treatment to obtain an impurity-removed material. The impurity removal method according to the preferred method can further improve the yield of cyclopentyl benzene hydroperoxide.

[0081] In the present application, the peroxidation method can be a method commonly used in the art, and preferably, the peroxidation method comprises: mixing a peroxidation catalyst, the impurity-removed material and an optional initiator to obtain a homogeneous solution, introducing an oxygen-containing gas into the homogeneous solution, and performing peroxidation at 50-130°C to obtain cyclopentyl benzene hydroperoxide.

[0082] In the present application, the peroxidation step is preferably a batch reaction.

[0083] In the present application, peroxidation of cyclopentyl benzene can be achieved at 50-130°C, and preferably, the peroxidation temperature is 85-120°C, such as 85, 90, 95, 100, 105, 110, 120°C and any range between any two values. In the preferred range, higher conversion rate of cyclopentyl benzene and selectivity and yield of cyclopentyl benzene hydroperoxide can be obtained.

[0084] In the present application, the peroxidation time can not be particularly limited, and preferably, the peroxidation time is 2-24h, and more preferably 8-15h.

[0085] In the present application, the peroxidation catalyst can be a peroxidation catalyst commonly used in the art, and preferably, the peroxidation catalyst is selected from imines or N-OH-containing compounds.

[0086] Preferably, the peroxidation catalyst is selected from at least one of N-hydroxyphthalimide, 4-amino-N-hydroxyphthalimide, 3-amino-N-hydroxyphthalimide, tetrabromo-N-hydroxyphthalimide, tetrachloro-N-hydroxyphthalimide, N-hydroxychlorobridged imide, N-hydroxycedurimide, N-hydroxytrimellitimide, N-hydroxybenzene-1,2,4-trimellitimide, N,N'-dihydroxy(succinimide), N,N'-dihydroxy(benzophenone-3,3',4,4'-tetramellitimide), N-hydroxymaleimide, pyridine-2,3-dicarboxylic imide, N-hydroxysuccinimide, N-hydroxy(tartaric imide), N-hydroxy-5-norbornene-2,3-dicarboxylic imide, exo-N-hydroxy-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic imide, N-hydroxy-cis-cyclohexane-1,2-dicarboxylic imide, N-hydroxy-cis-4-cyclohexene-1,2-dicarboxylic imide, sodium salt of N-hydroxynaphthalimide, N-hydroxy-o-benzenedisulfonimide, and N,N',N"-trihydroxyisocyanuric acid, more preferably N-hydroxyphthalimide (NHPI). Under the preferred conditions, the effect of peroxidation can be improved.

[0087] In the present application, the amount of the peroxidation catalyst can be selected within a wide range, preferably, the amount of the peroxidation catalyst is 0.01-10% by weight, based on the weight of cyclopentylbenzene, such as 0.01, 0.02, 0.05, 0.08, 0.1, 0.2, 0.5, 0.8, 1, 2, 5, 8, 10% by weight, and any range between any two values, preferably 0.05-0.5% by weight.

[0088] The initiator can be, for example, a peroxide initiator or an azo initiator, preferably, the initiator is a peroxide initiator.

[0089] In the present application, the peroxide initiator can be a peroxide initiator conventionally used in the art, preferably selected from at least one of hydroperoxy initiators, diacyl peroxide initiators, dialkyl peroxide initiators, diester peroxide initiators, and organic acid / ketone peroxide initiators, more preferably a hydroperoxy initiator.

[0090] In the present application, preferably, the hydroperoxy initiator is selected from at least one of cyclopentylbenzene hydroperoxide, t-butyl hydroperoxide, cyclopentyl-1-phenyl-1-hydroperoxide, cyclohexyl-1-phenyl-1-hydroperoxide, pinane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide.

[0091] In the present application, preferably, the peroxide diacyl initiator is selected from at least one of dibenzoyl peroxide, dibenzoyl peroxide, di-4-chlorobenzoyl peroxide, di-2,4-dichlorobenzoyl peroxide, dibenzoyl peroxide, and di-4-chlorobenzoyl peroxide.

