CN112679294B - Preparation method and application of isopropylbenzene - Google Patents
Preparation method and application of isopropylbenzene Download PDFInfo
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Abstract
The invention provides a preparation method of isopropylbenzene, the obtained isopropylbenzene and application thereof, wherein the preparation method comprises the following steps: the hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol and hydrogen are used as raw materials, and the cumene is obtained through a first catalyst bed layer and a second catalyst bed layer which are connected in series; the catalyst filling amount of the first catalyst bed layer is larger than that of the second catalyst bed layer, the reaction temperature of the first catalyst bed layer is lower than that of the second catalyst bed layer, and the liquid phase volume space velocity is higher than that of the second catalyst bed layer. The method realizes the preparation of the isopropylbenzene by converting the alpha, alpha-dimethylbenzyl alcohol with high activity and high selectivity, and improves the running stability of the device and the quality of the isopropylbenzene; the obtained isopropylbenzene product has low impurity content and excellent performance, obtains better technical effect, and has wide industrial application value.
Description
Technical Field
The invention relates to cumene preparation, in particular to cumene preparation by utilizing alpha, alpha-dimethylbenzyl alcohol hydrogenolysis.
Background
Propylene Oxide (PO) is an important organic chemical raw material, and is mainly used for producing polyether polyol, propylene glycol ether and the like, wherein the consumption proportion of the polyether polyol is about 70%. Currently, commercial processes for PO production mainly include chlorohydrin process, co-oxidation process (PO/SM) and cumene peroxide recycle process (CHP). The process has the following advantages: the conversion rate and the selectivity of the whole process are very high; the product only has PO, is not influenced by the fluctuation of the price of the byproduct styrene, and can bring more stable economic benefit to manufacturers; the process flow is relatively simple, the fixed investment is 1/3 lower than that of the PO/SM method, and the CHP process has lower requirement on equipment corrosion resistance. In the technology for producing propylene oxide by the CHP method, a large amount of alpha, alpha-dimethylbenzyl alcohol (DMBA) is generated in the propylene epoxidation process, cumene is required to be generated through hydrogenolysis reaction, and the cumene is oxidized to generate CHP and is participated in the reaction cycle again. The quality of cumene is mainly that the impurity content such as ethylbenzene, isopropyl cyclohexane, alpha-methyl styrene, and cumene directly affect the stability of the operation of the oxidation unit and the epoxidation unit and the quality of PO products.
U.S. Pat. No. 3,182 discloses a process for preparing cumene by catalytic hydrogenolysis of α, α -dimethylbenzyl alcohol by the technique of H 2 The catalyst is a hydrogen source, cu-Cr is used as a catalyst, the conversion rate of alpha, alpha-dimethylbenzyl alcohol reaches 99 percent, but the selectivity is lower than 98 percent, and Cr element is used in the preparation of the catalyst, so that the environment pollution is serious.
Chinese patent CN102464567A proposes a method for preparing isopropylbenzene by hydrogenolysis of alpha, alpha-dimethylbenzyl alcohol, which adopts a CuO-ZnO-Al2O3-MgO-MnO catalyst and mainly solves the problems of poor catalyst stability and serious environmental pollution in the prior art.
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% at a reaction temperature lower than 160 ℃, and the strong acidity of the carrier in this patent obviously leads to polymerization of methyl styrene as an intermediate product of dehydration of α, α -dimethylbenzyl alcohol, increasing the content of α -methylstyrene, cumene and other heavy components in the cumene product.
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 the isopropylbenzene is lower than 98.5%, so that the impurity content in the isopropylbenzene product is higher.
The active metals commonly used at present include noble metals such as Pt and Pd, and Ni, co, cu, and the like. Because different metal types have different hydrogenation activities, the hydrogenation performance is required to be modulated through the load capacity, the number of active centers and modification, so that the AMS intermediate product is selectively hydrogenated to isopropylbenzene, and side reactions such as deep hydrogenation, polymerization and the like are inhibited. The hydrogenolysis catalyst with high activity and high selectivity is prepared by selecting proper carrier-supported metal, so that the coupling of two reactions of dehydration and hydrogenation is realized.
In the prior art, more improvement of activity and selectivity of alpha, alpha-dimethylbenzyl alcohol hydrogenolysis by improving a catalyst appears, and the technical problem of how to control the yield and the product quality of cumene in the design and development of a hydrogenolysis process is less involved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of isopropylbenzene, which adopts alpha, alpha-dimethylbenzyl alcohol to hydrogenate and prepare the isopropylbenzene, and mainly solves the technical problems of unstable downstream process operation and poor product quality caused by impurities such as isopropyl cyclohexane, alpha-dimethylbenzyl alcohol, alpha-methylstyrene, and isopropylbenzene in the isopropylbenzene production technology in the prior art. Provides a preparation method of isopropylbenzene, which converts alpha, alpha-dimethylbenzyl alcohol with high activity and high selectivity to prepare the isopropylbenzene, and improves the running stability of the device and the quality of the isopropylbenzene.
The invention aims to provide a preparation method of cumene, which comprises the following steps: the hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol and hydrogen are used as raw materials, and the cumene is obtained through a first catalyst bed layer and a second catalyst bed layer which are connected in series (contact reaction); the catalyst filling amount of the first catalyst bed layer is larger than that of the second catalyst bed layer, the reaction temperature of the first catalyst bed layer is lower than that of the second catalyst bed layer, and the liquid phase volume space velocity is higher than that of the second catalyst bed layer.
