CN112661585A - Method for preparing isopropylbenzene by hydrogenolysis of alpha, alpha dimethyl benzyl alcohol and application - Google Patents
Method for preparing isopropylbenzene by hydrogenolysis of alpha, alpha dimethyl benzyl alcohol and application Download PDFInfo
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Abstract
The invention provides a method for preparing isopropylbenzene by hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol and application thereof, wherein the method comprises the following steps: introducing a hydrocarbon material of alpha, alpha-dimethylbenzyl alcohol into a de-weighting tower, mixing the de-weighted material with hydrogen, sending the mixture into a catalyst bed layer, and reacting to obtain isopropylbenzene; the catalyst bed layer is filled with a catalyst, and the catalyst comprises a carrier, and an active component and an auxiliary agent which are loaded on the carrier. According to the invention, a heavy component such as PO oligomer existing in the raw material is removed by a heavy component removal tower, then the hydrocarbon material containing alpha, alpha-dimethyl benzyl alcohol and hydrogen gas pass through a catalyst bed layer at a proper temperature in the presence of a supported Pd catalyst, and cumene hydroperoxide in the heavy component removal tower is hydrogenated to alpha, alpha-dimethyl benzyl alcohol and more than 99 percent of alpha, alpha-dimethyl benzyl alcohol and then is hydrogenated and dehydrated to the cumene.
Description
Technical Field
The invention relates to cumene preparation, in particular to the hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol to prepare the cumene, for example, the product of preparing propylene oxide by the reaction of cumene hydroperoxide and propylene is used for preparing the cumene by the hydrogenolysis of a tower material after the propylene oxide is separated by rectification.
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 methods for producing PO include chlorohydrin process, co-oxidation process (PO/SM) and cumene hydroperoxide cycle process (CHP). The process has the following advantages: the conversion rate and the selectivity of the whole process are very high; the product is only PO, is not influenced by the price fluctuation of the by-product styrene, and can bring more stable economic benefit for manufacturers; the process flow is relatively simple, the fixed investment ratio is 1/3 lower than that of a PO/SM method, and the CHP process has lower requirements on equipment corrosion prevention. In the technology of producing propylene oxide by CHP method, a large amount of alpha, alpha-dimethyl benzyl alcohol (DMBA) is generated in the propylene epoxidation process, cumene is generated by hydrogenolysis reaction, and CHP is generated after the cumene is oxidized and participates in the reaction cycle again. The quality of cumene is mainly the content of impurities such as alpha-methyl styrene and PO oligomer, and the cumene and the like directly influence the running stability of an oxidation unit and an epoxidation unit and the quality of a PO product.
U.S. Pat. No. 6,139 proposes a process for preparing cumene by catalytic hydrogenolysis of alpha, alpha-dimethylbenzyl alcoholA process of using H as a technique2The Cu-Cr is used as a hydrogen source, the conversion rate of alpha, alpha-dimethylbenzyl alcohol reaches 99%, but the selectivity is lower than 98%, and the Cr element is used in the preparation of the catalyst, so that the environmental pollution is serious.
Chinese patent CN102464567A proposes a method for preparing isopropylbenzene by hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol, which adopts CuO-ZnO-Al2O3The MgO-MnO catalyst mainly solves the problems of poor catalyst stability and serious environmental pollution in the prior art.
Chinese patent CN101733093A reports that alumina or zeolite loaded metal Pd or a mixture of Pd and Pt is used as a reaction, the conversion rate of alpha, alpha-dimethylbenzyl alcohol is more than 99.5 percent, the selectivity of isopropylbenzene is more than 99.5 percent under the condition that the reaction temperature is lower than 160 ℃, and the stronger acidity of a carrier in the patent can obviously cause the polymerization of methyl styrene which is an intermediate product of dehydration of the alpha, alpha-dimethylbenzyl alcohol, and increase the contents of the alpha-methyl styrene, the isopropylbenzene and other heavy components in the isopropylbenzene product.
Chinese patent CN104230640A proposes to adopt Pd/SiO2The catalyst can realize 100 percent conversion of alpha, alpha-dimethyl benzyl alcohol at the reaction temperature of 180 ℃, but the selectivity of the isopropyl benzene is lower than 98.5 percent, so that the impurity content in the isopropyl benzene product is higher.
The active metals commonly used at present comprise noble metals such as Pt and Pd, Ni, Co, Cu and the like. Because different metal species have different hydrogenation activities, the hydrogenation performance needs to be adjusted through loading capacity, the number of active centers and modification, on one hand, selective hydrogenation of the intermediate product AMS to cumene is realized, and on the other hand, 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 the catalyst for improving the activity and selectivity of the hydrogenolysis of the alpha, alpha-dimethylbenzyl alcohol appears, and less technical problem is involved in the design and development of the hydrogenolysis process for controlling the quality of the isopropylbenzene product.