[0092] In the present application, preferably, the peroxide diester initiator is selected from at least one of t-amyl peroxy-3,5,5-trimethyl hexanoate, 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, ethyl 3,3-bis(t-amylperoxy)butyrate, ethyl 3,3-bis(t-butylperoxy)butyrate, and butyl 1,1,3,3-tetramethylperoxy neodecanoate.

[0093] In the present application, preferably, the peroxide diester initiator is selected from at least one of t-amyl peroxy-3,5,5-trimethyl hexanoate, 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, ethyl 3,3-bis(t-amylperoxy)butyrate, ethyl 3,3-bis(t-butylperoxy)butyrate, and butyl 1,1,3,3-tetramethylperoxy neodecanoate.

[0094] In the present application, preferably, the peroxide organic acid / ketone initiator is selected from at least one of peroxoacetic acid, 3-chloroperoxybenzoic acid, disuccinyl peroxide, diperazelaic acid, methyl ethyl ketone peroxide, methyl ethyl(methyl)ketone peroxide, methyl isobutyl ketone peroxide, acetylacetone peroxide, and cyclohexanone peroxide.

[0095] In the present application, the azo initiator can be an azo initiator commonly used in the art, preferably, a perazobisisobutyronitrile and / or a perazobisisoheptyl nitrile.

[0096] In the present application, most preferably, the initiator is a peroxide cyclopentyl benzene. Compared with other initiators, using peroxide cyclopentyl benzene as the initiator can improve the selectivity of peroxide cyclopentyl benzene.

[0097] In the present application, the amount of the initiator can be selected in a wide range, preferably, the amount of the initiator is 0-10% by weight, based on the weight of the cyclopentyl benzene, 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 0.01-5% by weight. In the preferred range, the peroxidation effect can be improved.

[0098] In the present application, the weight of the cyclopentyl benzene is based on the theoretical value.

[0099] In the present application, the oxygen-containing gas used can be an oxygen-containing gas commonly used in the art, such as air, pure oxygen, or a mixture of oxygen and other gases, and the type is not particularly limited. Preferably, the concentration of oxygen in the oxygen-containing gas is 20-100% by volume.

[0100] In the present application, the amount of the oxygen-containing gas can be selected in a wide range, preferably, the volume of the oxygen-containing gas introduced per minute per mole of cyclopentyl benzene is 0.2-8 L / (min·mol), such as 0.2, 0.4, 0.6, 0.8, 1, 2, 3, 4, 5, 6, 7, 8 L / (min·mol), and any range between any two values. In the preferred range, higher conversion of cyclopentyl benzene and selectivity and yield of peroxide cyclopentyl benzene can be obtained.

[0101] In the present application, the hydrogenation and impurity removal method can also be used for hydrogenation and impurity removal of other materials containing the above-mentioned impurities. It should be understood that in the case of different raw materials, the cyclopentadiene can be other types of diene compounds.

[0102] The second aspect of the present application provides a system for preparing peroxide cyclopentyl benzene from cyclopentene, which comprises:

[0103] A hydrogenation unit for diene hydrogenation treatment of the aralkylation raw material to obtain a hydrogenated material;

[0104] An aralkylation unit for aralkylation of cyclopentene to obtain a cyclopentyl benzene-containing material;

[0105] a decontamination unit for decontaminating the cyclopentylbenzene-containing raw material to obtain a decontaminated material;

[0106] a peroxidation unit for peroxidizing the cyclopentylbenzene to obtain a hydroperoxy cyclopentylbenzene;

[0107] The decontamination unit comprises at least one of a water washing module, a dehydration module, a desulfurization module and a dechlorination module.

[0108] The operation mode and conditions of the system have been described in detail in the first aspect and will not be repeated here.