In the invention, the reaction process of two catalyst beds is regulated and controlled, including regulation and control among reaction temperature, liquid phase volume space velocity and catalyst filling amount, specifically, the filling amount of a first catalyst bed is obviously higher than that of a second catalyst bed, but the first catalyst bed is controlled to be at low temperature and high space velocity to carry out most reactions; then, the unreacted raw materials are further reacted on a second bed layer (with small filling amount and metal-containing auxiliary agent) with high temperature and low space velocity.
In a preferred embodiment, the second catalyst bed is packed with a second catalyst comprising metal Pd and/or its oxides, metal promoters and/or their oxides, and a support.
In a further preferred embodiment, the metal promoter is selected from at least one of Fe, co, ni, ca, mg, cu, preferably from at least one of Ni, mg and Cu.
In a preferred embodiment, the first catalyst bed is packed with a first catalyst comprising metallic Pd and/or oxide, and a support.
In a further preferred embodiment, the content of metallic Pd and/or its oxide in the first catalyst bed is from 0.006g/L to 30g/L, preferably from 0.06g/L to 10g/L.
In a preferred embodiment, the content of metal Pd and/or its oxide in the second catalyst is 0.006g/L to 30g/L; the content of the metal auxiliary agent and/or the oxide thereof is 0.0001 g/L-2.0 g/L.
In a further preferred embodiment, the content of metal Pd and/or its oxide in the second catalyst is from 0.06g/L to 10g/L; the content of the metal auxiliary agent and/or the oxide thereof is 0.001 g/L-1.2 g/L.
In a preferred embodiment, the support is selected from at least one of alumina, silica, zirconia and activated carbon, preferably alumina.
In a preferred embodiment, the source of the metal Pd is selected from at least one of chloropalladac acid, palladium ammine complex and palladium nitrate; the source of the metal auxiliary and/or the oxide thereof is not particularly limited, and is, for example, but not limited to, at least one of a chloride of the metal auxiliary, a nitric acid compound of the metal auxiliary, an acetic acid compound of the metal auxiliary, and the like.
In a preferred embodiment, the second catalyst comprises phosphorus and/or oxides thereof and optionally silica.
In a further preferred embodiment, the content of phosphorus and/or its oxide in the catalyst is 10g/L to 100g/L, preferably 20g/L to 60g/L, based on the content of phosphorus element therein.
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.
In a still further preferred embodiment, the silica content in the catalyst is from 0 to 600g/L, preferably from 0 to 400g/L, for example from 0 to 200g/L. Wherein the content of the silicon dioxide is calculated by the molecular content thereof.
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. After the silicon modification is adopted, the pore diameter of the catalyst is enlarged, and the diffusion speed of reactants and products is improved, so that the conversion rate and the selectivity are improved. In addition, it has been found that the siliceous catalyst has better dehydration activity and also contributes to the acceleration of the hydrogenolysis reaction rate.
In a preferred embodiment, the second catalyst further comprises a promoter, preferably the promoter is a sulfur-containing compound, the source of which is a sulfur-containing organic compound.
Preferably, the carrier, the active components and the auxiliary agent loaded on the carrier are taken as a catalyst main body, and the auxiliary catalyst is loaded on the catalyst main body.
In a further preferred embodiment, in the second catalyst, the content of the cocatalyst is 0 to 5g/L, preferably 0.01 to 1g/L, wherein the cocatalyst is used in an amount based on the amount of elemental sulfur used therein.
In the present invention, the source of the sulfur-containing compound is not particularly limited, but is preferably, but not limited to, at least one of t-nonyl polysulfide, t-butyl polysulfide, thiophene, etc.
The sulfur-containing organic matter is preferentially adsorbed on the low coordination unsaturated active center on the surface of the second 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 better inhibited, the growth of metal crystal grains and the excessive hydrogenation of cumene to isopropyl cyclohexane are avoided, meanwhile, the generation of cumene (2, 3-dimethyl-2, 3-diphenyl butane) 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 volume ratio of the catalyst loading of the first catalyst bed to the catalyst loading of the second catalyst bed is (1-6): 1, preferably (2 to 4): 1.
in the invention, the filling amount of the first catalyst bed is obviously higher than that of the second catalyst bed, so that raw materials react as much as possible in the first catalyst bed, and if the rest is not completely reacted, the raw materials enter the second catalyst bed to react at a slightly high temperature and a slightly low volume space velocity. Specifically, when the concentration of reactants in the raw materials is higher, the heat release amount in the reaction process is larger, so that the first bed layer adopts a liquid phase circulation mode, the total volume airspeed is high, the effect of heat is achieved, the formation of excessive temperature and local hot spots of the bed layer is prevented, and the selectivity and the stability of the catalyst are facilitated; while the second bed adopts a high temperature and a low space velocity, thereby realizing high conversion of a small amount of residual reactants.
In a preferred embodiment, the reaction temperature of the first catalyst bed is 130-190 ℃, the reaction pressure is 0.1-5 MPa, and the liquid phase volume space velocity is 1.0-20 h -1 。
Wherein the liquid phase is fresh oil, and the fresh oil refers to raw material feeding which is not diluted by liquid phase circulation.
In a further preferred embodiment, the reaction temperature of the first catalyst bed is 150-170 ℃, the reaction pressure is 0.5-3.0 MPa, and the liquid phase volume space velocity is 1-5 h -1 The circulation ratio is 2-8.
