CN114436728B - Method for preparing isopropylbenzene by using alpha, alpha dimethyl benzyl alcohol and application - Google Patents

Method for preparing isopropylbenzene by using alpha, alpha dimethyl benzyl alcohol and application Download PDF

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CN114436728B
CN114436728B CN202011116359.7A CN202011116359A CN114436728B CN 114436728 B CN114436728 B CN 114436728B CN 202011116359 A CN202011116359 A CN 202011116359A CN 114436728 B CN114436728 B CN 114436728B
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alpha
dimethylbenzyl alcohol
cumene
catalyst
metallic
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CN114436728A (en
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赵多
刘仲能
马文迪
吕宇皓
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/20—Sulfiding
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
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    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
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    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14—Phosphorus; Compounds thereof
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    • C07C2527/14—Phosphorus; Compounds thereof
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a method for preparing isopropylbenzene by utilizing alpha, alpha-dimethylbenzyl alcohol and application thereof, wherein the method comprises the following steps: in the presence of a catalyst and hydrogen, a hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol and isopropyl benzene reacts to obtain isopropyl benzene, wherein the hydrocarbon material contains the isopropyl benzene with the weight percentage of x percent, and when the weight percentage of x percent is less than or equal to 0.1 percent, the reaction temperature is controlled to be 180-220 ℃; when 0.1 percent < x percent is less than or equal to 0.5 percent, controlling the reaction temperature to be (200+x is 100) to 250 ℃; when 0.5% < x%, the reaction temperature was controlled at (220+x 80) to 320 ℃. Different conditions are selected according to different content of the isopropyl benzene in the raw materials, so that the isopropyl benzene generates isopropyl benzene free radical and methyl styrene, and the isopropyl benzene free radical generated in the conversion of benzyl alcohol is quenched in time. The method can be widely applied to the manufacture of isopropyl benzene and epoxypropane by using alpha, alpha-dimethylbenzyl alcohol.

Description

Method for preparing isopropylbenzene by using alpha, alpha dimethyl benzyl alcohol and application
Technical Field
The invention belongs to the field of cumene preparation, and particularly relates to the preparation of cumene by utilizing alpha, alpha-dimethylbenzyl alcohol, in particular to the preparation of cumene by hydrogenolysis of a hydrocarbon byproduct containing alpha, alpha-dimethylbenzyl alcohol, which is generated during propylene oxide production.
Background
Propylene Oxide (PO) is the third largest propylene derivative, other than polypropylene and acrylonitrile, and is an important basic organic chemical raw material. At present, the production process of PO mainly comprises four types: a chlorohydrin method, a co-oxidation method for co-producing styrene PO/SM method and a co-producing tertiary butanol PO/TBA method, a hydrogen peroxide direct oxidation method (HPPO method) and a cumene oxidation method (CHP method).
The chlorohydrin method has serious pollution, and the development of PO production technology is mainly focused on the development of a green and environment-friendly new process. Wherein, the co-oxidation method is influenced by the market of the joint product, and the HPPO process has higher potential safety hazard.
In the technology for producing propylene oxide by the CHP method, a large amount of byproducts containing alpha, alpha-dimethylbenzyl alcohol (DMBA) are generated in the propylene epoxidation process, cumene is generated by hydrogenolysis reaction, and the cumene is participated in the reaction cycle again. This byproduct, which contains α, α -dimethylbenzyl alcohol (DMBA), also contains a small amount of dicumyl benzene (the right-hand product in formula 3), which is produced by dimerization of two cumene units, thus resulting in an increase in cumene unit consumption.
The specific reaction process is shown in equations (1), (2), (3) and (4).
U.S. patent No. 7442843B2 proposes a process for improving the yield of cumene, which adopts a palladium-based catalyst, and uses alpha, alpha-dimethylbenzyl alcohol and hydrogen as raw materials to produce cumene through hydrogenolysis or dehydration hydrogenation, wherein the hydrogen contains 0.1-10% of CO, so that the conversion rate of dimethylbenzyl alcohol and the selectivity of cumene can be obviously improved. Chinese patent CN101733093a reports that using alumina or zeolite supported metal Pd or a mixture of Pd and Pt as a reaction, the conversion rate of α, α -dimethylbenzyl alcohol is greater than 99.5% and the selectivity of cumene is greater than 99.5% under the condition that the reaction temperature is lower than 160 ℃, under the reaction condition of this patent, the early stage of the Pd catalyst is very easy to cause cumene to produce hydrogenated isopropyl cyclohexane, and the strong acidity of the carrier in this patent can obviously cause polymerization of methyl styrene, which is a dehydration intermediate product of α, α -dimethylbenzyl alcohol, this patent does not mention the technical problem of catalyst stability. Chinese patent CN104230640A proposes the use of Pd/SiO 2 The catalyst can realize 100% conversion of alpha, alpha-dimethylbenzyl alcohol at the reaction temperature of 180 ℃, but the selectivity of isopropylbenzene is lower than 98.5%.