Disclosure of Invention
Aiming at the defects of the prior art, the invention mainly provides a method for preparing cumene by hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol, and mainly solves the technical problems of unstable downstream process operation and poor product quality caused by the fact that a cumene product obtained in a cumene production technology in the prior art contains impurities such as alpha, alpha-dimethyl benzyl alcohol, alpha-methyl styrene, cumin and the like. The method can realize the conversion of the alpha, alpha-dimethyl benzyl alcohol to prepare the isopropylbenzene with high activity and high selectivity, and improve the running stability of the device and the quality of the isopropylbenzene.
One of the objects of the present invention is to provide a method for preparing isopropylbenzene by hydrogenolysis of α, α -dimethylbenzyl alcohol, comprising: firstly, introducing a hydrocarbon material of alpha, alpha-dimethyl benzyl alcohol into a de-weighting tower, mixing the de-weighted material with hydrogen, and sending the mixture into a catalyst bed layer to obtain the isopropyl benzene.
In a preferred embodiment, a catalyst is filled on the catalyst bed layer, and the catalyst comprises a carrier and an active component and an auxiliary agent which are loaded on the carrier.
In a further preferred embodiment, the active component comprises metallic palladium and/or an oxide thereof, and the promoter comprises a metal promoter and/or an oxide thereof, preferably, the metal promoter is selected from at least one of Fe, Co, Ni, Ca, Mg, Cu.
In a further preferred embodiment, the content of metallic palladium and/or its oxide in the catalyst is from 0.006g/L to 30g/L, preferably from 0.1g/L to 10 g/L; the content of the metal promoter and/or the oxide thereof is 0.0001g/L to 2.0g/L, preferably 0.01g/L to 0.5 g/L.
Wherein, the content of the metal Pd and/or the oxide thereof is calculated by the content of palladium element, and the content of the metal auxiliary agent and/or the oxide thereof is calculated by the content of metal element.
According to the invention, a heavy component such as PO oligomer existing in the raw material is removed by a heavy component removal tower, then the hydrocarbon material containing alpha, alpha-dimethyl benzyl alcohol and hydrogen gas pass through a catalyst bed layer at a proper temperature in the presence of a supported Pd catalyst, and cumene hydroperoxide in the heavy component removal tower is hydrogenated to alpha, alpha-dimethyl benzyl alcohol and more than 99 percent of alpha, alpha-dimethyl benzyl alcohol and then is hydrogenated and dehydrated to the cumene.
In a preferred embodiment, the catalyst comprises phosphorus and/or its oxides and optionally silica.
In a further preferred embodiment, the content of phosphorus and/or its oxide in the catalyst is from 10g/L to 100g/L, preferably from 20g/L to 60g/L, in terms of the content of phosphorus element therein.
In a further preferred embodiment, the silica content in the catalyst is 0 to 600g/L, preferably 0 to 400g/L, for example 0 to 200 g/L. Wherein the content of the silica is calculated by the content of the molecules.
Wherein, the silicon dioxide modification (especially the modified alumina carrier matrix) can improve the activity and stability of the catalyst. When only silicon dioxide is used as a carrier substrate, because the action between the active component and the carrier is weak, Pd grains are easy to aggregate and grow at the reaction temperature, and the stability of the catalyst is not facilitated, an alumina carrier substrate is preferably used. After the modification by silicon, the aperture 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 silicon-containing catalyst has better dehydration activity and is also beneficial to accelerating the hydrogenolysis reaction rate.
In the present invention, the support is selected from at least one of silica, zirconia, alumina and activated carbon; the source of the metallic palladium and/or the oxide thereof is particularly limited, such as, but not limited to, at least one of chloropalladic acid, palladium-ammonia complex and palladium nitrate; the source of the metal promoter and/or the oxide thereof is not particularly limited, and examples thereof include, but are not limited to, at least one of a chloride of the metal promoter, a nitric acid compound of the metal promoter, an acetic acid compound of the metal promoter, and the like. The source of phosphorus is not particularly limited, but is preferably, but not limited to, at least one of phosphoric acid, potassium dihydrogen phosphate, phosphorous acid, calcium phosphate, and the like.
In a preferred embodiment, the catalyst further comprises a cocatalyst, preferably a sulfur-containing compound, the source of which is a sulfur-containing organic compound.
Preferably, the carrier, the active component and the auxiliary agent loaded on the carrier are used as a catalyst main body, and the cocatalyst is loaded on the catalyst main body.
In a further preferred embodiment, the content of the promoter in the catalyst is 0-5 g/L, preferably 0.01-1 g/L, wherein the usage amount of the promoter is calculated by the usage amount of sulfur element.
In the present invention, the source of the sulfur-containing compound is not particularly limited, and is preferably, but not limited to, at least one of tert-nonyl polysulfide, tert-butyl polysulfide, thiophene and the like.
