CN108658727B - Propylene oxidation process - Google Patents

Propylene oxidation process Download PDF

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Publication number
CN108658727B
CN108658727B CN201710203580.8A CN201710203580A CN108658727B CN 108658727 B CN108658727 B CN 108658727B CN 201710203580 A CN201710203580 A CN 201710203580A CN 108658727 B CN108658727 B CN 108658727B
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molecular sieve
titanium
aluminum
catalyst
reaction
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CN108658727A (en
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史春风
林民
朱斌
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta

Abstract

The present disclosure relates to a process for the oxidation of propylene, the process comprising: the method comprises the step of carrying out contact reaction on propylene, an oxidant and water in the presence of a catalyst, wherein the catalyst contains a titanium-silicon molecular sieve and a silicon-aluminum molecular sieve, or the catalyst contains a titanium-silicon-aluminum molecular sieve. The propylene oxidation reaction by adopting the method disclosed by the invention can greatly improve the selectivity of propylene glycol in the product, and the catalytic oxidation activity and the catalytic activity stability of the catalyst are better.

Description

Propylene oxidation process
Technical Field
The present disclosure relates to a process for the oxidation of propylene.
Background
Propylene Glycol (PG), also known as propylene glycol, 1,2 propylene glycol, is an important raw material for the preparation of unsaturated polyesters, epoxy resins, polyurethane resins, wherein unsaturated polyesters can be used in large amounts for surface coatings and reinforced plastics. Propylene glycol is excellent in viscosity and hygroscopicity and is non-toxic, and thus is widely used as a moisture absorbent, an anti-freezing agent, a lubricant and a solvent in the food, pharmaceutical and cosmetic industries. In the food industry, propylene glycol reacts with fatty acids to form propylene glycol fatty acid esters, mainly used as food emulsifiers; propylene glycol is also an excellent solvent for flavors and colors. Propylene glycol is commonly used in the pharmaceutical industry as a solvent, softener, excipient, etc. for the manufacture of various ointments and salves, and also as a solvent, softener, etc. for cosmetics because of its good miscibility with various fragrances. Propylene glycol is also used as a tobacco humectant, mold inhibitor, lubricant for food processing equipment, and solvent for food marking inks. In addition, aqueous solutions of propylene glycol are effective antifreeze agents. In the prior art, 1, 2-propylene glycol is mainly produced by the reconversion of propylene derivatives, a large amount of water is needed to inhibit the production of polyethylene glycol in the reaction process, and the process is simultaneously used for the industrial production of raw material propylene derivatives (propylene oxide), and has the problems of complex process, large investment, large byproduct quantity, serious pollution and the like.
Therefore, aiming at the defects of the prior art, the research of a novel process for preparing propylene glycol, which is environment-friendly and simple, has very important practical significance.
Disclosure of Invention
It is an object of the present disclosure to provide a process for the oxidation of propylene which can greatly increase the selectivity of propylene glycol in the product.
In order to achieve the above object, the present disclosure provides a propylene oxidation process, comprising: the method comprises the step of carrying out contact reaction on propylene, an oxidant and water in the presence of a catalyst, wherein the catalyst contains a titanium-silicon molecular sieve and a silicon-aluminum molecular sieve, or the catalyst contains a titanium-silicon-aluminum molecular sieve.
Alternatively, the molar ratio of propylene to oxidant is 1: (0.1-10), preferably 1: (0.2-5); the weight ratio of the propylene to the catalyst to the water is (0.5-150): 1: (1-200), preferably (1-100): 1: (2-150); the reaction conditions are as follows: the temperature is 40-150 ℃, and the pressure is 0.1-3 MPa.
Alternatively, when the catalyst contains a titanium silicalite molecular sieve and a silicoaluminophosphate molecular sieve, the weight ratio of the titanium silicalite molecular sieve to the silicoaluminophosphate molecular sieve is (0.1-10): 1.
optionally, the titanium silicalite molecular sieve is at least one selected from an MFI-type titanium silicalite molecular sieve, an MEL-type titanium silicalite molecular sieve, an MWW-type titanium silicalite molecular sieve, a hexagonal-structure titanium silicalite molecular sieve and an MRE-type titanium silicalite molecular sieve; the silicon-aluminum molecular sieve is at least one selected from FAU type silicon-aluminum molecular sieve, MEL type silicon-aluminum molecular sieve, MWW type silicon-aluminum molecular sieve, MOR structure silicon-aluminum molecular sieve, TUN structure silicon-aluminum molecular sieve, BEA type silicon-aluminum molecular sieve and MFI type silicon-aluminum molecular sieve.