In the prior art, there is more of the improvement of the activity of hydrogenolysis of α, α -dimethylbenzyl alcohol and cumene selectivity by improving the process or catalyst, thereby improving the yield of cumene. The technical problems of how to reduce the formation of the isopropyl benzene in the hydrogenolysis reaction process or how to further reduce the unit consumption of the isopropyl benzene in the propylene oxide production technology, especially the control or conversion of the isopropyl benzene impurities in the epoxidation product, are less involved.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a method for preparing isopropyl benzene by utilizing alpha, alpha-dimethylbenzyl alcohol, in particular to a method for preparing isopropyl benzene by utilizing alpha, alpha-dimethylbenzyl alcohol containing isopropyl benzene impurities, different reaction conditions are selected and thermodynamic control is carried out according to different content of the isopropyl benzene impurities in raw materials, so that the isopropyl benzene generates free radicals and alpha-methylstyrene, the free radicals and the alpha-methylstyrene generate hydrogenation to generate isopropyl benzene respectively, and meanwhile, the isopropyl benzene free radicals possibly generated in the benzyl alcohol conversion process are quenched in time to generate the isopropyl benzene, thereby reducing the unit consumption of the isopropyl benzene.
One of the objects of the present invention is to provide a method for producing cumene using α, α -dimethylbenzyl alcohol, comprising: in the presence of a catalyst and hydrogen, a hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol reacts to obtain isopropylbenzene, wherein the hydrocarbon material contains the isopropylbenzene, the weight percentage of which (the isopropylbenzene) is x percent, and when x percent is less than or equal to 0.1 percent, the reaction temperature is controlled to be 180-220 ℃; when 0.1 percent < x percent is less than or equal to 0.5 percent, controlling the reaction temperature to be (200+x is 100) to 250 ℃; when 0.5% < x% (preferably 0.5% < x.ltoreq.1%), the reaction temperature is controlled to be (220+x.80) to 320 ℃.
The inventors found that, when the temperature for producing cumene is controlled by the method of the present invention, it is possible to decompose cumene contained in the raw material itself into cumene and to suppress the formation of cumene in the hydrogenolysis process, and as a result, the obtained cumene product contains almost no cumene (only 1 to 10 ppm).
In a preferred embodiment, the catalyst comprises a support, metallic palladium, optionally a co-metal and optionally a non-metallic promoter, wherein the metallic palladium, optionally a co-metal and optionally a non-metallic promoter are supported on the support.
The source of metallic palladium is not particularly limited, and is, for example, but not limited to, at least one of palladium chloride, palladium nitrate, palladium chloride acid, and the like.
In a further preferred embodiment, the support is selected from at least one of silica, alumina and activated carbon (preferably alumina); and/or the auxiliary metal is selected from at least one of metallic copper, metallic zinc, metallic cobalt, metallic tin, metallic nickel and metallic silver, and/or the non-metallic auxiliary agent is selected from sulfur and/or phosphorus.
The source of the metal promoter is not particularly limited, and is, for example, but not limited to, at least one of a metal promoter chloride, an active metal promoter nitrate compound, an active metal promoter acetate compound, and the like. Sulfur is derived from sulfur-containing organics such as, but not limited to, at least one of t-nonyl polysulfide, t-butyl polysulfide, dimethyl disulfide, and the like. The source of phosphorus is not particularly limited, but is preferably at least one of phosphoric acid, potassium dihydrogen phosphate, phosphorous acid, calcium phosphate, and the like.
The inventor finds that the hydrogenation activity and stability of the catalyst can be obviously improved after the carrier is modified by phosphorus through a great amount of experimental researches. Especially, when the auxiliary active component (auxiliary active metal) is introduced into the catalyst, the catalyst has obvious technical effects in improving the conversion rate of alpha, alpha-dimethylbenzyl and the selectivity of isopropylbenzene.
In a preferred embodiment, the metallic palladium is present in an amount of 0.06g/L to 30g/L, the co-metal is present in an amount of 0.0006g/L to 1.0g/L and the non-metallic adjunct is present in an amount of 10g/L to 100g/L based on 1L of support.
In a further preferred embodiment, the metallic palladium is present in an amount of 0.5g/L to 20g/L, the co-metal is present in an amount of 0.01g/L to 1.0g/L, the phosphorus is present in an amount of 2g/L to 100g/L (preferably 5g/L to 80 g/L), and the sulfur is present in an amount of 0.0001g/L to 3g/L (preferably 0.01g/L to 1g/L, preferably 0.05g/L to 0.2 g/L) based on 1L of the support.
Wherein the content of the metal palladium is calculated based on the content of palladium element, the content of the auxiliary metal is calculated based on the content of auxiliary metal element, the content of phosphorus is calculated based on the content of phosphorus element, and the content of sulfur is calculated based on the content of sulfur element.
The sulfur-containing organic matter is preferentially adsorbed on the low coordination unsaturated active center on the surface of the catalyst to form a local poisoning phenomenon of an unstable active center on the catalyst, so that the local overheating of the catalyst caused by higher initial activity of the catalyst can be well inhibited, the growth of metal crystal grains and the excessive hydrogenation of cumene to isopropyl cyclohexane are avoided, meanwhile, the generation of cumene can be effectively controlled, and the selectivity of cumene is increased while the operation stability of the catalyst is obviously improved.
In a preferred embodiment, the non-metallic auxiliary optionally further comprises silica;
wherein, the catalyst activity and stability can be improved by adopting silicon dioxide modification (especially modified alumina carrier matrix). When only silica is used as the carrier matrix, the Pd grains are easy to aggregate and grow up at the reaction temperature due to weak interaction between the active component and the carrier, which is unfavorable for the stability of the catalyst, so that the alumina carrier matrix is preferably used.
In a further preferred embodiment, the silica content is from 6 to 300g/L (preferably from 20 to 200 g/L) based on 1L of support. Wherein the content of the silicon dioxide is calculated by the molecular content thereof.
Wherein, after the silicon modification is adopted, the pore diameter of the catalyst is enlarged, and the diffusion speed of reactants and products is improved, thereby improving the conversion rate and the selectivity. In addition, it has been found that the siliceous catalyst has better hydrogenolysis activity and also contributes to the acceleration of the hydrogenolysis reaction rate.