In a preferred embodiment, the reaction temperature of the second catalyst bed is 150-230 ℃, the reaction pressure is 0.1-5 MPa, and the liquid phase volume space velocity is 2.0-10 h -1 。
In a further preferred embodiment, the reaction temperature of the second catalyst bed is 160-190 ℃, the reaction pressure is 0.5-3 MPa, and the liquid phase volume space velocity is 4-8 h -1 。
The two-stage bed operation is adopted, the process is more flexible, the operation elasticity is high, and the high-selectivity conversion of the dimethylbenzyl alcohol can be realized.
In a preferred embodiment, the volume ratio of hydrogen to liquid phase in the first catalyst bed is 300 to 1000, preferably 400 to 800, wherein the liquid phase refers to a hydrocarbon feed containing α, α -dimethylbenzyl alcohol.
In a preferred embodiment, the volume ratio of hydrogen to liquid phase in the second catalyst bed is from 100 to 800, preferably from 200 to 400, wherein the liquid phase refers to the hydrocarbon material after treatment with the first catalyst bed.
In a preferred embodiment, the first catalyst bed is a liquid phase recycle process with a recycle ratio of from 1 to 10.
In a preferred embodiment, the hydrocarbon feed containing α, α -dimethylbenzyl alcohol comprises predominantly α, α -dimethylbenzyl alcohol.
In a further preferred embodiment, the hydrocarbon material of the α, α -dimethylbenzyl alcohol further comprises cumene, acetophenone, α -methylstyrene and cumyl benzene.
In a still further preferred embodiment, the hydrocarbon feed of α, α -dimethylbenzyl alcohol further comprises cumene hydroperoxide, preferably in an amount of 1 to 2000ppm.
In a preferred embodiment, the hydrocarbon material of the alpha, alpha-dimethylbenzyl alcohol comprises 0.01-99.99 wt% of alpha, alpha-dimethylbenzyl alcohol, 0-99.9 wt% of isopropylbenzene, 0.01-0.5 wt% of isopropylbenzene, 0.01-0.15 wt% of n-propylbenzene, 0.01-0.2 wt% of cumene hydroperoxide, 0.1-1.5 wt% of acetophenone and 0.01-0.5 wt% of alpha-methylstyrene.
For example, the hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol is tower kettle material obtained by rectifying the product of the reaction of cumene hydroperoxide and propylene to prepare propylene oxide and separating propylene oxide.
According to the invention, hydrocarbon materials containing alpha, alpha-dimethylbenzyl alcohol and hydrogen pass through a first catalyst bed layer at a lower temperature in the presence of a supported Pd catalyst, cumene hydroperoxide in the hydrocarbon materials is completely hydrogenated to alpha, alpha-dimethylbenzyl alcohol, and more than 95% of the alpha, alpha-dimethylbenzyl alcohol is hydrogenated and dehydrated to cumene; the second catalyst bed layer realizes complete hydrogenation conversion of residual alpha, alpha-dimethylbenzyl alcohol to isopropylbenzene at a higher temperature.
The hydrogenation method can realize the high-selectivity conversion of the alpha, alpha-dimethylbenzyl alcohol to the isopropylbenzene, effectively control the generation of the isopropylbenzene, the methyl styrene polymer and other heavy components, and simultaneously inhibit the excessive hydrogenation of the isopropylbenzene to the isopropyl cyclohexane. The quality of the isopropylbenzene product is improved while the operation stability of the catalyst is obviously improved. In the invention, the conversion rate of the dimethylbenzyl alcohol can reach more than 99.9%, and the complete conversion is basically realized.
In the invention, under the working conditions that the reaction temperature of the first section catalyst bed layer is 150 ℃, the pressure is 1.5MPa, the reaction temperature of the second section catalyst bed layer is 170 ℃, the pressure is 1.3MPa, the content of cumene hydroperoxide in the hydrogenated product cumene is 0ppm, the content of alpha-methylstyrene is 5ppm, the content of alpha, alpha-dimethylbenzyl alcohol is less than 50ppm, the increment of cumene is <100ppm, and the selectivity of cumene is more than 99.8%. The cumene product obtained by the preparation method disclosed by the invention has low impurity content and excellent performance, achieves a better technical effect, and has wide industrial application value.
The second catalyst of the present invention is prepared as follows:
step 1, mixing a phosphorus-containing compound (preferably an aqueous solution of the phosphorus-containing compound) with a carrier, drying and roasting to obtain a phosphorus-containing carrier;
Step 2, adding the phosphorus-containing carrier into a palladium compound-containing solution, drying and roasting to obtain an oxidation state catalyst precursor;
and 3, carrying out reduction treatment on the oxidation state catalyst precursor to obtain a pre-reduced catalyst precursor.
In a preferred embodiment, step 1' is optionally performed after step 1 and before step 2:
step 1': mixing the carrier containing phosphorus with aqueous solution of silica gel, drying and roasting to obtain the carrier containing phosphorus/silicon dioxide.
In a preferred embodiment, in step 1, step 2 and step 1', the drying is performed as follows: drying at 60-200 ℃ for 4-36 hours, preferably at 80-150 ℃ for 6-12 hours, more preferably at 110 ℃ for 8 hours.
In the present invention, the phosphorus-containing compound described in step 1 is not particularly limited, but is preferably at least one of phosphoric acid, potassium dihydrogen phosphate, phosphorous acid, calcium phosphate, ammonium hydrogen phosphate, and the like.
In a preferred embodiment, in step 1, step 2 and step 1', the firing temperature is 400 to 700 ℃, preferably 400 to 600 ℃.
In a preferred embodiment, in step 2, the solution of palladium-containing compound further comprises a metal-containing auxiliary compound.