[0109] It should be understood that the temperature and pressure involved in the present application may fluctuate in actual operation, such as a temperature fluctuation of 3℃ up and down, and a pressure fluctuation of 0.1 MPa up and down.

[0110] The present application will be described in detail below by way of examples.

[0111] In the following examples, the water content is measured by the electric quantity method;

[0112] The cyclopentadiene content is measured by mass spectrometric analysis;

[0113] The nitrogen-containing compound content is measured by mass spectrometric analysis;

[0114] The oxygen-containing compound content is measured by mass spectrometric analysis;

[0115] The sulfur-containing compound content is measured by mass spectrometric analysis;

[0116] The chlorine-containing compound content is measured by mass spectrometric analysis;

[0117] The cyclopentylbenzene and hydroperoxy cyclopentylbenzene contents are measured by gas chromatographic analysis.

[0118] Unless otherwise specified, each reagent and material is commercially available.

[0119] In the following examples, the cyclopentene raw material contains 3000 ppm of cyclopentadiene, 1200 ppm of oxygen-containing compounds, 1100 ppm of nitrogen-containing compounds, 1400 ppm of water, 800 ppm of sulfur-containing compounds and 2100 ppm of chlorine-containing compounds, and the balance is cyclopentene. It should be understood that the impurity content in the cyclopentene raw material may fluctuate, but the fluctuation range is within 100 ppm, and the fluctuation range of the sulfur-containing compound content is within 50 ppm.

[0120] In the following examples, the molecular sieves used are purchased from Petrochemical Scientific Research Institute of China Petroleum Chemical Industry Co., Ltd.

[0121] Preparation Example

[0122] An appropriate amount of Na2PdCl4 was dissolved in water to form a homogeneous solution; then 3 times the weight of calcium carbonate was added to the solution at room temperature, and stirred at room temperature for 12 h, washed, dried, and calcined at 400°C for 5 h; finally, treated at 400°C in a hydrogen atmosphere for 4 h to obtain a diene selective hydrogenation catalyst. The amount of Na2PdCl4 was adjusted so that the Pd content in the diene selective hydrogenation catalyst was 0.5% and 1.0% by weight, respectively, to obtain a 0.5% Pd / CaCO3 catalyst and a 1% Pd / CaCO3 catalyst, respectively.

[0123] Example 1

[0124] This example is used to illustrate a method for preparing peroxycyclopentylbenzene from cyclopentene

[0125] (1) Hydrogenation

[0126] The cyclopentene raw material was mixed with hydrogen and preheated together in a preheater, and then fed into a selective hydrogenation reactor for hydrogenation treatment in the presence of a 0.5% Pd / CaCO3 catalyst. The molar ratio of cyclopentene to hydrogen was 1:0.1, the hydrogenation temperature was 75°C, the hydrogen pressure was maintained at 0.3 MPa, and the mass space velocity was 3 h -1 .

[0127] The content of cyclopentadiene in the material after hydrogenation treatment was determined, and the specific results are shown in Table 1.

[0128] (2) Arylalkylation

[0129] The hydrogenated material obtained in step (1) and benzene were used as reaction raw materials to perform arylalkylation in the presence of AlCl3 to obtain a material containing cyclopentylbenzene. The molar ratio of benzene to cyclopentene was 6:1, the reaction temperature was 120°C, the reaction pressure was 0.5 MPa, and the mass space velocity was 0.5 h -1 .

[0130] The conversion rate of cyclopentene and the yield of cyclopentylbenzene in the material obtained by the reaction were determined and calculated, and the specific results are shown in Table 2.

[0131] (3) Impurity removal

[0132] The material containing cyclopentylbenzene was fed into a water washing tower at a water washing temperature of 40°C and a material / water volume ratio of 1:10; the material from the water washing tower was fed into a dehydration tower to contact with 4A molecular sieves at a dehydration temperature of 30°C, a pressure of 0.5 MPa, and a mass space velocity of 10 h -1 .