Optionally, the titanium silicalite molecular sieve is at least one selected from a titanium silicalite molecular sieve with an MFI structure, a titanium silicalite molecular sieve with an MEL structure, a titanium silicalite molecular sieve with a BEA structure, a titanium silicalite molecular sieve with an MWW structure, a titanium silicalite molecular sieve with an MOR structure, a titanium silicalite molecular sieve with a TUN structure, and a titanium silicalite molecular sieve with a two-dimensional hexagonal structure.
Optionally, the step of preparing the titanium silicalite molecular sieve comprises:
(1) mixing a first discharging agent and an organic acid solution, pulping, carrying out first heat treatment on the obtained slurry, and separating to obtain a first solid, wherein the first discharging agent is a discharging agent of a reaction device which takes a titanium-silicon molecular sieve as an active component of a catalyst, and the conditions of the first heat treatment are as follows: the temperature is 20-45 ℃ and the time is 1-30 h;
(2) mixing the first solid, an aluminum source, a titanium source and an alkali source in the presence of an aqueous solvent, and then carrying out second heat treatment, wherein the conditions of the second heat treatment are as follows: the temperature is 100 ℃ and 200 ℃, and the time is 0.5-25 h;
or, the preparation steps of the titanium-silicon-aluminum molecular sieve comprise:
a. mixing and pulping a second discharging agent and an organic acid solution, carrying out third heat treatment on the obtained slurry, and separating to obtain a second solid, wherein the second discharging agent is a discharging agent of a reaction device which takes a silicon-aluminum molecular sieve as an active component of a catalyst, and the conditions of the third heat treatment are as follows: the temperature is 50-150 ℃, and the time is 0.5-40 h;
b. Mixing the second solid, a titanium source and an alkali source in the presence of an aqueous solvent, and then carrying out fourth heat treatment, wherein the conditions of the fourth heat treatment are as follows: the temperature is 100 ℃ and 200 ℃, and the time is 0.5-25 h.
Optionally, the weight ratio of the first discharging agent, the titanium source, the aluminum source, the organic acid, the alkali source and the water is 100: (0.1-10): (0.1-10): (0.005-50): (0.5-50): (20-1000), the first discharging agent is SiO2The organic acid is counted as H+The alkali source is counted by N when containing nitrogen element, and the alkali source is counted by OH when not containing nitrogen element-Counting; the concentration of the organic acid solution is more than 0.1 mol/L.
Optionally, the discharging agent of the reaction device with the titanium silicalite molecular sieve as the catalyst active component in the step (1) is at least one selected from the group consisting of a discharging agent of an ammoximation reaction device, a discharging agent of a hydroxylation reaction device and a discharging agent of an epoxidation reaction device;
preferably, the titanium silicalite molecular sieve in step (1) is a titanium silicalite molecular sieve of MFI structure, and the activity of the first discharging agent is 50% or less of the activity of the titanium silicalite molecular sieve when fresh.
Alternatively, the aluminum source and the alkali source are mixed in the presence of an aqueous solvent to obtain a mixed solution, and then the mixed solution is mixed with the first solid and the titanium source before the second heat treatment is performed.
Optionally, the weight ratio of the second discharging agent, the titanium source, the organic acid, the alkali source and the water is 100: (0.1-10): (0.005-50): (0.5-50): (20-1000), the second discharging agent is SiO2The organic acid is counted as H+The alkali source is counted as N when containing nitrogen element, and the alkali source is counted as OH when not containing nitrogen element-Counting; the concentration of the organic acid solution is more than 0.1 mol/L.
Optionally, the discharging agent of the reaction device with the silicon-aluminum molecular sieve as the catalyst active component in the step a is a discharging agent of a synthesis reaction device of hydrogen sulfide and methanol;
preferably, the silicoaluminophosphate molecular sieve in step a is a silicoaluminophosphate molecular sieve of MFI structure, and the activity of the second discharging agent is 50% or less of the activity of the silicoaluminophosphate molecular sieve when fresh.