The sulfur-containing organic matter is preferentially adsorbed to 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 high initial activity of the catalyst can be well inhibited, the growth of metal crystal grains and the over hydrogenation of the isopropylbenzene to the isopropylcyclohexane are avoided, the generation of the isopropylbenzene (2, 3-dimethyl-2, 3-diphenylbutane) can be effectively controlled, the operation stability of the catalyst is obviously improved, and the selectivity of the isopropylbenzene is increased.
In a preferred embodiment, the heavy component removal tower is a rectifying tower, a heavy component-containing material flow is extracted from the tower bottom, and a heavy component-removed hydrocarbon material is extracted from the tower top.
The method is characterized in that the light component materials and the heavy component materials are separated by evaporating and condensing the feeding liquid for multiple times by utilizing different volatility of each component in the feeding.
In a further preferred embodiment, the discharge proportion of the tower bottom is 0.4-0.8%, preferably 0.45-0.6%.
Wherein, the heavy components in the tower bottom are very little, which only accounts for 0.45-0.6% of the feeding ratio, and the materials are intermittently discharged after being accumulated in the actual operation.
Wherein, the hydrocarbon material of the alpha, alpha-dimethyl benzyl alcohol is subjected to the heavy component removal treatment through the rectification treatment, the heavy component is discharged from the tower kettle, and the heavy component removed hydrocarbon material is extracted from the tower top and then mixed with hydrogen to enter the catalyst bed layer.
In a preferred embodiment, the tower kettle temperature of the de-heavy tower is 170-200 ℃, the operation pressure is-0.040-0.1 MPa, and the liquid phase volume space velocity is 1-6 h-1。
In a preferred embodiment, the reaction temperature of the catalyst bed layer is 150-250 ℃, the reaction pressure is 0.1-5 MPa, and the liquid phase volume space velocity is 1-6 h-1。
In a preferred embodiment, the volume ratio of the hydrogen to the liquid phase is (300-800): 1, preferably (400-800): 1, wherein the liquid phase refers to the hydrocarbon material treated by the de-heavy tower.
In a preferred embodiment, the catalyst bed layer adopts a liquid phase circulation process, and the circulation ratio is preferably 1-10.
In a preferred embodiment, the hydrocarbon material of the α, α -dimethylbenzyl alcohol comprises 0.01% to 99.999% of α, α -dimethylbenzyl alcohol, 0.01% to 0.1% of cumene hydroperoxide, and 0 to 99.9% of an inert solvent, wherein the inert solvent is preferably cumene.
The inert solvent is required to have substantially no activity on the reactants and products, and examples thereof include long-chain alkanes (octane, dodecane) and aromatic monocyclic aromatic hydrocarbons (benzene, toluene, ethylbenzene, n-propylbenzene, n-butylbenzene, cumene).
In a preferred embodiment, the hydrocarbon feed of α, α -dimethylbenzyl alcohol further comprises acetophenone, α -methylstyrene, n-propylbenzene, and n-butylbenzene.
In a further preferred embodiment, the hydrocarbon material containing α, α -dimethylbenzyl alcohol further includes cumene hydroperoxide, preferably, the cumene hydroperoxide is in a mass percentage of 1 to 2000 ppm.
Particularly, the hydrocarbon material of the alpha, alpha-dimethyl benzyl alcohol comprises 50-60% of the hydrocarbon material of the alpha, alpha-dimethyl benzyl alcohol, 40-50% of cumene, 500-2000 ppm of cumene hydroperoxide and 1.4% of other hydrocarbons.
In a preferred embodiment, the hydrocarbon material of α, α -dimethylbenzyl alcohol is selected from a bottom liquid of a process for preparing propylene oxide by a cumene hydroperoxide method after propylene oxide is separated, or is obtained by reducing cumene hydroperoxide.
The method can realize the high-selectivity conversion of the alpha, alpha-dimethyl benzyl alcohol to the isopropylbenzene, and effectively control the generation of the heavy components such as the isopropylbenzene, the methyl styrene polymer and the like, because the catalyst shows better activity and selectivity after the weight of the raw materials is removed, and the selectivity of the isopropylbenzene is increased while the operation stability of the catalyst is obviously improved. For example, under the conditions that the temperature of a tower kettle of a de-heaving tower is 190 ℃, the pressure is-0.04 MPa, the reaction temperature of a catalyst bed is 160 ℃ and the pressure is 2.0MPa, the cumene hydroperoxide content in the product cumene is 0ppm, the alpha-methyl styrene content is 8ppm, the alpha, alpha-dimethyl benzyl alcohol content is 1210ppm, the cumene content is less than 100ppm, and the selectivity of the cumene reaches 99.88%. The cumene product prepared by the technology has low impurity content, excellent performance, better technical effect and wide industrial utilization value.
The catalyst of the 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 solution containing a palladium compound, drying and roasting to obtain an oxidation state catalyst precursor;
and 3, reducing the oxidation state catalyst precursor to obtain a pre-reduction 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 the 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 carried out as follows: drying at 60-200 deg.C for 4-36 hr, preferably at 80-150 deg.C for 6-12 hr, more preferably at 110 deg.C for 8 hr.