In a preferred embodiment, the catalyst is prepared as follows:
optionally step 1, mixing the carrier with an optional phosphorus-containing compound (preferably an aqueous solution of the phosphorus-containing compound) matrix, drying and roasting to obtain a phosphorus-containing carrier I;
optional step 2: mixing the carrier or the carrier I with aqueous solution of silica gel, drying and roasting to obtain the carrier II containing phosphorus and/or silicon.
Step 3, adding the carrier, the carrier I or the carrier II into a solution containing a palladium compound and an optional auxiliary metal compound, drying and roasting to obtain an oxidation state catalyst precursor I;
step 4, adding the oxidation state catalyst precursor I into a solution of a sulfur-containing compound, and drying to obtain an oxidation state catalyst precursor II;
and 5, carrying out reduction treatment on the oxidation state catalyst precursor I or the oxidation state catalyst precursor II to obtain the catalyst.
In the preparation of the catalyst according to the invention, the drying is carried out as follows: drying at 60-200 ℃ for 4-36 hours, preferably 80-150 ℃ for 6-12 hours, more preferably 110 ℃ for 8 hours; and/or the roasting temperature is 400-700 ℃, preferably 400-500 ℃; and/or, reducing with hydrogen, preferably the reducedThe temperature is 40 to 300 ℃, preferably 200 to 300 ℃, more preferably 250 ℃; the volume space velocity of hydrogen is 50-500 h -1 Preferably 80 to 150 hours -1 More preferably 100h -1 。
In the presence of a supported palladium catalyst, the catalyst realizes the hydrogenolysis of alpha, alpha-dimethylbenzyl alcohol and isopropyl benzene at a higher temperature to prepare isopropyl benzene. The hydrogenation method of the invention effectively controls the generation of heavy components such as cumene and methyl styrene polymer, increases the conversion rate of alpha, alpha-dimethylbenzyl alcohol, obviously improves the operation stability of the catalyst, increases the yield of the cumene, and reduces the unit consumption of the cumene for producing propylene oxide.
In a preferred embodiment, in the reaction, the reaction pressure is controlled to be 1.0 to 5.0MPa, preferably 2.0 to 3.0MPa.
In a preferred embodiment, in the reaction, the liquid phase volume space velocity is controlled to be 1.0 to 30 hours -1 Preferably 8 to 20 hours -1 。
In a preferred embodiment, the molar ratio of hydrogen to α, α -dimethylbenzyl alcohol in the reaction is greater than 4, preferably greater than 5.
In a preferred embodiment, in the reaction, a liquid phase circulation process is used, the circulation ratio being 1 to 10, preferably 3 to 8.
In a preferred embodiment, the hydrocarbon feed comprising α, α -dimethylbenzyl alcohol further comprises cumene.
In a further preferred embodiment, the hydrocarbon material containing α, α -dimethylbenzyl alcohol contains 10 to 90% by weight of α, α -dimethylbenzyl alcohol, 10 to 89% by weight of cumene, and 0 to 1% by weight of co-cumene.
Among them, the content of the dicumyl benzene is preferably 0.01 to 1wt%, for example, 0.01 to 0.1wt%, 0.1 to 0.5wt%, 0.5 to 1wt%, 0.1 to 1wt%.
In a still further preferred embodiment, the weight ratio of α, α dimethylbenzyl alcohol to cumene is (0.2 to 4): 1, preferably (1 to 4): 1.
In a preferred embodiment, the hydrocarbon material containing α, α -dimethylbenzyl alcohol further comprises acetophenone, methylstyrene, n-propylbenzene, n-butylbenzene, and the like.
Wherein, the hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol can be selected from tower bottom liquid after propylene oxide is separated in the process of preparing propylene oxide by a cumene hydroperoxide method or is obtained after the cumene hydroperoxide is reduced.
In a preferred embodiment, the hydrocarbon material contains the cumene in an amount of x% by weight, wherein when x% is less than or equal to 0.1%, the reaction temperature is controlled to be 200-220 ℃ (preferably 220 ℃ is not included); when 0.1 percent of the catalyst is less than or equal to 0.5 percent of the catalyst, controlling the reaction temperature to be 220-240 ℃; when 0.5% < x% (preferably 0.5% < x% +.ltoreq.1%), the reaction temperature is controlled at 240 to 300 ℃ (preferably 240 ℃ is not contained).
In a further preferred embodiment, the hydrocarbon material contains cumene in an amount of x% by weight, wherein when x is less than or equal to 0.1%, the catalyst bed temperature is controlled to be 200-210 ℃; when 0.1 percent of the catalyst is less than or equal to 0.5 percent of the catalyst, controlling the temperature of the catalyst bed to be 220-230 ℃; when 0.5% < x% (preferably 0.5% < x% < 1%), the catalyst bed temperature is controlled to 270 to 300 ℃.
Wherein, when the concentration of cumene in the raw material is higher than 1%, the concentration of cumene may be added thereto to be 0.1%, 0.1% < x% < 0.5% or 0.5% < x% < 1%, or 0.1% < x% < 0.5% or 0.5% < x% < 1% may be diluted to 0.1% or less, and the concentration of 0.5% < x < 1% may be diluted to 0.1% or 0.1% < x% < 0.5%.