[0133] The material exiting the dehydration tower is fed into the desulfurization tower and contacted with Cu / β type molecular sieves. The desulfurization temperature is 20℃, the pressure is 0.6MPa, and the mass hourly space velocity is 0.25h. -1 The copper loading in the Cu / β type molecular sieve is 20% by weight.

[0134] The material exiting the desulfurization tower is fed into the dechlorination tower and contacted with Na2CO3 / X type molecular sieves. After dechlorination, the purified material is obtained. The temperature for removing chlorine-containing compounds is 20℃, the pressure is 0.7MPa, and the mass hourly space velocity is 0.3h. -1 The Na2CO3 loading in the Na2CO3 / X type molecular sieve is 15% by weight.

[0135] The impurity content of the purified material was determined, and the specific results are shown in Table 1.

[0136] (4) Peroxide

[0137] The purified material obtained in step (2) is mixed evenly with cumene hydroperoxide, and the amount of cumene hydroperoxide is 1.0% by weight of the purified material; then it is heated to react at 120°C; at the same time, air is bubbled into the reaction solution; the volume of oxygen-containing gas introduced per mole of cyclopentylbenzene per minute is 4 L / (min·mol), and the reaction lasts for 8 hours.

[0138] The conversion rate of cyclopentylbenzene and the yield of cyclopentylbenzene peroxide in the reaction product were determined and calculated. The specific results are shown in Table 3.

[0139] Example 2

[0140] This embodiment illustrates the method for preparing cyclopentylbenzene peroxide from cyclopentene.

[0141] (1) Hydrogenation

[0142] Cyclopentene feedstock and benzene (molar ratio of benzene to cyclopentene 6:1) were mixed with hydrogen and preheated in a preheater before being fed into a selective hydrogenation reactor for hydrogenation in the presence of a 1 wt% Pd / CaCO3 catalyst. The molar ratio of cyclopentene to hydrogen was 1:0.05, the hydrogenation temperature was 55°C, the hydrogen pressure was maintained at 0.8 MPa, and the mass hourly space velocity (HHSV) was 8 h⁻¹. -1 .

[0143] The content of cyclopentadiene in the hydrogenated material was determined, and the specific results are shown in Table 1.

[0144] (2) Arylalkylation

[0145] The hydrogenated material obtained in step (1) was used as a reactant and subjected to an arylalkylation reaction in the presence of Hβ molecular sieves to obtain a material containing cyclopentylbenzene. The reaction temperature was 150℃; the reaction pressure was 0.5 MPa; and the mass hourly space velocity (HHSV) was 1.2 h⁻¹. -1 .

[0146] The conversion rate of cyclopentene and the yield of cyclopentylbenzene in the reaction products were determined and calculated. The specific results are shown in Table 2.

[0147] (3) Removal of impurities

[0148] The material containing cyclopentylbenzene was fed into a water washing tower at a washing temperature of 20°C and a material / water volume ratio of 1:5. The material exiting the water washing tower was then fed into a dehydration tower where it was contacted with 3A molecular sieves at a dehydration temperature of 35°C, a pressure of 0.4 MPa, and a mass hourly space velocity of 20 h⁻¹. -1 .

[0149] The material exiting the dehydration tower is fed into the desulfurization tower and contacted with Cu / Y type molecular sieves. The desulfurization temperature is 20℃, the pressure is 1.8MPa, and the mass hourly space velocity is 0.25h. -1 The copper loading in the Cu / Y type molecular sieve is 15% by weight.

[0150] The material exiting the desulfurization tower is fed into the dechlorination tower and contacted with Na2CO3 / X type molecular sieves. After dechlorination, the purified material is obtained. The temperature for removing chlorine-containing compounds is 20℃, the pressure is 0.8MPa, and the mass hourly space velocity is 0.3h. -1 The Na2CO3 loading in the Na2CO3 / X type molecular sieve is 20% by weight.

[0151] The impurity content of the purified material was determined, and the specific results are shown in Table 1.

[0152] (4) Peroxide

[0153] Peroxidation was performed according to the method described in step (4) of Example 1.