In the present invention, the phosphorus-containing compound 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 calcination temperature is 400 to 700 ℃, preferably, 400 to 600 ℃.
In a preferred embodiment, in step 2, the solution containing the palladium compound further contains a compound containing a metal promoter.
In the present invention, the support is not particularly limited, and preferably may 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, but is preferably, but not limited to, at least one of palladium chloride, palladium nitrate, chloropalladic acid, and the like; the metal-containing assistant compound is not particularly limited, such as but not limited to at least one of a metal-containing assistant chloride, a metal-containing assistant nitric acid compound, a metal-containing assistant acetic acid compound, and the like, and preferably, the metal assistant is selected from at least one of metal copper, metal zinc, metal cobalt, metal tin, metal nickel, and metal silver, such as metal copper.
In a preferred embodiment, in step 3, the reduction treatment is carried out with hydrogen.
In a further preferred embodiment, in step 3, the temperature of the reduction is 20 to 300 ℃, preferably 20 to 100 ℃, for example 35 ℃; the volume space velocity of the hydrogen is 50-500 h-1Preferably 80 to 150 hours-1More preferably 100h-1。
In a preferred embodiment, the method further comprises step 4:
and 4, adding the pre-reduced catalyst precursor into a solution containing a sulfur compound, and drying to obtain the catalyst.
In a further preferred embodiment, the sulfur-containing compound is selected from at least one of tert-nonyl polysulfide, tert-butyl polysulfide, thiophene, dimethyl disulfide.
In the preparation method of the second catalyst of the present invention, based on 1L of the carrier: the dosage of the palladium-containing compound is 0.06 g/L-30 g/L, preferably, the dosage of the palladium-containing compound is 0.1 g/L-10 g/L based on the dosage of palladium element; and/or the amount of the compound containing the metal auxiliary agent is 0.0001-2.0 g/L, preferably 0.01-0.5 g/L based on the amount of the metal element; and/or the dosage of the phosphorus-containing compound is 10 g/L-100 g/L, preferably 20 g/L-60 g/L, wherein the dosage of the phosphorus-containing compound is calculated by the dosage of phosphorus element; and/or the using amount of the sulfur-containing organic matter is 0-5 g/L, preferably 0.01-1 g/L, more preferably 0.05-0.2 g/L, wherein the using amount of the sulfur-containing organic matter is calculated by the using amount of a sulfur element in the sulfur-containing organic matter; and/or the dosage of the silica gel is 0-600 g/L, preferably 0-400 g/L, such as 0-200 g/L, wherein the dosage of the silica gel is calculated by the dosage of silicon dioxide in the silica gel.
In the preparation method of the catalyst of the present invention, the solution is a solution in which the solute is fully dissolved in the good solvent, and is preferably an aqueous solution.
The second purpose of the invention is to provide the application of the method for preparing the isopropylbenzene by the hydrogenolysis of the alpha, alpha-dimethyl benzyl alcohol in the preparation of the propylene oxide.
The invention also aims to provide a preparation method of propylene oxide, which comprises the following steps:
step I, oxidizing cumene serving as a raw material to obtain cumene hydroperoxide;
step II, cumene hydroperoxide reacts with propylene to obtain propylene oxide and alpha, alpha-dimethyl benzyl alcohol;
III, rectifying and separating the epoxypropane to obtain a hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol;
and IV, treating the obtained hydrocarbon material containing the alpha, alpha-dimethyl benzyl alcohol by using the method which is one of the purposes of the invention to obtain the isopropyl benzene, and recycling the isopropyl benzene to the step I.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein. In the above, the various technical solutions can in principle be combined with each other to obtain a new technical solution, which should also be considered as specifically disclosed in the present invention.
Compared with the prior art, the invention has the following beneficial effects: (1) the method solves the technical problems of unstable downstream process operation and poor product quality caused by the fact that the cumene product obtained in the cumene production technology in the prior art contains impurities such as alpha, alpha-dimethyl benzyl alcohol, alpha-methyl styrene, cumene and the like; (2) the method can convert the alpha, alpha-dimethyl benzyl alcohol to prepare the isopropylbenzene with high activity and high selectivity, and improve the running stability of the device and the quality of the isopropylbenzene.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
It is to be further understood that the various features described in the following detailed description may be combined in any suitable manner without departing from the scope of the invention. The invention is 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
| Composition of raw materials | The weight composition is wt% |
| Isopropyl benzene | 41.29 |
| N-propylbenzene | 0.08 |
| Methyl styrene | 0.12 |
| Acetophenone | 1.02 |
| Alpha, alpha-dimethylbenzyl alcohol | 55.26 |
| And isopropyl benzene | 0.27 |
| Cumene hydroperoxide | 0.056 |
| Other sums | 1.94 |
Wherein, the content of each component in the table 1 is detected by gas chromatography.