According to the method, the catalyst bed temperature is controlled according to the content of the cumene in the raw materials, the content of the cumene in the hydrogenation product is less than 100ppm under a proper working condition, the conversion rate of alpha, alpha-dimethylbenzyl alcohol is more than 99.6%, the selectivity of the cumene is more than 99.7%, and the catalyst continuously and stably runs for 200 hours, so that a better technical effect is obtained, and the method has wide industrial application value.
It is a second object of the present invention to provide the use of the process according to one of the objects of the present invention for the preparation of propylene oxide.
The invention also aims to provide a preparation method of propylene oxide, which comprises the following steps:
1) Cumene hydroperoxide is obtained by cumene oxidation;
2) In the presence of a solid catalyst, cumene hydroperoxide reacts with excessive propylene to obtain propylene oxide and alpha, alpha-dimethylbenzyl alcohol;
3) Separating propylene oxide by rectification to obtain a hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol;
4) The hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol is treated by the method of one of the purposes of the invention to obtain isopropylbenzene, and the isopropylbenzene is recycled to the step 1).
Wherein cumene hydroperoxide is present during the propylene oxide production and under the action of this peroxide cumene forms free radicals, which are easily formed and cumene is formed, whereas in step 4) the reaction is rendered prone to free radical quenching by thermodynamic control.
The endpoints of the ranges and any values disclosed in the present invention are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts the specific catalyst to carry out the reaction, and simultaneously regulates and controls the reaction temperature skillfully according to the content of the cumene in the raw materials, under the combined action of the catalyst and the reaction temperature, not only the energy consumption is saved, but also the yield of the product is ensured;
(2) Under proper working conditions, the method provided by the invention has the advantages that the content of the cumene in the hydrogenation product is less than 100ppm, the conversion rate of the alpha, alpha-dimethylbenzyl alcohol is greater than 99.6%, the selectivity of the cumene is greater than 99.7%, and the catalyst continuously and stably runs for 200 hours, so that a better technical effect is obtained, and the method has wide industrial application value.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
In addition, the specific features described in the following embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, so long as the concept of the present invention is not deviated, and the technical solution formed thereby is a part of the original disclosure of the present specification, and also falls within the protection scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
Content of cumene in hydrogenation product (ppm) =w 1 t
Conversion (%) = (W) of α, α -dimethylbenzyl alcohol 2 0 -W 2 t )/W 2 0 ×100％；
Cumene selectivity (%) = [ (W) 3 t -W 3 0 )/M 2 /(W 2 0 -W 2 t )/M 1 ]×100％
W 1 0 : the quality of the cumene in the raw materialThe weight percentage content; w (W) 1 t The quality of the cumene in the hydrogenation product;
W 2 0 : the mass of the alpha, alpha-dimethylbenzyl alcohol in the raw material; w (W) 2 t : the mass of the alpha, alpha-dimethylbenzyl alcohol in the hydrogenation product;
W 3 0 : the quality of the isopropylbenzene in the raw materials; w (W) 3 t : the quality of cumene in the hydrogenation product;
M 1 is the molar molecular weight of alpha, alpha-dimethylbenzyl alcohol; m is M 2 Is the molar molecular weight of cumene.
[ example 1 ]
1. Catalyst preparation
The catalyst carrier was prepared by mixing 1 liter of alumina with 600 g of an aqueous phosphoric acid solution containing 20g of P, drying at 110℃for 8 hours, and calcining at 400℃for 4 hours.
The above-mentioned carrier 1 liter was mixed with 2000 g of an aqueous solution of palladium chloride acid containing 3.0 g of palladium, dried at 110℃for 8 hours, and calcined at 500℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I.
The above 1L of the catalyst precursor I was mixed with 1000 g of a polysulfide-cyclohexane solution containing 0.2g of sulfur, and dried at 40℃for 8 hours to prepare a sulfur-modified palladium-based catalyst precursor II. Reducing the catalyst precursor II with hydrogen for 4 hours at a reduction temperature of 250 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation operation was performed in a fixed bed reactor, the reactor was charged with the catalyst prepared as described above, and the hydrogenation operation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol was performed in a continuous manner, and the composition of the hydrocarbon feed of α, α -dimethylbenzyl alcohol was shown in table 1.
The operating conditions were as follows:
reaction temperature: 210 DEG C
Reaction pressure: 2.0MPa
Raw material fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluation are shown in Table 6.
[ example 2 ]
1. Catalyst preparation
The catalyst carrier was prepared by mixing 1 liter of alumina with 600 g of an aqueous phosphoric acid solution containing 20g of P, drying at 110℃for 8 hours, and calcining at 400℃for 4 hours.
The above-mentioned carrier 1 liter was mixed with 2000 g of an aqueous solution of palladium chloride acid containing 3.0 g of palladium, dried at 110℃for 8 hours, and calcined at 500℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I.
The above 1L of the catalyst precursor I was mixed with 1000 g of a polysulfide-cyclohexane solution containing 0.2g of sulfur, and dried at 40℃for 8 hours to prepare a sulfur-modified palladium-based catalyst precursor II. Reducing the catalyst precursor II with hydrogen for 4 hours at a reduction temperature of 250 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation operation was performed in a fixed bed reactor, which was filled with the catalyst prepared as described above, and the hydrogenation operation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol was performed in a continuous manner, and the composition of the hydrocarbon feed of α, α -dimethylbenzyl alcohol was shown in table 2.
The operating conditions were as follows:
reaction temperature: 230 DEG C
Reaction pressure: 2.0MPa
Raw material fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluation are shown in Table 6.
[ example 3 ]
1. Catalyst preparation
The catalyst carrier was prepared by mixing 1 liter of alumina with 600 g of an aqueous phosphoric acid solution containing 20g of P, drying at 110℃for 8 hours, and calcining at 400℃for 4 hours.