In the present invention, the carrier is not particularly limited, and may preferably include at least one selected from the group consisting of alumina, silica, and activated carbon, preferably alumina; the palladium-containing compound is not particularly limited, and is preferably but not limited to at least one of palladium chloride, palladium nitrate, palladium chloride acid, and the like; the metal-containing auxiliary compound is not particularly limited, and for example, but not limited to, at least one of a metal-containing auxiliary chloride, a metal-containing auxiliary nitrate compound, a metal-containing auxiliary acetate compound, and the like, and preferably, the metal auxiliary is at least one selected from the group consisting of metallic copper, metallic zinc, metallic cobalt, metallic tin, metallic nickel, and metallic silver, for example, metallic copper.
In a preferred embodiment, in step 3, the reduction treatment is performed with hydrogen.
In a further preferred embodiment, in step 3, the temperature of the reduction is between 20 and 300 ℃, preferably between 100 and 300 ℃; the volume space velocity of hydrogen is 50-500 h -1 Preferably 80 to 150 hours -1 More preferably 100h -1 。
In a preferred embodiment, the method further comprises step 4:
and step 4, adding the pre-reduced catalyst precursor into a solution of a sulfur-containing compound, and drying to obtain the catalyst.
In a further preferred embodiment, the sulfur-containing compound is selected from at least one of t-nonyl polysulfide, t-butyl polysulfide, thiophene, dimethyl disulfide.
In the preparation method of the second catalyst of the invention, the catalyst is based on 1L carrier: the palladium-containing compound is used in an amount of 0.006g/L to 30g/L, preferably, the palladium-containing compound is used in an amount of 0.06g/L to 10g/L, based on the amount of palladium element used therein; and/or the metal-containing auxiliary compound is used in an amount of 0.0001 to 2.0g/L, preferably 0.001 to 1.2g/L, based on the amount of the metal element therein; and/or the phosphorus-containing compound is used in an amount of 10g/L to 100g/L, preferably 20g/L to 60g/L, wherein the phosphorus-containing compound is used in an amount based on the amount of phosphorus element used therein; and/or the amount of the sulfur-containing organic matter is 0 to 5g/L, preferably 0.01g/L to 1g/L, more preferably 0.05g/L to 0.2g/L, wherein the amount of the sulfur-containing organic matter is calculated based on the amount of sulfur element used therein; and/or the amount of silica gel is from 0 to 600g/L, preferably from 0 to 400g/L, for example from 0 to 200g/L, wherein the amount of silica gel is based on the amount of silica used therein.
In the preparation method of the catalyst, the solution is formed by fully dissolving the solute in the good solvent, and is preferably an aqueous solution.
It is a further 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.
In a preferred embodiment, a process for the preparation of propylene oxide is carried out as follows:
step 1, cumene hydroperoxide is obtained through cumene oxidation;
step 2, reacting cumene hydroperoxide with propylene to obtain propylene oxide and alpha, alpha-dimethylbenzyl alcohol;
step 3, obtaining hydrocarbon materials containing alpha, alpha-dimethylbenzyl alcohol after separating epoxypropane by rectification;
and 4, treating the obtained hydrocarbon material containing the alpha, alpha-dimethylbenzyl alcohol by using the method disclosed by the invention to obtain isopropylbenzene, and recycling the isopropylbenzene back to the step 1 for recycling.
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 obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically disclosed in the present invention. In the above, 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 in the present invention.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method realizes the preparation of the isopropylbenzene by converting the alpha, alpha-dimethylbenzyl alcohol with high activity and high selectivity, and improves the running stability of the device and the quality of the isopropylbenzene.
(2) The cumene product obtained by the preparation method disclosed by the invention has low impurity content and excellent performance, achieves a better technical effect, and 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.
The composition of the raw materials used in the experiment is shown in Table 1.
Table 1: composition of raw materials
Wherein, the content of each component in the table 1 is obtained by gas chromatography detection.
In the analysis of the product:
cumene selectivity (%) = [ (W) t 2 -W 0 2 )/(W 0 1 -W t 1 )]×100％；
w 0 1 : the mass percentage of the alpha, alpha-dimethylbenzyl alcohol in the raw material; w (w) t 1 : the mass percentage of the alpha, alpha-dimethylbenzyl alcohol in the product;
w 0 2 : the raw materials comprise the following components in percentage by mass; w (w) t 2 : the product comprises the following components in percentage by mass. And (3) main composition analysis of the catalyst: the composition of specific elements in the catalyst is measured by an X-ray fluorescence analysis method, different elements have characteristic X-ray spectrums with different wavelengths, the fluorescence intensity of each spectrum is in a certain relation with the concentration of the elements, and qualitative and quantitative analysis can be performed by measuring the wavelength and the intensity of the characteristic X-ray spectrum of the element to be measured.
Remarks 1L catalyst weight is 550-580 g
[ example 1 ]
1. Catalyst preparation
a. First catalyst bed catalyst preparation
1 liter of the alumina carrier 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 450℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 Palladium-based catalysts were obtained, and the specific composition of the catalysts is shown in table 2.
b. Second catalyst bed catalyst preparation
1 liter of an alumina carrier was mixed with 2000 g of an aqueous solution of chloropalladate-nickel nitrate containing 3.0 g of palladium and 0.3 g of nickel, dried at 110℃for 8 hours and calcined at 550℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 Palladium-based catalysts were obtained, and the specific composition of the catalysts is shown in table 2.