In the analysis of the product:
cumene selectivity (%) - (W)t 2-W0 2)/(W0 1-Wt 1)]×100％；
w0 1: the mass percentage of the alpha, alpha-dimethyl benzyl alcohol in the raw material; w is at 1: the mass percentage of the alpha, alpha-dimethyl benzyl alcohol in the product;
w0 2: the mass percentage of the isopropyl benzene in the raw material; w is at 2: the cumene in the product is in percentage by mass.
Analysis of main composition of catalyst: the specific element composition in the catalyst is determined by an X-ray fluorescence analysis method, different elements have characteristic X-ray spectra with different wavelengths, the fluorescence intensity of each spectral line has a certain relation with the concentration of the element, and qualitative and quantitative analysis can be carried out by determining the wavelength and the intensity of the characteristic X-ray spectral line of the element to be determined.
[ example 1 ]
1. Catalyst preparation
1 liter of alumina carrier is mixed with 2000 grams of chloropalladate-cobalt acetate mixed aqueous solution containing 3.0 grams of palladium and 1.0 gram of cobalt, and the mixture is dried for 8 hours at 110 ℃ and roasted for 4 hours at 550 ℃ to prepare an oxidation state palladium-based catalyst precursor I.
Reducing the oxidized palladium-based catalyst precursor I for 4 hours by using hydrogen, wherein the reduction temperature is 35 ℃, and the volume space velocity of the hydrogen is 100 hours-1To obtain the palladium-based catalyst, the specific composition of the catalyst is shown in Table 2.
2. Catalyst evaluation
The hydrogenation operation of the hydrocarbon material containing the alpha, alpha-dimethyl benzyl alcohol is carried out in a continuous mode, the material firstly passes through a raw material de-weighting tower and then is mixed with hydrogen to pass through a hydrogenation catalyst bed layer, and the operation conditions are as follows:
2.1 raw material de-weighting tower
Temperature of the column bottom: 190 deg.C
Tower pressure: -0.04MPa
Fresh oil volume space velocity: 2h-1
Reflux ratio: 4
The discharge proportion of the tower kettle: 0.5 percent
2.2 catalyst bed
Temperature: 160 deg.C
Pressure: 2.0MPa
Liquid phase volume space velocity: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio 500
The average results of the 200 hour evaluations are shown in table 3.
[ example 2 ]
1. Catalyst preparation
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 20 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier.
Mixing 1L of the carrier with 2000 g of chloropalladate-cobalt acetate mixed aqueous solution containing 3.0 g of palladium and 1.0 g of cobalt, drying at 110 ℃ for 8 hours, and roasting at 550 ℃ for 4 hours to obtain an oxidation state palladium-based catalyst precursor I.
Reducing the oxidized palladium-based catalyst precursor I for 4 hours by using hydrogen, wherein the reduction temperature is 35 ℃, and the volume space velocity of the hydrogen is 100 hours-1To obtain the palladium-based catalyst, the main composition of which is shown in Table 2.
2. Catalyst evaluation
The hydrogenation operation of the hydrocarbon material containing the alpha, alpha-dimethyl benzyl alcohol is carried out in a continuous mode, the material firstly passes through a raw material de-weighting tower and then is mixed with hydrogen to pass through a hydrogenation catalyst bed layer, and the operation conditions are as follows:
2.1 raw material de-weighting tower
Temperature of the column bottom: 190 deg.C
Tower pressure: -0.04MPa
Fresh oil volume space velocity: 2h-1
Reflux ratio: 4
The discharge proportion of the tower kettle: 0.5 percent
2.2 catalyst bed
Temperature: 160 deg.C
Pressure: 2.0MPa
Liquid phase volume space velocity: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio 500
The average results of the 200 hour evaluations are shown in table 3.
[ example 3 ]
1. Catalyst preparation
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 50 grams of P, 600 grams of aqueous solution are mixed, dried for 8 hours at 110 ℃, and roasted for 4 hours at 400 ℃, thus obtaining the catalyst carrier.
Mixing 1L of the carrier with 2000 g of chloropalladate-cobalt acetate mixed aqueous solution containing 3.0 g of palladium and 1.0 g of cobalt, drying at 110 ℃ for 8 hours, and roasting at 550 ℃ for 4 hours to obtain an oxidation state palladium-based catalyst precursor I.
Reducing the oxidized palladium-based catalyst precursor I for 4 hours by using hydrogen, wherein the reduction temperature is 35 ℃, and the volume space velocity of the hydrogen is 100 hours-1To obtain the palladium-based catalyst, the specific composition of the catalyst is shown in Table 2.