The above carrier 1 liter was mixed with 2000 g of an aqueous solution of chloropalladate-copper nitrate containing 3.0 g of palladium and 1.0g of copper, and dried at 110℃for 8 hours and calcined at 500℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I.
The above 1L of the catalyst precursor I was mixed with 1000 g of a polysulfide-cyclohexane solution containing 0.2g of sulfur, and dried at 40℃for 8 hours to prepare a sulfur-modified palladium-based catalyst precursor II.
Reducing the catalyst precursor II with hydrogen for 4 hours at a reduction temperature of 250 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation operation was performed in a fixed bed reactor, which was filled with the catalyst prepared as described above, and the hydrogenation operation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol was performed in a continuous manner, and the composition of the hydrocarbon feed of α, α -dimethylbenzyl alcohol was shown in table 2.
The operating conditions were as follows:
reaction temperature: 230 DEG C
Reaction pressure: 2.0MPa
Raw material fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluation are shown in Table 6.
[ example 4 ]
1. Catalyst preparation
The catalyst carrier was prepared by mixing 1 liter of alumina with 600 g of an aqueous phosphoric acid solution containing 20g of P, drying at 110℃for 8 hours, and calcining at 400℃for 4 hours.
The above-mentioned carrier 1 liter was mixed with 2000 g of an aqueous solution of palladium chloride acid containing 3.0 g of palladium, dried at 110℃for 8 hours, and calcined at 500℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I.
Mixing 1L of the catalyst precursor I with a polysulfide-cyclohexane solution containing 0.2g of sulfur1000 g of the mixture was dried at 40℃for 8 hours to prepare a sulfur-modified palladium-based catalyst precursor II. Reducing the catalyst precursor II with hydrogen for 4 hours at a reduction temperature of 250 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation operation was performed in a fixed bed reactor, which was filled with the catalyst prepared as described above, and the hydrogenation operation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol was performed in a continuous manner, and the composition of the hydrocarbon feed of α, α -dimethylbenzyl alcohol was shown in table 3.
The operating conditions were as follows:
reaction temperature: 280 DEG C
Reaction pressure: 2.0MPa
Raw material fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluation are shown in Table 6.
[ example 5 ]
1. Catalyst preparation
The catalyst carrier was prepared by mixing 1 liter of alumina with 600 g of an aqueous phosphoric acid solution containing 20g of P, drying at 110℃for 8 hours, and calcining at 400℃for 4 hours.
The above-mentioned carrier 1 liter was mixed with 2000 g of an aqueous solution of palladium chloride acid containing 3.0 g of palladium, dried at 110℃for 8 hours, and calcined at 500℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. The above 1L of the catalyst precursor I was mixed with 1000 g of a polysulfide-cyclohexane solution containing 0.2g of sulfur, and dried at 40℃for 8 hours to prepare a sulfur-modified palladium-based catalyst precursor II.
Reducing the catalyst precursor II with hydrogen for 4 hours at a reduction temperature of 250 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation operation was carried out in a fixed bed reactor, the reactor was charged with the catalyst prepared as described above, and the hydrogenation operation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol was carried out in a continuous manner, and the composition of the hydrocarbon feed containing cumene at the outlet of the reactor was shown in table 4.
The operating conditions are as follows:
reaction temperature: 300 DEG C
Reaction pressure: 2.0MPa
Raw material fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluation are shown in Table 4.
[ example 6 ]
The procedure of example 3 was repeated, except that: the catalyst further comprises silica.
1 liter of alumina was mixed with 600 g of an aqueous phosphoric acid solution containing 20g of P, and dried at 110℃for 8 hours and calcined at 400℃for 4 hours to prepare a catalyst carrier containing P.
Mixing the catalyst carrier 1L containing P with SiO 2 600 g of silica gel aqueous solution with the mass concentration of 5% is mixed, dried and roasted at 500 ℃ to obtain a carrier containing P/Si;
the above-mentioned P/Si-containing carrier (1 liter) was mixed with 2000 g of an aqueous solution of chloropalladate-cupric nitrate containing 3.0 g of palladium and 1.0g of copper, and dried at 110℃for 8 hours and calcined at 500℃for 4 hours to obtain an oxidized palladium-based catalyst precursor I.
The above 1L of the catalyst precursor I was mixed with 1000 g of a polysulfide-cyclohexane solution containing 0.2g of sulfur, and dried at 40℃for 8 hours to prepare a sulfur-modified palladium-based catalyst precursor II. Reducing the catalyst precursor II with hydrogen for 4 hours at a reduction temperature of 250 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained. The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation operation was performed in a fixed bed reactor, which was filled with the catalyst prepared as described above, and the hydrogenation operation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol was performed in a continuous manner, and the composition of the hydrocarbon feed of α, α -dimethylbenzyl alcohol was shown in table 2.
The operating conditions were as follows:
reaction temperature: 230 DEG C
Reaction pressure: 2.0MPa
Raw material fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluation are shown in Table 6.
[ example 7 ]
1 liter of alumina was mixed with 600 g of an aqueous phosphoric acid solution containing 5g of P, and dried at 110℃for 8 hours and calcined at 400℃for 4 hours to prepare a catalyst carrier containing P.