2. Catalyst evaluation
The hydrogenation of a hydrocarbon feed containing α, α -dimethylbenzyl alcohol was carried out in a continuous manner, said feed passing through a first catalyst bed and then through a second catalyst bed, the catalyst loading of the two catalyst beds being in a volume ratio of 4: the operating conditions for both reactors were as follows:
first catalyst bed:
reaction temperature: 150 DEG C
Reaction pressure: 1.5MPa
Fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio: 400
A second catalyst bed:
reaction temperature: 170 DEG C
Reaction pressure: 1.3MPa
Liquid phase volume space velocity: 8h -1
Hydrogen/fresh oil volume ratio: 200
The average results of the 200 hour evaluation are shown in Table 3.
[ example 2 ]
1. Catalyst preparation
a. First catalyst bed catalyst preparation
1 liter of the alumina carrier 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 450℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 Palladium-based catalysts were obtained, and the specific composition of the catalysts is shown in table 2.
b. Second catalyst bed catalyst preparation
1 liter of an alumina carrier was mixed with 2000 g of an aqueous solution of palladium chloride acid-nickel nitrate-magnesium nitrate containing 3.0 g of palladium, 0.2 g of nickel and 0.1 g of magnesium, and dried at 110℃for 8 hours and calcined at 550℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 Palladium-based catalysts were obtained, and the specific composition of the catalysts is shown in table 2.
2. Catalyst evaluation
The hydrogenation of a hydrocarbon feed containing α, α -dimethylbenzyl alcohol was carried out in a continuous manner, said feed passing through a first catalyst bed and then through a second catalyst bed, the catalyst loading of the two catalyst beds being in a volume ratio of 4: the operating conditions for both reactors were as follows:
First catalyst bed:
reaction temperature: 150 DEG C
Reaction pressure: 1.5MPa
Fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio: 400
A second catalyst bed:
reaction temperature: 170 DEG C
Reaction pressure: 1.3MPa
Liquid phase volume space velocity: 8h -1
Hydrogen/fresh oil volume ratio: 100
The average results of the 200 hour evaluation are shown in Table 3.
[ example 3 ]
1. Catalyst preparation
a. First catalyst bed catalyst preparation
1 liter of the alumina carrier 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 450℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 Palladium-based catalysts were obtained, and the specific composition of the catalysts is shown in table 2.
b. Second catalyst bed catalyst preparation
1 liter of an alumina carrier was mixed with 2000 g of an aqueous solution of chloropalladate-cupric nitrate containing 3.0 g of palladium and 0.3 g of Cu, and dried at 110℃for 8 hours, and calcined at 550℃for 4 hours, to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 Palladium-based catalysts were obtained, and the specific composition of the catalysts is shown in table 2.
2. Catalyst evaluation
The hydrogenation operation of the hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol is carried out in a continuous mode, wherein the material passes through a first catalyst bed layer after the material is de-weighted, and then passes through a second catalyst bed layer, and the volume ratio of the catalyst loading amounts of the two catalyst bed layers is 4: the operating conditions for both reactors were as follows:
first catalyst bed:
reaction temperature: 150 DEG C
Reaction pressure: 1.5MPa
Fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio: 400
A second catalyst bed:
reaction temperature: 170 DEG C
Reaction pressure: 1.3MPa
Liquid phase volume space velocity: 8h -1
Hydrogen/fresh oil volume ratio: 100
The average results of the 200 hour evaluation are shown in Table 3.
[ example 4 ]
The procedure of example 2 was repeated, except that the second catalyst was prepared differently:
the catalyst carrier was prepared by mixing 1 liter of alumina with 600 g of an aqueous phosphoric acid solution containing 60 g 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 1.0 g of copper, and dried at 110℃for 8 hours and calcined at 500℃for 4 hours to prepare an oxidized palladium-based catalyst precursor.
The oxidation state palladium-based catalyst precursor is reduced by hydrogen for 4 hours, the reduction temperature is 35 ℃, and the hydrogen volume space velocity is 100 hours -1 A reduced palladium-based catalyst precursor is obtained.
The above-mentioned reduced palladium-based catalyst precursor (1 liter) was impregnated with 550 g of a cyclohexane solution containing 0.1 g of t-nonyl polysulfide, and dried at 110℃to obtain a catalyst. The main composition and properties of the catalyst are shown in tables 2 and 3, respectively.
Examples 5 to 8
The procedure of example 4 was repeated, except that: the P content in the aqueous phosphoric acid solution was 100 g, 10 g, 20 g, 40 g, respectively, and di-t-nonyl polysulfide having sulfur content of 0.01g, 0.05g, 0.2 g, and 1g, respectively, was used.
In examples 5 to 8, the hydrogenolysis effect of α, α -dimethylbenzyl alcohol was similar to that of example 4, specifically, cumene hydroperoxide content in cumene hydrogenation product was 0ppm, α -methylstyrene content was less than 15ppm, α, α -dimethylbenzyl alcohol content was less than 200ppm, and the cumene increment was less than 100ppm, and the cumene selectivity was >99.8%.
[ example 9 ]
The procedure of example 2 was repeated, except that: the preparation of the catalyst is different, and specifically comprises the following steps:
1 liter of alumina was mixed with 600 g of an aqueous phosphoric acid solution containing 27 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 5% aqueous silica gel solution is mixed, dried and roasted at 500 ℃ to obtain the product containing P/SiO 2 Is a carrier of (a).
The mixture containing P/SiO 2 The carrier 1L of (C) was mixed with 2000 g of an aqueous solution of chloropalladate-copper nitrate containing 3.0 g of palladium and 1.0 g of copper, and dried at 110℃for 8 hours and calcined at 500℃for 4 hours to prepare an oxidized palladium-based catalyst precursor.