2. Catalyst evaluation
The hydrogenation operation of the hydrocarbon material containing the alpha, alpha-dimethyl benzyl alcohol is carried out in a continuous mode, the material firstly passes through a raw material de-weighting tower and then is mixed with hydrogen to pass through a hydrogenation catalyst bed layer, and the operation conditions are as follows:
2.1 raw material de-weighting tower
Temperature of the column bottom: 190 deg.C
Tower pressure: -0.04MPa
Fresh oil volume space velocity: 2h-1
Reflux ratio: 4
The discharge proportion of the tower kettle: 0.5 percent
2.2 catalyst bed
Temperature: 160 deg.C
Pressure: 2.0MPa
Liquid phase volume space velocity: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio 500
The average results of the 200 hour evaluations are shown in table 3.
[ example 4 ]
1. Catalyst preparation
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 60 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier.
1 liter of the carrier is mixed with 2000 g of chloropalladate-copper nitrate aqueous solution containing 3.0 g of palladium and 1.0 g of copper, and the mixture is dried at 110 ℃ for 8 hours and roasted at 500 ℃ for 4 hours to prepare the precursor of the oxidation state palladium-based catalyst.
Reducing the oxidized palladium-based catalyst precursor for 4 hours by using hydrogen, wherein the reduction temperature is 35 ℃, and the volume space velocity of the hydrogen is 100 hours-1To obtain the reduced palladium-based catalyst precursor.
1L of the reduced palladium-based catalyst precursor was impregnated with 550 g of a cyclohexane solution containing 0.1g of a tertiary nonyl polysulfide, and dried at 110 ℃ to obtain a catalyst. The main composition of the catalyst is shown in table 2.
2. Catalyst evaluation
The hydrogenation operation of the hydrocarbon material containing the alpha, alpha-dimethyl benzyl alcohol is carried out in a continuous mode, the material firstly passes through a raw material de-weighting tower and then is mixed with hydrogen to pass through a hydrogenation catalyst bed layer, and the operation conditions are as follows:
2.1 raw material de-weighting tower
Temperature of the column bottom: 190 deg.C
Tower pressure: -0.04MPa
Fresh oil volume space velocity: 2h-1
Reflux ratio: 4
The discharge proportion of the tower kettle: 0.5 percent
2.2 catalyst bed
Temperature: 160 deg.C
Pressure: 2.0MPa
Liquid phase volume space velocity: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio 500
The average results of the 200 hour evaluations are shown in table 3.
[ examples 5 to 8 ]
The procedure of example 4 was repeated except that: 600g of an aqueous phosphoric acid solution containing 35 g of P was used, and 0.01g, 0.05g, 0.2g and 1g of a di-tert-nonyl polysulfide containing sulfur were used, respectively. The main composition and properties of the catalyst are shown in tables 2 and 3, respectively.
The catalyst evaluation of example 4 was repeated and, likewise, both the α, α -dimethylbenzyl alcohol conversion and the cumene selectivity were higher.
[ example 9 ]
1. Catalyst preparation
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 is mixed with 600 grams of phosphoric acid aqueous solution containing 27 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier containing P.
Mixing the P-containing catalyst carrier 1L with SiO2600g of silica gel water solution with the mass concentration of 5 percent are mixed, dried and roasted at 500 ℃ to obtain the product containing P/SiO2The vector of (1).
The above-mentioned P/SiO-containing layer21 liter of the carrier 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, dried at 110 ℃ for 8 hours, and calcined at 500 ℃ for 4 hours to prepare an oxidized palladium-based catalyst precursor.
Reducing the oxidized palladium-based catalyst precursor for 4 hours by using hydrogen, wherein the reduction temperature is 35 ℃, and the volume space velocity of the hydrogen is 100 hours-1To obtain the reduced palladium-based catalyst precursor.
1 liter of the reduced palladium-based catalyst precursor was impregnated with 550 g of a cyclohexane solution containing 0.1g of a tertiary nonyl polysulfide, to obtain a palladium-based catalyst. The main composition of the catalyst is shown in table 2.
2. Catalyst evaluation
The hydrogenation operation of the hydrocarbon material containing the alpha, alpha-dimethyl benzyl alcohol is carried out in a continuous mode, the material firstly passes through a raw material de-weighting tower and then is mixed with hydrogen to pass through a hydrogenation catalyst bed layer, and the operation conditions are as follows:
2.1 raw material de-weighting tower
Temperature of the column bottom: 190 deg.C
Tower pressure: -0.04MPa
Fresh oil volume space velocity: 2h-1
Reflux ratio: 4
The discharge proportion of the tower kettle: 0.5 percent
2.2 catalyst bed
Temperature: 160 deg.C
Pressure: 2.0MPa
Liquid phase volume space velocity: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio 500
The average results of the 200 hour evaluations are shown in table 3.
[ examples 10 to 12 ]
The procedure of example 9 was repeated except that: the concentrations of the aqueous silica gel solutions were 10%, 20% and 30%, respectively.
The main composition and properties of the catalyst are shown in tables 2 and 3, respectively.
[ example 13 ]
1. Catalyst preparation
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 10 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier.