Mixing the catalyst carrier 1L containing P with SiO 2 200g of silica gel aqueous solution with the mass concentration of 5% is mixed, dried and roasted at 500 ℃ to obtain a carrier containing P/Si;
the above-mentioned P/Si-containing carrier (1 liter) was mixed with 2000 g of an aqueous solution of chloropalladate-copper nitrate containing 5.0 g of palladium and 0.05g of copper, and dried at 110℃for 8 hours and calcined at 500℃for 4 hours to obtain an oxidized palladium-based catalyst precursor I.
The above 1L of the catalyst precursor I was mixed with 1000 g of a polysulfide-cyclohexane solution containing 0.01g of sulfur, and dried at 40℃for 8 hours to prepare a sulfur-modified palladium-based catalyst precursor II. Reducing the catalyst precursor II with hydrogen for 4 hours at a reduction temperature of 250 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation operation was performed in a fixed bed reactor, the reactor was charged with the catalyst prepared as described above, and the hydrogenation operation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol was performed in a continuous manner, and the composition of the hydrocarbon feed of α, α -dimethylbenzyl alcohol was shown in table 1.
The operating conditions were as follows:
reaction temperature: 200 DEG C
Reaction pressure: 1.6MPa
Raw material fresh oil volume space velocity: 2.2h -1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 6
The content of the cumin in the hydrogenated product is less than 100ppm, the conversion rate of the alpha, alpha-dimethylbenzyl alcohol is more than 99.6%, and the selectivity of the cumin the product is more than 99.7%.
[ example 8 ]
1 liter of alumina was mixed with 600 g of an aqueous phosphoric acid solution containing 40 g of P, dried at 110℃for 8 hours, and calcined at 400℃for 4 hours to prepare a catalyst carrier containing P.
Mixing the catalyst carrier 1L containing P with SiO 2 600 g of silica gel aqueous solution with the mass concentration of 20 percent is mixed, dried and roasted at the temperature of 500 ℃ to obtain a carrier containing P/Si;
the above-mentioned P/Si-containing carrier (1 liter) was mixed with 2000 g of an aqueous solution of chloropalladate-copper nitrate containing 1.0g of palladium and 0.5g of copper, and dried at 110℃for 8 hours and calcined at 500℃for 4 hours to obtain an oxidized palladium-based catalyst precursor I.
The above 1L of the catalyst precursor I was mixed with 1000 g of a polysulfide-cyclohexane solution containing 0.1 g of sulfur, and dried at 40℃for 8 hours to prepare a sulfur-modified palladium-based catalyst precursor II. Reducing the catalyst precursor II with hydrogen for 4 hours at a reduction temperature of 250 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation operation was performed in a fixed bed reactor, which was filled with the catalyst prepared as described above, and the hydrogenation operation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol was performed in a continuous manner, and the composition of the hydrocarbon feed of α, α -dimethylbenzyl alcohol was shown in table 2.
The operating conditions were as follows:
reaction temperature: 220 DEG C
Reaction pressure: 2.8MPa of raw material fresh oil volume space velocity: 2.5h -1
Liquid phase circulation ratio: 5
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 6
The content of the cumin in the hydrogenated product is less than 100ppm, the conversion rate of the alpha, alpha-dimethylbenzyl alcohol is more than 99.6%, and the selectivity of the cumin the product is more than 99.7%.
[ example 9 ]
1 liter of alumina was mixed with 600 g of an aqueous phosphoric acid solution containing 60 g of P, dried at 110℃for 8 hours, and calcined at 400℃for 4 hours to prepare a catalyst carrier containing P.
Mixing the catalyst carrier 1L containing P with SiO 2 600 g of silica gel aqueous solution with the mass concentration of 10 percent is mixed, dried and roasted at the temperature of 500 ℃ to obtain a carrier containing P/Si;
the above-mentioned P/Si-containing carrier (1 liter) was mixed with 2000 g of an aqueous solution of chloropalladate-copper nitrate containing 10.0 g of palladium and 0.01g of copper, and dried at 110℃for 8 hours and calcined at 500℃for 4 hours to obtain an oxidized palladium-based catalyst precursor I.
The above 1L of the catalyst precursor I was mixed with 1000 g of a polysulfide-cyclohexane solution containing 0.5g of sulfur, and dried at 40℃for 8 hours to prepare a sulfur-modified palladium-based catalyst precursor II. Reducing the catalyst precursor II with hydrogen for 4 hours at a reduction temperature of 250 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation operation was performed in a fixed bed reactor, which was filled with the catalyst prepared as described above, and the hydrogenation operation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol was performed in a continuous manner, and the composition of the hydrocarbon feed of α, α -dimethylbenzyl alcohol was shown in table 3.
The operating conditions were as follows:
reaction temperature: 270 DEG C
Reaction pressure: 3.0MPa
Raw material fresh oil volume space velocity: 2.8h -1
Liquid phase circulation ratio: 6
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 10
The content of the cumin in the hydrogenated product is less than 100ppm, the conversion rate of the alpha, alpha-dimethylbenzyl alcohol is more than 99.6%, and the selectivity of the cumin the product is more than 99.7%.
Comparative example 1
1. Catalyst preparation
The catalyst carrier was prepared by mixing 1 liter of alumina with 600 g of an aqueous phosphoric acid solution containing 20g of P, drying at 110℃for 8 hours, and calcining at 400℃for 4 hours.
The above-mentioned carrier 1 liter was mixed with 2000 g of an aqueous solution of palladium chloride acid containing 3.0 g of palladium, dried at 110℃for 8 hours, and calcined at 500℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I.