Optionally, the organic acid is at least one selected from naphthenic acid, peracetic acid, and propionic acid; the alkali source is at least one selected from ammonia, aliphatic amine, aliphatic alcohol amine and quaternary ammonium base; the aluminum source is at least one selected from aluminum sol, aluminum salt, aluminum hydroxide and aluminum oxide; the titanium source is inorganic titanium salt and/or organic titanate.
Optionally, the oxidizing agent is at least one selected from the group consisting of hydrogen peroxide, t-butyl hydroperoxide, cumene peroxide, cyclohexyl hydroperoxide, peroxyacetic acid, and peroxypropionic acid.
Optionally, the method further comprises: the reaction is carried out in the presence of a solvent, wherein the solvent is at least one selected from acetone, butanone, acetonitrile, propionitrile, phenylacetonitrile, acetic acid and propionic acid, and the weight ratio of the solvent to the catalyst is (1-200): 1.
through the technical scheme, the method disclosed by the invention overcomes the problems of complex process, equipment corrosion, harmful emission and the like of the traditional production method, the selectivity of propylene glycol in a product can be greatly improved by adopting the method for propylene oxidation reaction, and the catalytic oxidation activity and the catalytic activity stability of the catalyst are good.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The present disclosure provides a process for the oxidation of propylene, the process comprising: the method comprises the step of carrying out contact reaction on propylene, an oxidant and water in the presence of a catalyst, wherein the catalyst contains a titanium-silicon molecular sieve and a silicon-aluminum molecular sieve, or the catalyst contains a titanium-silicon-aluminum molecular sieve.
The inventor of the present disclosure finds, through a large number of experimental studies, that in the process of propylene oxidation reaction, when a catalyst is a composition containing a titanium silicalite molecular sieve and a silicon-aluminum molecular sieve, or a titanium silicalite molecular sieve, the selectivity of propylene glycol in a product can be greatly improved under certain conditions, propylene oxide and propylene glycol can be obtained after the product is separated, and unreacted propylene and the like can be directly returned to a reaction device for recycling without purification and separation.
In order to obtain the desired reaction effect, the molar ratio of propylene to oxidant may be 1: (0.1-10), preferably 1: (0.2-5); the weight ratio of propylene, catalyst and water may be (0.5-150): 1: (1-200), preferably (1-100): 1: (2-150).
According to the present disclosure, when the catalyst contains a titanium silicalite molecular sieve and a silicoaluminophosphate molecular sieve, the weight ratio of the titanium silicalite molecular sieve to the silicoaluminophosphate molecular sieve may be (0.1-10): 1. wherein, the content of titanium oxide in the titanium silicalite molecular sieve can be 0.1-5 wt%, preferably 0.5-4 wt%; the content of alumina in the silicoaluminophosphate molecular sieve may be from 0.1 to 5 wt%, preferably from 0.1 to 2 wt%, based on the total weight of the silicoaluminophosphate molecular sieve. When the catalyst is a composition containing a titanium-silicon molecular sieve and a silicon-aluminum molecular sieve, the titanium-silicon molecular sieve and the silicon-aluminum molecular sieve can be directly obtained by mechanical mixing.
According to the present disclosure, the titanium silicalite molecular sieve may be at least one selected from an MFI type titanium silicalite molecular sieve, an MEL type titanium silicalite molecular sieve, an MWW type titanium silicalite molecular sieve, a hexagonal structure titanium silicalite molecular sieve and an MRE type titanium silicalite molecular sieve, and more preferably at least one selected from a TS-1 molecular sieve, a TS-2 molecular sieve, a Ti-MCM-22 molecular sieve, a Ti-MCM-41 molecular sieve, a Ti-SBA-15 molecular sieve and a Ti-ZSM-48 molecular sieve; the silicoaluminophosphate molecular sieve may be at least one selected from the group consisting of FAU type silicoaluminophosphate molecular sieves, BEA type silicoaluminophosphate molecular sieves, MEL type silicoaluminophosphate molecular sieves, MWW type silicoaluminophosphate molecular sieves, MOR structure silicoaluminophosphate molecular sieves, TUN structure silicoaluminophosphate molecular sieves and MFI type silicoaluminophosphate molecular sieves, and more preferably at least one selected from the group consisting of ZSM-5 molecular sieves, β molecular sieves, X molecular sieves, Y molecular sieves and MCM-22 molecular sieves. The titanium silicalite molecular sieves and the silicoaluminophosphate molecular sieves can be prepared according to the prior art and can also be obtained commercially.