Mixing 1L of the carrier with 2000 g of chloropalladate-cobalt acetate mixed aqueous solution containing 30.0 g of palladium and 0.001 g of cobalt, drying at 110 ℃ for 8 hours, and roasting at 550 ℃ for 4 hours to prepare an oxidation state palladium-based catalyst precursor I.
Reducing the oxidized palladium-based catalyst precursor I for 4 hours by using hydrogen, wherein the reduction temperature is 35 ℃, and the volume space velocity of the hydrogen is 100 hours-1To obtain the palladium-based catalyst.
2. Catalyst evaluation
The hydrogenation operation of the hydrocarbon material containing the alpha, alpha-dimethyl benzyl alcohol is carried out in a continuous mode, the material firstly passes through a raw material de-weighting tower and then is mixed with hydrogen to pass through a hydrogenation catalyst bed layer, and the operation conditions are as follows:
2.1 raw material de-weighting tower
Temperature of the column bottom: 170 deg.C
Tower pressure: -0.04MPa
Fresh oil volume space velocity: 6h-1
Reflux ratio: 4
The discharge proportion of the tower kettle: 0.5 percent
2.2 catalyst bed
Temperature: 150 ℃ C
Pressure: 5.0MPa
Liquid phase volume space velocity: 1h-1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio 400.
In this example, the starting material can be converted to alpha, alpha-dimethylbenzyl alcohol with high activity and high selectivity to produce cumene.
[ example 14 ]
1. Catalyst preparation
1 liter of alumina is mixed with 600 grams of phosphoric acid aqueous solution containing 100 grams of P, and the mixture is dried for 8 hours at the temperature of 110 ℃ and roasted for 4 hours at the temperature of 400 ℃ to prepare the catalyst carrier.
1 liter of the carrier is mixed with 2000 g of chloropalladate-cobalt acetate mixed aqueous solution containing 0.006g of palladium and 2.0g of cobalt, and the mixture is dried at 110 ℃ for 8 hours and roasted at 550 ℃ for 4 hours to prepare an oxidation state palladium-based catalyst precursor I.
Reducing the oxidized palladium-based catalyst precursor I for 4 hours by using hydrogen, wherein the reduction temperature is 35 ℃, and the volume space velocity of the hydrogen is 100 hours-1To obtain the palladium-based catalyst.
2. Catalyst evaluation
The hydrogenation operation of the hydrocarbon material containing the alpha, alpha-dimethyl benzyl alcohol is carried out in a continuous mode, the material firstly passes through a raw material de-weighting tower and then is mixed with hydrogen to pass through a hydrogenation catalyst bed layer, and the operation conditions are as follows:
2.1 raw material de-weighting tower
Temperature of the column bottom: 200 deg.C
Tower pressure: -0.1MPa
Fresh oil volume space velocity: 1h-1
Reflux ratio: 4
The discharge proportion of the tower kettle: 0.5 percent
2.2 catalyst bed
Temperature: 250 deg.C
Pressure: 0.1MPa
Liquid phase volume space velocity: 6h-1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio 800.
In this example, the starting material can be converted to alpha, alpha-dimethylbenzyl alcohol with high activity and high selectivity to produce cumene.
[ COMPARATIVE EXAMPLE 1 ]
1. Catalyst preparation
Mixing 1L of the carrier with 2000 g of chloropalladate-cobalt acetate mixed aqueous solution containing 3.0 g of palladium and 1.0 g of cobalt, drying at 110 ℃ for 8 hours, and roasting at 550 ℃ for 4 hours to obtain an oxidation state palladium-based catalyst precursor I. Reducing the oxidized palladium-based catalyst precursor I for 4 hours by using hydrogen, wherein the reduction temperature is 35 ℃, and the volume space velocity of the hydrogen is 100 hours-1To obtain the palladium-based catalyst, the specific composition of the catalyst 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 being passed through a bed of hydrogenation catalyst under the following operating conditions:
catalyst bed
Temperature: 160 deg.C
Pressure: 2.0MPa
Liquid phase volume space velocity: 2h-1
Liquid phase circulation ratio: 4
Hydrogen/fresh oil volume ratio 500
The average results of the 200 hour evaluations are shown in table 3.
Table 2:
TABLE 3
Claims (10)
1. A method for preparing isopropylbenzene by hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol, which comprises the following steps: firstly, introducing a hydrocarbon material of alpha, alpha-dimethyl benzyl alcohol into a de-weighting tower, mixing the de-weighted material with hydrogen, and sending the mixture into a catalyst bed layer to obtain the isopropyl benzene.
2. The method of claim 1,
the catalyst bed layer is filled with a catalyst, and the catalyst comprises a carrier, and an active component and an auxiliary agent which are loaded on the carrier; preferably, the first and second electrodes are formed of a metal,
the active component comprises metallic palladium and/or an oxide thereof; and/or
The auxiliary agent comprises a metal auxiliary agent and/or an oxide thereof, and preferably, the metal auxiliary agent is selected from at least one of Fe, Co, Ni, Ca, Mg and Cu.