The oxidation state palladium-based catalyst precursor is reduced by hydrogen for 4 hours, the reduction temperature is 35 ℃, and the hydrogen volume space velocity is 100 hours -1 A reduced palladium-based catalyst precursor is obtained.
The above-mentioned reduced palladium-based catalyst precursor (1 liter) was impregnated with 550 g of a cyclohexane solution containing 0.1 g of t-nonyl polysulfide to obtain a palladium-based catalyst. The main composition and properties of the catalyst are shown in tables 2 and 3, respectively.
Examples 10 to 12
The procedure of example 9 was repeated, except that: the concentration of the aqueous silica gel solution was 10%, 20% and 30%, respectively.
In examples 10 to 12, the hydrogenolysis effect of α, α -dimethylbenzyl alcohol was similar to that of example 9, specifically, cumene hydroperoxide content in cumene hydrogenation product was 0ppm, α -methylstyrene content was less than 15ppm, α, α -dimethylbenzyl alcohol content was less than 200ppm, and the cumene increment was less than 100ppm, and the cumene selectivity was >99.8%.
[ example 13 ]
1. Catalyst preparation
a. First catalyst bed catalyst preparation
1 liter of an alumina carrier was mixed with 2000 g of an aqueous solution of palladium chloride acid containing 10 g of palladium, dried at 110℃for 8 hours, and calcined at 450℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
b. Second catalyst bed catalyst preparation
1 liter of an alumina carrier was mixed with 2000 g of an aqueous solution of chloropalladate-copper nitrate containing 10 g of palladium and 0.001 g of Cu, dried at 110℃for 8 hours, and calcined at 550℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
2. Catalyst evaluation
The hydrogenation operation of the hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol is carried out in a continuous mode, wherein the material passes through a first catalyst bed layer after the material is de-weighted, and then passes through a second catalyst bed layer, and the volume ratio of the catalyst loading amounts of the two catalyst bed layers is 4: the operating conditions for both reactors were as follows:
First catalyst bed:
reaction temperature: 170 DEG C
Reaction pressure: 0.5MPa
Fresh oil volume space velocity: 1h -1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio: 800
A second catalyst bed:
reaction temperature: 190 DEG C
Reaction pressure: 0.5MPa
Liquid phase volume space velocity: 4h -1
Hydrogen/fresh oil volume ratio: 400.
[ example 14 ]
1. Catalyst preparation
a. First catalyst bed catalyst preparation
1 liter of the alumina carrier was mixed with 2000 g of an aqueous solution of palladium chloride acid containing 0.06 g of palladium, dried at 110℃for 8 hours, and calcined at 450℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
b. Second catalyst bed catalyst preparation
1 liter of an alumina carrier was mixed with 2000 g of an aqueous solution of chloropalladate-cupric nitrate containing 0.06 g of palladium and 1.2 g of Cu, and dried at 110℃for 8 hours, and calcined at 550℃for 4 hours, to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 A palladium-based catalyst is obtained.
2. Catalyst evaluation
The hydrogenation operation of the hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol is carried out in a continuous mode, wherein the material passes through a first catalyst bed layer after the material is de-weighted, and then passes through a second catalyst bed layer, and the volume ratio of the catalyst loading amounts of the two catalyst bed layers is 2: the operating conditions for both reactors were as follows:
first catalyst bed:
reaction temperature: 130 DEG C
Reaction pressure: 3MPa of
Fresh oil volume space velocity: 5h -1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio: 1000
A second catalyst bed:
reaction temperature: 160 DEG C
Reaction pressure: 3MPa of
Liquid phase volume space velocity: 10h -1
Hydrogen/fresh oil volume ratio: 600.
comparative example 1
1. Catalyst preparation
a. First catalyst bed catalyst preparation
1 liter of an alumina carrier was mixed with 2000 g of an aqueous solution of chloropalladate-nickel nitrate containing 3.0 g of palladium and 0.3 g of nickel, dried at 110℃for 8 hours and calcined at 550℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 Palladium-based catalysts were obtained, and the specific composition of the catalysts is shown in table 2.
b. Second catalyst bed catalyst preparation
1 liter of the alumina carrier 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 450℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 Palladium-based catalysts were obtained, and the specific composition of the catalysts is shown in table 2.
2. Catalyst evaluation
The hydrogenation of a hydrocarbon feed containing α, α -dimethylbenzyl alcohol was carried out in a continuous manner, said feed passing through a first catalyst bed and then through a second catalyst bed, the catalyst loading of the two catalyst beds being in a volume ratio of 4: the operating conditions for both reactors were as follows:
first catalyst bed:
reaction temperature: 150 DEG C
Reaction pressure: 1.5MPa
Fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio: 400
A second catalyst bed:
reaction temperature: 170 DEG C
Reaction pressure: 1.3MPa
Liquid phase volume space velocity: 8h -1
Hydrogen/fresh oil volume ratio: 100
The average results of the 200 hour evaluation are shown in Table 3.
Comparative example 2
1. Catalyst preparation
1 liter of an alumina carrier was mixed with 2000 g of an aqueous solution of chloropalladate-nickel nitrate containing 3.0 g of palladium and 0.3 g of nickel, dried at 110℃for 8 hours and calcined at 550℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 Palladium-based catalysts were obtained, and the specific composition of the catalysts is shown in table 2.
2. Catalyst evaluation
The hydrogenation operation of the hydrocarbon material containing the alpha, alpha-dimethylbenzyl alcohol is carried out in a continuous mode, the material passes through only one catalyst bed after the material is de-weighted, the catalyst loading of the one catalyst bed is the same as that of the material adopting two catalyst beds, and the specific operation conditions are as follows:
reaction temperature: 150 DEG C
Reaction pressure: 1.5MPa
Fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio: 400
The average results of the 200 hour evaluation are shown in Table 3.