[0154] The conversion rate of cyclopentylbenzene and the yield of cyclopentylbenzene peroxide in the reaction product were determined and calculated. The specific results are shown in Table 3.

[0155] Example 3

[0156] This embodiment illustrates the method for preparing cyclopentylbenzene peroxide from cyclopentene.

[0157] (1) Hydrogenation

[0158] Hydrogenation was performed according to the method described in step (1) of Example 2, except that the molar ratio of benzene to cyclopentene was 8:1. The content of cyclopentadiene in the material after hydrogenation was determined, and the specific results are shown in Table 1.

[0159] (2) Arylalkylation

[0160] Arylalkylation was performed according to the method described in step (1) of Example 2 to obtain a material containing cyclopentylbenzene. The conversion rate of cyclopentene and the yield of cyclopentylbenzene in the reacted material were determined and calculated, and the specific results are shown in Table 2.

[0161] (3) Removal of impurities

[0162] The material containing cyclopentylbenzene was fed into a water washing tower at a washing temperature of 50°C and a material / water volume ratio of 1:15. The material exiting the water washing tower was then fed into a dehydration tower where it was contacted with 5A molecular sieves at a dehydration temperature of 32°C, a pressure of 0.35 MPa, and a mass hourly space velocity of 5 h⁻¹. -1 .

[0163] The material exiting the dehydration tower is fed into the desulfurization tower and contacted with Cu / USY type molecular sieves. The desulfurization temperature is 30℃, the pressure is 0.8MPa, and the mass hourly space velocity is 4h. -1 The copper loading in the Cu / USY type molecular sieve is 25% by weight.

[0164] The material exiting the desulfurization tower is fed into the dechlorination tower and contacted with a Na2CO3 / MOR type molecular sieve. After dechlorination, the purified material is obtained. The temperature for removing chlorine-containing compounds is 20℃, the pressure is 0.7MPa, and the mass hourly space velocity is 0.3h. -1 The Na2CO3 loading in the Na2CO3 / MOR type molecular sieve is 10% by weight.

[0165] The impurity content of the purified material was determined, and the specific results are shown in Table 1.

[0166] (4) Peroxide

[0167] Peroxidation was performed according to the method described in step (4) of Example 1.

[0168] The conversion rate of cyclopentylbenzene and the yield of cyclopentylbenzene peroxide in the reaction product were determined and calculated. The specific results are shown in Table 3.

[0169] Example 4

[0170] This embodiment illustrates the method for preparing cyclopentylbenzene peroxide from cyclopentene.

[0171] The procedure is performed according to the method described in Example 1, except that no washing or dehydration is performed.

[0172] The conversion rate of cyclopentene and the yield of cyclopentylbenzene in the reaction products were determined and calculated. The specific results are shown in Table 2.

[0173] The conversion rate of cyclopentylbenzene and the yield of cyclopentylbenzene peroxide in the reaction product were determined and calculated. The specific results are shown in Table 3.

[0174] Example 5

[0175] This embodiment illustrates the method for preparing cyclopentylbenzene peroxide from cyclopentene.

[0176] The procedure was carried out according to the method in Example 3, except that no desulfurization treatment was performed.

[0177] The conversion rate of cyclopentene and the yield of cyclopentylbenzene in the reaction products were determined and calculated. The specific results are shown in Table 2.

[0178] The conversion rate of cyclopentylbenzene and the yield of cyclopentylbenzene peroxide in the reaction product were determined and calculated. The specific results are shown in Table 3.

[0179] Example 6

[0180] This embodiment illustrates the method for preparing cyclopentylbenzene peroxide from cyclopentene.

[0181] The procedure was carried out according to the method in Example 3, except that no dechlorination treatment was performed.

[0182] The conversion rate of cyclopentene and the yield of cyclopentylbenzene in the reaction products were determined and calculated. The specific results are shown in Table 2.