3. The method according to claim 2, wherein the content of the metallic palladium and/or the oxide thereof in the catalyst is 0.006g/L to 30g/L, and the content of the metal promoter and/or the oxide thereof is 0.0001g/L to 2.0 g/L.
4. The process according to claim 2, characterized in that the catalyst comprises phosphorus and/or its oxides and optionally silica;
preferably, the content of phosphorus and/or oxides thereof in the catalyst is 10 g/L-100 g/L, preferably 20 g/L-60 g/L, calculated by the content of phosphorus element;
more preferably, in the catalyst, the content of silicon dioxide is 0-600 g/L, preferably 0-400 g/L, and the content of silicon dioxide is calculated by the content of molecules.
5. The method according to claim 2, wherein the catalyst further comprises a co-catalyst, preferably the co-catalyst is a sulfur-containing compound derived from sulfur-containing organics;
more preferably, in the catalyst, the content of the cocatalyst is 0-5 g/L, preferably 0.01-1 g/L, wherein the amount of the cocatalyst is calculated by the amount of sulfur element therein.
6. The method of claim 1,
the tower kettle temperature of the de-weighting tower is 170-200 ℃, the operating pressure is-0.040-0.1 MPa, and the liquid phase volume space velocity is 1-6 h-1(ii) a And/or
The reaction temperature of the catalyst bed layer is 150-250 ℃, the reaction pressure is 0.1-5 MPa, and the liquid phase volume space velocity is 1-6 h-1。
7. The method according to any one of claims 1 to 6, wherein the volume ratio of hydrogen to liquid phase is (300 to 800):1, preferably (400 to 800): 1.
8. The method as claimed in claim 7, wherein the hydrocarbon material of α, α -dimethylbenzyl alcohol comprises 0.01% to 99.999% of α, α -dimethylbenzyl alcohol, 0.001% to 0.1% of cumene hydroperoxide, and 0% to 99.9% of inert solvent, preferably cumene;
preferably, the hydrocarbon material of the alpha, alpha-dimethylbenzyl alcohol further comprises acetophenone, alpha-methylstyrene, n-propylbenzene and n-butylbenzene.
9. Use of the process for the hydrogenolysis of α, α -dimethylbenzyl alcohol to prepare isopropylbenzene according to any one of claims 1 to 8 in the preparation of propylene oxide.
10. A method for preparing propylene oxide comprises the following steps:
step I, oxidizing cumene serving as a raw material to obtain cumene hydroperoxide;
step II, cumene hydroperoxide reacts with propylene to obtain propylene oxide and alpha, alpha-dimethyl benzyl alcohol;
III, rectifying and separating the epoxypropane to obtain a hydrocarbon material containing alpha, alpha-dimethylbenzyl alcohol;
step IV, treating the obtained hydrocarbon material containing the alpha, alpha-dimethyl benzyl alcohol by using the method of any one of claims 1 to 8 to obtain isopropyl benzene, and recycling the isopropyl benzene to the step I.
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| CN112159370A (en) * | 2020-09-15 | 2021-01-01 | 中国石油化工股份有限公司 | Reaction system and method of CHPPO device |
| CN114956947A (en) * | 2022-05-24 | 2022-08-30 | 万华化学集团股份有限公司 | Separation method for preparing isopropylbenzene by hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol |
| WO2023070262A1 (en) * | 2021-10-25 | 2023-05-04 | 万华化学集团股份有限公司 | DEVICE AND METHOD FOR PRODUCING CUMENE BY HYDROGENOLYSIS OF α,α-DIMETHYLBENZYL ALCOHOL |
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| CN104109140A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Epoxypropane production method |
| CN104230640A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Alpha, alpha-dimethylbenzyl alcohol hydrogenolysis method for preparing isopropyl benzene |
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| WO2005005402A2 (en) * | 2003-06-30 | 2005-01-20 | Shell Internationale Research Maatschappij B.V. | Process for producing alkylene oxide |
| CN104109140A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Epoxypropane production method |
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| CN112159370A (en) * | 2020-09-15 | 2021-01-01 | 中国石油化工股份有限公司 | Reaction system and method of CHPPO device |
| WO2023070262A1 (en) * | 2021-10-25 | 2023-05-04 | 万华化学集团股份有限公司 | DEVICE AND METHOD FOR PRODUCING CUMENE BY HYDROGENOLYSIS OF α,α-DIMETHYLBENZYL ALCOHOL |
| CN114956947A (en) * | 2022-05-24 | 2022-08-30 | 万华化学集团股份有限公司 | Separation method for preparing isopropylbenzene by hydrogenolysis of alpha, alpha-dimethyl benzyl alcohol |
| CN114956947B (en) * | 2022-05-24 | 2023-05-30 | 万华化学集团股份有限公司 | Separation method for preparing isopropylbenzene by hydrogenolysis of alpha, alpha-dimethylbenzyl alcohol |
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