[ comparative example 3 ]
1. Catalyst preparation
1 liter of the alumina carrier 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 450℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 Palladium-based catalysts were obtained, and the specific composition of the catalysts is shown in table 2.
2. Catalyst evaluation
The hydrogenation operation of the hydrocarbon material containing the alpha, alpha-dimethylbenzyl alcohol is carried out in a continuous mode, the material passes through only one catalyst bed after the material is de-weighted, the catalyst loading of the one catalyst bed is the same as that of the material adopting two catalyst beds, and the specific operation conditions are as follows:
reaction temperature: 150 DEG C
Reaction pressure: 1.5MPa
Fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio: 400
The average results of the 200 hour evaluation are shown in Table 3.
[ comparative example 4 ]
1. Catalyst preparation
1 liter of an alumina carrier was mixed with 2000 g of an aqueous solution of chloropalladate-nickel nitrate containing 3.0 g of palladium and 0.3 g of nickel, dried at 110℃for 8 hours and calcined at 550℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 35 ℃ and a hydrogen volume space velocity of 100 hours -1 Palladium-based catalysts were obtained, and the specific composition of the catalysts is shown in table 2.
2. Catalyst evaluation
The hydrogenation of a hydrocarbon feed containing α, α -dimethylbenzyl alcohol is carried out in a continuous manner, said feed passing through only one catalyst bed, said one catalyst bed having the same catalyst loading as when two catalyst beds are employed, the specific operating conditions being as follows:
Reaction temperature: 170 DEG C
Reaction pressure: 1.3MPa
Liquid phase volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio: 400
The average results of the 200 hour evaluation are shown in Table 3.
Comparative example 5
1. Catalyst preparation
1 liter of the alumina carrier 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 450℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 35 ℃ and a hydrogen volume space velocity of 100 hours -1 Palladium-based catalysts were obtained, and the specific composition of the catalysts is shown in table 2.
2. Catalyst evaluation
The hydrogenation of a hydrocarbon feed containing α, α -dimethylbenzyl alcohol is carried out in a continuous manner, said feed passing through only one catalyst bed, said one catalyst bed having the same catalyst loading as when two catalyst beds are employed, the specific operating conditions being as follows:
reaction temperature: 170 DEG C
Reaction pressure: 1.3MPa
Liquid phase volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio: 400
The average results of the 200 hour evaluation are shown in Table 3.
[ comparative example 6 ]
1. Catalyst preparation
a. First catalyst bed catalyst preparation
1 liter of the alumina carrier 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 450℃for 4 hours to prepare an oxidized palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 Palladium-based catalysts were obtained, and the specific composition of the catalysts is shown in table 2.
b. Second catalyst bed catalyst preparation
1 liter of alumina carrier was mixed with 2000 g of an aqueous solution of chloropalladate-nickel nitrate containing 3.0 g of palladium and 0.3 g of nickel, and dried at 110℃for 8 hoursRoasting at 550 ℃ for 4 hours to obtain the oxidation state palladium-based catalyst precursor I. Reducing the oxidation state palladium-based catalyst precursor I by hydrogen for 4 hours at a reduction temperature of 300 ℃ and a hydrogen volume space velocity of 100 hours -1 Palladium-based catalysts were obtained, and the specific composition of the catalysts is shown in table 2.
2. Catalyst evaluation
The hydrogenation of a hydrocarbon feed containing α, α -dimethylbenzyl alcohol was carried out in a continuous manner, said feed passing through a first catalyst bed and then through a second catalyst bed, the catalyst loading of the two catalyst beds being in a volumetric ratio of 1: the operating conditions for both reactors were as follows:
First catalyst bed:
reaction temperature: 150 DEG C
Reaction pressure: 1.5MPa
Fresh oil volume space velocity: 2h -1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio: 400 second catalyst bed:
reaction temperature: 170 DEG C
Reaction pressure: 1.3MPa
Liquid phase volume space velocity: 8h -1
Hydrogen/fresh oil volume ratio: 400
The average results of the 200 hour evaluation are shown in Table 3.
Table 2: catalyst main composition
Table 3:
as can be seen from table 3:
(1) Comparing example 1 with comparative example 1, wherein the two catalyst beds are arranged in opposite directions, it can be seen that the product of comparative example 1 has higher alpha-methylstyrene content, increased cumene and higher alpha, alpha-dimethylbenzyl alcohol content than that of example 3;
(2) Comparing comparative examples 2 to 5 with example 1 and example 3, respectively, wherein each of comparative examples 2 to 5 employs a single catalyst bed packed with the same amount of catalyst, it can be seen that the products of comparative examples 2 to 5 have higher levels of cumene hydroperoxide, alpha-methylstyrene, and cumene boost, and alpha, alpha-dimethylbenzyl alcohol than the examples, particularly the alpha, alpha-dimethylbenzyl alcohol, demonstrating the high conversion of alpha, alpha-dimethylbenzyl alcohol by the process of the present invention;
(3) Comparing comparative example 6 with examples 1 and 3, respectively, wherein the catalyst loading of the first catalyst bed was lower than that of the second catalyst bed in comparative example 6, it can be seen that the incremental amount of cumene and the α, α -dimethylbenzyl alcohol content were significantly higher in the product of comparative example 6.