[0183] The conversion rate of cyclopentylbenzene and the yield of cyclopentylbenzene peroxide in the reaction product were determined and calculated. The specific results are shown in Table 3.

[0184] Comparative Example 1

[0185] This comparative example illustrates the method for preparing hydrogen peroxide cyclopentylbenzene from reference cyclopentene.

[0186] Hydrogen peroxide cyclopentylbenzene was prepared according to the method described in Example 1, except that the alkylation feedstock was not hydrogenated, and the feedstock containing cyclopentylbenzene was not purified.

[0187] The conversion rate of cyclopentene and the yield of cyclopentylbenzene in the reaction products were determined and calculated. The specific results are shown in Table 2.

[0188] The conversion rate of cyclopentylbenzene and the yield of cyclopentylbenzene peroxide in the reaction product were determined and calculated. The specific results are shown in Table 3.

[0189] Comparative Example 2

[0190] This comparative example illustrates the method for preparing hydrogen peroxide cyclopentylbenzene from reference cyclopentene.

[0191] The operation was carried out according to the method of Example 1, except that step (3) was performed before step (2), that is, the raw material containing cyclopentene was hydrogenated and impurity removed in sequence and then arylalkylated, and then the raw material containing cyclopentylbenzene was peroxidized to obtain cyclopentylbenzene peroxide.

[0192] The conversion rate of cyclopentene and the yield of cyclopentylbenzene in the reaction product were determined and calculated, and the specific results are shown in Table 2. The impurity content in the cyclopentylbenzene-containing product was determined, and the specific results are shown in Table 1. The conversion rate of cyclopentylbenzene and the yield of cyclopentylbenzene peroxide in the reaction product were determined and calculated, and the specific results are shown in Table 3.

[0193] Table 1

[0194]

[0195]

[0196] Table 2

[0197] No. Cyclopentene conversion / % Cyclopentylbenzene selectivity / % Cyclopentylbenzene 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

[0198] Table 3

[0199] No. Cyclopentylbenzene conversion / % Hydrogen peroxide cyclopentylbenzene selectivity / % Hydrogen peroxide cyclopentylbenzene 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

[0200] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A process for the preparation of hydroperoxy cyclopentyl benzene from cyclopentene, characterized in that, The method comprises: carrying out diene hydrogenation treatment on an aralkylation raw material, then aralkylating to obtain a cyclopentyl benzene-containing material, carrying out impurity removal on the cyclopentyl benzene-containing material, and then peroxidizing to obtain hydrogen peroxide cyclopentyl benzene; The diene hydrogenation treatment comprises: contacting the aralkylation raw material with hydrogen in the presence of a diene selective hydrogenation catalyst to obtain a hydrogenated material. The aralkylation raw material is a cyclopentene-containing raw material, and the method comprises: carrying out diene hydrogenation treatment on the cyclopentene-containing raw material, then aralkylating the hydrogenated material and benzene. Alternatively, the aralkylation raw material is a cyclopentene and benzene-containing raw material, and the method comprises: sequentially carrying out diene hydrogenation treatment and aralkylation on the cyclopentene and benzene-containing raw material. The molar ratio of benzene to cyclopentene is 4-7:

1. The content of cyclopentadiene in the hydrogenated material is less than 50 ppm, based on the total weight of the hydrogenated material. The diene selective hydrogenation catalyst comprises a first carrier and a catalytically active component of palladium, The content of the catalytically active component of palladium is 0.1-3% by weight, based on the total weight of the catalyst. The first carrier is selected from at least one of calcium carbonate, activated carbon and barium sulfate. The impurity removal comprises: sequentially carrying out water washing and dehydration treatment on the cyclopentyl benzene-containing material to obtain a dehydrated material, carrying out desulfurization treatment on the dehydrated material to obtain a desulfurized material, and carrying out dechlorination treatment on the desulfurized material to obtain an impurity-removed material. The water washing is carried out at a temperature of 20-40°C and a volume ratio of the cyclopentyl benzene-containing material to water of 1:5-10.