The above 1L of the catalyst precursor I was mixed with 1000 g of a polysulfide-cyclohexane solution containing 0.2g of sulfur, and dried at 40℃for 8 hours to prepare a sulfur-modified palladium-based catalyst precursor II. Reducing the catalyst precursor II with hydrogen for 4 hours at a reduction temperature of 250 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
2. Catalyst evaluation
The hydrogenation operation was performed in a fixed bed reactor, the reactor was charged with the catalyst prepared as described above, and the hydrogenation operation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol was performed in a continuous manner, and the composition of the hydrocarbon feed of α, α -dimethylbenzyl alcohol was shown in table 1.
The operating conditions were as follows:
reaction temperature: 160 DEG C
Reaction pressure: 2.0MPa
Raw material fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluation are shown in Table 6.
Comparative example 2
1. Catalyst preparation
The catalyst carrier was prepared by mixing 1 liter of alumina with 600 g of an aqueous phosphoric acid solution containing 20g of P, drying at 110℃for 8 hours, and calcining at 400℃for 4 hours.
The above-mentioned carrier 1 liter was mixed with 2000 g of an aqueous solution of palladium chloride acid containing 3.0 g of palladium, dried at 110℃for 8 hours, and calcined at 500℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I.
The above 1L of the catalyst precursor I was mixed with 1000 g of a polysulfide-cyclohexane solution containing 0.2g of sulfur, and dried at 40℃for 8 hours to prepare a sulfur-modified palladium-based catalyst precursor II.
Reducing the catalyst precursor II with hydrogen for 4 hours at a reduction temperature of 250 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation operation was performed in a fixed bed reactor, which was filled with the catalyst prepared as described above, and the hydrogenation operation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol was performed in a continuous manner, and the composition of the hydrocarbon feed of α, α -dimethylbenzyl alcohol was shown in table 2.
The operating conditions were as follows:
reaction temperature: 200 DEG C
Reaction pressure: 2.0MPa
Raw material fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluation are shown in Table 6.
[ comparative example 3 ]
1. Catalyst preparation
The catalyst carrier was prepared by mixing 1 liter of alumina with 600 g of an aqueous phosphoric acid solution containing 20g of P, drying at 110℃for 8 hours, and calcining at 400℃for 4 hours.
The above-mentioned carrier 1 liter was mixed with 2000 g of an aqueous solution of palladium chloride acid containing 3.0 g of palladium, dried at 110℃for 8 hours, and calcined at 500℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I.
The above 1L of the catalyst precursor I was mixed with 1000 g of a polysulfide-cyclohexane solution containing 0.2g of sulfur, and dried at 40℃for 8 hours to prepare a sulfur-modified palladium-based catalyst precursor II.
The catalyst precursor is preparedII reducing with hydrogen for 4 hours at 250 ℃ with a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation operation was performed in a fixed bed reactor, which was filled with the catalyst prepared as described above, and the hydrogenation operation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol was performed in a continuous manner, and the composition of the hydrocarbon feed of α, α -dimethylbenzyl alcohol was shown in table 3.
The operating conditions were as follows:
reaction temperature: 220 DEG C
Reaction pressure: 2.0MPa
Raw material fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluation are shown in Table 6.
[ comparative example 4 ]
1. Catalyst preparation
The catalyst carrier was prepared by mixing 1 liter of alumina with 600 g of an aqueous phosphoric acid solution containing 20g of P, drying at 110℃for 8 hours, and calcining at 400℃for 4 hours.
The above-mentioned carrier 1 liter was mixed with 2000 g of an aqueous solution of palladium chloride acid containing 3.0 g of palladium, dried at 110℃for 8 hours, and calcined at 500℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I.
The above 1L of the catalyst precursor I was mixed with 1000 g of a polysulfide-cyclohexane solution containing 0.2g of sulfur, and dried at 40℃for 8 hours to prepare a sulfur-modified palladium-based catalyst precursor II. Reducing the catalyst precursor II with hydrogen for 4 hours at a reduction temperature of 250 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
The specific composition of the catalyst is shown in Table 5.
2. Catalyst evaluation
The hydrogenation was carried out in a fixed bed reactor, which was charged with the catalyst prepared as described above, and the hydrogenation of the hydrocarbon feed containing α, α -dimethylbenzyl alcohol was carried out in a continuous manner, and the composition of the hydrocarbon feed of α, α -dimethylbenzyl alcohol was shown in table 4.
The operating conditions were as follows:
reaction temperature: 220 DEG C
Reaction pressure: 2.0MPa
Raw material fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/α, α -dimethylbenzyl alcohol molar ratio: 8
The average results of the 240 hour evaluation are shown in Table 4.
TABLE 1
Raw material composition 1 Weight composition w%
Cumene (isopropyl benzene) 46.3
N-propylbenzene 0.12
Methyl styrene 0.13
Acetophenone derivatives 0.82
Alpha, alpha-dimethylbenzyl alcohol 52.6
And isopropylbenzene 0.06
TABLE 2
Raw material composition 1 Weight composition w%
Cumene (isopropyl benzene) 45.9
N-propylbenzene 0.12
Methyl styrene 0.13
Acetophenone derivatives 0.82
Alpha, alpha-dimethylbenzyl alcohol 52.7
And isopropylbenzene 0.33
TABLE 3 Table 3
Raw material composition 2 Weight composition w%
Cumene (isopropyl benzene) 45.8
N-propylbenzene 0.12
Methyl styrene 0.13
Acetophenone derivatives 0.82
Alpha, alpha-dimethylbenzyl alcohol 52.5
And isopropylbenzene 0.63
TABLE 4 Table 4
Raw material composition 2 Weight composition w%
Cumene (isopropyl benzene) 45.7
N-propylbenzene 0.12
Methyl styrene 0.13
Acetophenone derivatives 0.81
Alpha, alpha-dimethylbenzyl alcohol 52.3
And isopropylbenzene 0.92
TABLE 5
TABLE 6
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The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.