Claims (20)
1. A method for preparing cumene, comprising: the hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol and hydrogen are used as raw materials, and the cumene is obtained through a first catalyst bed layer and a second catalyst bed layer which are connected in series; wherein, the first catalyst bed layer is filled with a first catalyst, which comprises metal Pd and/or oxide and a carrier; loading a second catalyst comprising metal Pd and/or oxide, metal auxiliary agent and/or oxide thereof and a carrier on the second catalyst bed; the catalyst filling amount of the first catalyst bed layer is larger than that of the second catalyst bed layer; the reaction temperature of the first catalyst bed layer is 130-190 ℃, the reaction pressure is 0.1-5 MPa, and the liquid phase volume space velocity is 1.0-20 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction temperature of the second catalyst bed layer is 150-230 ℃, the reaction pressure is 0.1-5 MPa, and the liquid phase volume space velocity is 2.0-10 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The first catalyst bed layer adopts a liquid phase circulation process, and the circulation ratio is 1-10; reaction temperature of the first catalyst bed Below and the liquid phase volume space velocity above the second catalyst bed.
2. The method according to claim 1, wherein the volume ratio of the catalyst loading of the first catalyst bed to the catalyst loading of the second catalyst bed is (2-6): 1.
3. the method according to claim 2, wherein the volume ratio of the catalyst loading of the first catalyst bed to the catalyst loading of the second catalyst bed is (2-4): 1.
4. the method of claim 1, wherein the step of determining the position of the substrate comprises,
in the first catalyst bed, the volume ratio of hydrogen to liquid phase is 300-1000; and/or
In the second catalyst bed, the volume ratio of the hydrogen to the liquid phase is 100-800.
5. The method of claim 4, wherein the step of determining the position of the first electrode is performed,
in the first catalyst bed, the volume ratio of the hydrogen to the liquid phase is 400-800; and/or
In the second catalyst bed, the volume ratio of the hydrogen to the liquid phase is 200-400.
6. The method of claim 1, wherein the step of determining the position of the substrate comprises,
the metal auxiliary agent is selected from at least one of Fe, co, ni, ca, mg, cu.
7. The method of claim 1, wherein the step of determining the position of the substrate comprises,
In the first catalyst bed, the content of metal Pd and/or oxide thereof is 0.006 g/L-30 g/L; and/or
In the second catalyst, the content of the metal Pd and/or the oxide thereof is 0.006 g/L-30 g/L; the content of the metal auxiliary agent and/or the oxide thereof is 0.0001 g/L-2.0 g/L.
8. The method of claim 7, wherein the step of determining the position of the probe is performed,
in the first catalyst bed, the content of metal Pd and/or oxide thereof is 0.06 g/L-10 g/L; and/or
In the second catalyst, the content of the metal Pd and/or the oxide thereof is 0.06 g/L-10 g/L; the content of the metal auxiliary agent and/or the oxide thereof is 0.001 g/L-1.2 g/L.
9. The method according to any of claims 1 to 8, characterized in that the second catalyst contains phosphorus and/or oxides thereof and optionally silica.
10. The method according to claim 9, wherein the content of phosphorus and/or its oxide in the catalyst is 10g/L to 100g/L in terms of the content of phosphorus element therein.
11. The method according to claim 10, wherein the content of phosphorus and/or its oxide in the catalyst is 20g/L to 60g/L in terms of the content of phosphorus element therein.
12. The method according to claim 9, wherein the content of silica in the catalyst is 0 to 600g/L, the content of silica being based on the content of molecules thereof.
13. The method according to claim 12, wherein the content of silica in the catalyst is 0 to 400g/L, the content of silica being based on the content of molecules thereof.
14. The method of claim 9, further comprising a promoter in the second catalyst, wherein the promoter is a sulfur-containing compound, and wherein the source is a sulfur-containing organic.
15. The method according to claim 14, wherein the content of the cocatalyst in the catalyst is 0 to 5g/L, wherein the amount of the cocatalyst is calculated on the amount of elemental sulfur used therein.
16. The method according to claim 15, wherein the content of the cocatalyst in the catalyst is 0.01 to 1g/L, wherein the amount of the cocatalyst is calculated on the amount of elemental sulfur used therein.
17. The method of claim 14, wherein the hydrocarbon material comprising α, α -dimethylbenzyl alcohol comprises substantially α, α -dimethylbenzyl alcohol.
18. The method of claim 17, wherein the hydrocarbon material comprising α, α -dimethylbenzyl alcohol further comprises cumene, acetophenone, α -methylstyrene, and cumyl benzene.
19. The method of claim 18, wherein the hydrocarbon feed comprising α, α -dimethylbenzyl alcohol further comprises cumene hydroperoxide.
20. Use of the process according to any one of claims 1 to 19 for the preparation of propylene oxide.
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| JP2022519509A JP2022549727A (en) | 2019-09-29 | 2020-09-29 | Catalyst for producing isopropylbenzene and its production method and use |
| US17/764,366 US20220331785A1 (en) | 2019-09-29 | 2020-09-29 | Catalyst for producing isopropylbenzene and the production method and use thereof |
| PCT/CN2020/118672 WO2021058019A1 (en) | 2019-09-29 | 2020-09-29 | Catalyst for use in production of cumene, and preparation method therefor and use thereof |
| EP20869646.8A EP4035771A4 (en) | 2019-09-29 | 2020-09-29 | Catalyst for use in production of cumene, and preparation method therefor and use thereof |
| BR112022005733A BR112022005733A2 (en) | 2019-09-29 | 2020-09-29 | Catalyst for the production of isopropylbenzene and the method of production and use of the same |
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