2. The method of claim 1, wherein, The hydrogenation is carried out at a temperature of 50-90°C and a pressure of 0.2-2 MPa.

3. The method of claim 1, wherein, The aralkylation comprises: aralkylating the hydrogenated material in the presence of an aralkylation catalyst to obtain a cyclopentyl benzene-containing material.

4. The method of claim 3, wherein, The aralkylation catalyst is a solid acid catalyst and / or an ionic liquid catalyst.

5. The method of claim 1, wherein, The conditions of the aralkylation include: temperature of 50-180℃; pressure of 0.1-3MPa; mass space velocity of 0.05-3h -1 .

6. The method of claim 5, wherein, The conditions of the aralkylation include: temperature of 80-150℃; pressure of 0.5-2 MPa; mass space velocity of 0.1-2 h -1 .

7. The method of any of claims 1-6, wherein, The water washing is carried out under conditions such that the content of nitrogen-containing compounds in the water-washed material is less than 100 ppm and the content of oxygen-containing compounds is less than 100 ppm.

8. The method of any of claims 1-6, wherein, The dehydration is carried out in the presence of a dehydration molecular sieve, and the dehydration is carried out under conditions such that the content of water in the dehydrated material is less than 600 ppm.

9. The method of claim 8, wherein, The conditions of the dehydration include: temperature of 20-45℃, pressure of 0.1-0.7MPa, mass space velocity of 5-20h -1 .

10. The method of claim 8, wherein, The dehydration molecular sieve is selected from at least one of 4A molecular sieve, 3A molecular sieve and 5A molecular sieve.

11. The method of any one of claims 1-6, wherein, The desulfurization is carried out in the presence of a desulfurization adsorbent, and the desulfurization is carried out under conditions such that the content of sulfur-containing compounds in the desulfurized material is less than 100 ppm.

12. The method of claim 11, wherein, The desulfurization adsorbent is selected from at least one of Cu / β molecular sieve, Cu / Y molecular sieve, Cu / USY molecular sieve, ZSM-5 molecular sieve, mordenite, MCM-41 molecular sieve and SBA-15 molecular sieve.

13. The method of claim 11, wherein, The desulfurization conditions include: temperature of 20-50℃, pressure of 0.6-2MPa, mass space velocity of 0.25-4h -1 .

14. The method of any one of claims 1-6, wherein, The dechlorination is carried out in the presence of a dechlorination adsorbent, and the dechlorination is carried out under conditions such that the content of chlorine-containing compounds in the dechlorinated material is less than 70 ppm.

15. The method of claim 14, wherein, The dechlorination adsorbent is selected from at least one of Na2CO3 / X type molecular sieve, Na2CO3 / Y type molecular sieve, Na2CO3 / MOR type molecular sieve, activated carbon and MCM-41 molecular sieve.

16. The method of claim 14, wherein, The dechlorination conditions include: temperature of 20-50℃, pressure of 0.3-1.5MPa, mass space velocity of 0.25-5h -1 .

17. The method of any one of claims 1-6, wherein, The peroxidation mode comprises mixing a peroxidation catalyst, the impurity-removed material and an optional initiator to obtain a homogeneous solution, introducing an oxygen-containing gas into the homogeneous solution, and carrying out peroxidation at 50-130 DEG C to obtain hydrogen peroxide cyclopentylbenzene.

18. The method of claim 17, wherein, The peroxidation time is 2-24 h.

19. The method of claim 18, wherein, The peroxidation time is 8-15 h.

20. The method of claim 17, wherein, The peroxidation catalyst is selected from imines or N-OH-containing compounds.

21. The method of claim 17, wherein, The initiator is a peroxide.

22. The method of claim 21, wherein, The initiator is an organic peroxide.

23. The method of claim 17, wherein, The amount of the peroxidation catalyst is 0.01-10 wt% based on the weight of cyclopentylbenzene, and the amount of the initiator is 0-10 wt%.

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