According to the present disclosure, the titanium-silicon-aluminum molecular sieve refers to a generic term for a type of zeolite in which titanium atoms and aluminum atoms substitute for a part of silicon atoms in the lattice framework. When the catalyst contains a titanium silicon aluminium molecular sieve, the titanium silicon aluminium molecular sieve can be common titanium silicon aluminium molecular sieve with various topological structures, such as: the titanium-silicon-aluminum molecular sieve can be at least one of a titanium-silicon-aluminum molecular sieve with an MFI structure, a titanium-silicon-aluminum molecular sieve with an MEL structure (such as TS-2), a titanium-silicon-aluminum molecular sieve with a BEA structure, a titanium-silicon-aluminum molecular sieve with an MWW structure, a titanium-silicon-aluminum molecular sieve with an MOR structure, a titanium-silicon-aluminum molecular sieve with a TUN structure, a titanium-silicon-aluminum molecular sieve with a two-dimensional hexagonal structure and a titanium-silicon-aluminum molecular sieve with other structures. The titanium-silicon-aluminum molecular sieve is preferably at least one of a titanium-silicon-aluminum molecular sieve with an MFI structure, a titanium-silicon-aluminum molecular sieve with an MEL structure and a titanium-silicon-aluminum molecular sieve with a BEA structure, and more preferably is a titanium-silicon-aluminum molecular sieve with an MFI structure.
According to the present disclosure, the titanium silicalite molecular sieve is used as a catalyst to achieve the purpose of the present disclosure, but the inventors of the present disclosure found in the research that the titanium silicalite molecular sieve prepared by a specific method is particularly beneficial for improving the selectivity of propylene glycol.
Thus, according to a preferred embodiment of the present disclosure, the step of preparing the titanium silicalite molecular sieve comprises:
(1) mixing and pulping a first discharging agent and an organic acid solution, carrying out first heat treatment on the obtained slurry, and separating to obtain a first solid, wherein the first discharging agent is a discharging agent of a reaction device which takes a titanium silicalite molecular sieve as a catalyst active component, and the conditions of the first heat treatment are as follows: the temperature is 20-45 ℃, and the time is 1-30h, preferably 1-24h, more preferably 10-20 h;
(2) mixing the first solid, an aluminum source, a titanium source and an alkali source in the presence of an aqueous solvent, and then carrying out second heat treatment, wherein the conditions of the second heat treatment are as follows: the temperature is 100-200 ℃, preferably 120-180 ℃, more preferably 140-170 ℃ and the time is 0.5-25h, preferably 2-24h, more preferably 5-20 h.
In the above preferred embodiment, the relative crystallinity of the first solid obtained after the first heat treatment may be 70 to 90%. The first discharging agent can be processed into a first solid with specific relative crystallinity under specific first heat treatment conditions, and then the second heat treatment is carried out, so that the titanium-silicon-aluminum molecular sieve with excellent catalytic performance can be obtained, and the selectivity of propylene glycol can be further improved when the titanium-silicon-aluminum molecular sieve is used in the reaction of the present disclosure. Wherein the relative crystallinity of the solid refers to the crystallinity of the solid relative to the fresh agent to which the discharge agent corresponds.
In the above preferred embodiment, the discharging agent of the reaction apparatus using the titanium silicalite as the catalyst active component may be discharging agent from various apparatuses using the titanium silicalite as the catalyst active component, for example, discharging agent from an oxidation reaction apparatus using the titanium silicalite as the catalyst active component. The oxidation reaction may be various oxidation reactions, for example, the discharging agent of the reaction apparatus using the titanium silicalite molecular sieve as the active component of the catalyst may be at least one of a discharging agent of an ammoximation reaction apparatus, a discharging agent of a hydroxylation reaction apparatus and a discharging agent of an epoxidation reaction apparatus, specifically at least one of a discharging agent of a cyclohexanone ammoximation reaction apparatus, a discharging agent of a phenol hydroxylation reaction apparatus and a discharging agent of a propylene epoxidation reaction apparatus, and preferably, the discharging agent is a catalyst that is deactivated by reaction in an alkaline environment, and therefore, for the purposes of the present invention, it is preferred that the first discharging agent is a discharging agent of a cyclohexanone ammoximation reaction apparatus (such as deactivated titanium silicalite TS-1, powdery molecular sieve having a particle size of 100-500 nm).