Claims (19)

1. A method for preparing cumene from α, α -dimethylbenzyl alcohol, comprising: in the presence of catalyst and hydrogen, hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol reacts to obtain isopropylbenzene, and the hydrocarbon material contains the isopropylbenzene with the weight percentage ofxIn percent, where, whenxWhen the percentage is less than or equal to 0.1%, controlling the reaction temperature to be 180-220 ℃; when 0.1%<xWhen the percentage is less than or equal to 0.5%, the reaction temperature is controlled to be (200 plus)x*100 -250 ℃; when 0.5%<x%When the reaction temperature was controlled to be (220 +)x*80 320 ℃; the catalystComprising a support, metallic palladium, optionally a co-metal and optionally a non-metallic promoter, wherein the metallic palladium, optionally a co-metal and optionally a non-metallic promoter are supported on the support.
2. The method of claim 1, wherein the step of determining the position of the substrate comprises,
controlling the reaction pressure to be 1.0-5.0 MPa; and/or
Controlling the volume space velocity of the liquid phase to be 1.0-30 h -1 。
3. The method of claim 2, wherein the step of determining the position of the substrate comprises,
controlling the reaction pressure to be 2.0-3.0 MPa; and/or
Controlling the volume space velocity of the liquid phase to be 8-20 h -1 。
4. The method of claim 1, wherein the step of determining the position of the substrate comprises,
adopting a liquid phase circulation process, wherein the circulation ratio is 1-10; and/or
The molar ratio of hydrogen to alpha, alpha-dimethylbenzyl alcohol is greater than 4.
5. The method of claim 4, wherein the step of determining the position of the first electrode is performed,
adopting a liquid phase circulation process, wherein the circulation ratio is 3-8; and/or
The molar ratio of hydrogen to alpha, alpha-dimethylbenzyl alcohol is greater than 5.
6. The method of claim 1, wherein the step of determining the position of the substrate comprises,
the carrier is at least one of silicon oxide, aluminum oxide and active carbon; and/or
The auxiliary metal is selected from at least one of metallic copper, metallic zinc, metallic cobalt, metallic tin, metallic nickel and metallic silver, and/or
The non-metallic auxiliary agent is selected from sulfur and/or phosphorus.
7. The method according to claim 6, wherein the content of the metallic palladium is 0.06g/L to 30g/L, the content of the auxiliary metal is 0.0006g/L to 1.0g/L, and the content of the non-metallic auxiliary agent is 10g/L to 100g/L, based on 1L of the carrier.
8. The method according to claim 7, wherein the content of metallic palladium is 0.5g/L to 20g/L, the content of auxiliary metal is 0.01g/L to 1.0g/L, the content of phosphorus is 2g/L to 100g/L, and the content of sulfur is 0.0001g/L to 3g/L, based on 1L of carrier.
9. The method of claim 6, wherein the non-metallic auxiliary agent optionally further comprises silica.
10. The method according to claim 9, wherein the content of silica is 6 to 300g/L based on 1L of carrier, wherein the content of silica is based on the content of its molecules.
11. The method according to claim 10, wherein the content of silica is 20 to 200g/L based on 1L of carrier, wherein the content of silica is based on the content of its molecules.
12. The method according to any one of claims 1 to 11, wherein the hydrocarbon material contains cumene in an amount of weight percentxIn% wherein,
when (when)xWhen the percentage is less than or equal to 0.1%, controlling the reaction temperature to be 200-220 ℃;
when 0.1%<xWhen the percentage is less than or equal to 0.5%, controlling the reaction temperature to be 220-240 ℃;
when 0.5%<x% of the reaction temperature is controlled to be 240-300 ℃.
13. The method according to claim 12, wherein the hydrocarbon material contains cumene in a weight percentage ofxIn% wherein,
when (when)xWhen the percentage is less than or equal to 0.1%, controlling the reaction temperature to be 200-210 ℃;
when 0.1%<xWhen the percentage is less than or equal to 0.5%, controlling the reaction temperature to be 220-230 ℃;
when 0.5%<x% of the reaction temperature is controlled to be 270-300 ℃.
14. The method of claim 12, wherein the hydrocarbon feed comprising α, α -dimethylbenzyl alcohol further comprises cumene.
15. The method of claim 14, wherein the hydrocarbon material containing α, α -dimethylbenzyl alcohol comprises 10 to 90wt% α, α -dimethylbenzyl alcohol, 10 to 89wt% cumene, and 0 to 1wt% naphtalene.
16. The method according to claim 12, wherein the weight ratio of α, α dimethylbenzyl alcohol to cumene is (0.2 to 4): 1.
17. The method according to claim 16, wherein the weight ratio of α, α dimethylbenzyl alcohol to cumene is (1-4): 1.
18. Use of the process according to any one of claims 1 to 17 for the preparation of propylene oxide.
19. A method for preparing propylene oxide, comprising the following steps:
1) Cumene hydroperoxide is obtained by cumene oxidation;
2) In the presence of a solid catalyst, cumene hydroperoxide reacts with excessive propylene to obtain propylene oxide and alpha, alpha-dimethylbenzyl alcohol;
3) Separating propylene oxide by rectification to obtain a hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol;
4) Treatment of a hydrocarbon feed containing α, α -dimethylbenzyl alcohol by a process according to any one of claims 1 to 17 to produce cumene, which is recycled to step 1).
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