The discharging agent is a deactivated catalyst under the condition that the activity of the catalyst cannot be recovered to 50% of the initial activity by adopting a conventional regeneration method such as solvent washing or roasting, and the like (the initial activity refers to the average activity of the catalyst within 1h under the same reaction condition, for example, in the actual cyclohexanone oximation reaction, the initial activity of the catalyst is generally more than 95%). The activity of the discharging agent varies depending on its source. Generally, the activity of the discharging agent can be 5-95% of the activity of the titanium silicalite when fresh (i.e., the activity of the fresh agent). Preferably, the activity of the first discharging agent may be less than 50% of the activity of the titanium silicalite molecular sieve in a fresh state, and more preferably, the activity of the first discharging agent may be 10-40% of the activity of the titanium silicalite molecular sieve in a fresh state. The activity of the titanium silicalite molecular sieve in the fresh state is generally more than 90 percent, and usually more than 95 percent.
The discharge agent can be derived from an industrial deactivator or a deactivated catalyst after reaction in the laboratory. Certainly, from the perspective of preparation effect, the method disclosed by the disclosure can also adopt a fresh molecular sieve such as a titanium silicalite molecular sieve as a raw material, which is only unsuitable from the perspective of cost control and the like.
In the preferred embodiment described above, the discharging agent of each apparatus is individually measured by the reaction of each apparatus, and the discharging agent of the present invention is obtained as long as it is ensured that the activity of the discharging agent is lower than that of the fresh catalyst under the same reaction conditions in the same apparatus. As mentioned before, the activity of the discharging agent is preferably less than 50% of the activity of the fresh catalyst.
In the preferred embodiment, the discharging agent of the cyclohexanone ammoximation reaction apparatus is taken as an example, and the activity is measured by the following method:
taking a TS-1 molecular sieve (prepared by the method described in Zeolite, 1992, Vol.12: 943-950), TiO22.1%) was placed in a 100mL slurry bed reactor with continuous feed and membrane separation means, and a mixture of water and 30 wt% hydrogen peroxide (water to hydrogen peroxide volume ratio of 10: 9) a mixture of cyclohexanone and tert-butanol was added at a rate of 10.5mL/h (the volume ratio of cyclohexanone to tert-butanol was 1: 2.5) adding 36 wt% ammonia water at the speed of 5.7mL/h, simultaneously adding the three material flows, continuously discharging at the corresponding speed, maintaining the reaction temperature at 80 ℃, sampling the product every 1h after the reaction is stable, analyzing the composition of a liquid phase by using a gas chromatography, calculating the conversion rate of cyclohexanone by using the following formula, and taking the conversion rate as the activity of the titanium-silicon molecular sieve. Conversion of cyclohexanone [ (molar amount of cyclohexanone charged-molar amount of unreacted cyclohexanone)/molar amount of cyclohexanone charged ]X 100%. Wherein the result of 1h is taken as the initial activity.
In the above preferred embodiment, the titanium silicalite molecular sieve can be common titanium silicalite molecular sieve with various topologies, such as: the titanium silicalite molecular sieve may be selected from one or more of a titanium silicalite molecular sieve of MFI structure (e.g., TS-1), a titanium silicalite molecular sieve of MEL structure (e.g., TS-2), a titanium silicalite molecular sieve of BEA structure (e.g., Ti-Beta), a titanium silicalite molecular sieve of MWW structure (e.g., Ti-MCM-22), a titanium silicalite molecular sieve of hexagonal structure (e.g., Ti-MCM-41, Ti-SBA-15), a titanium silicalite molecular sieve of MOR structure (e.g., Ti-MOR), a titanium silicalite molecular sieve of TUN structure (e.g., Ti-TUN), and a titanium silicalite molecular sieve of other structure (e.g., Ti-ZSM-48). Preferably, the titanium silicalite molecular sieve is selected from one or more of a titanium silicalite molecular sieve of an MFI structure, a titanium silicalite molecular sieve of an MEL structure and a titanium silicalite molecular sieve of a BEA structure. More preferably, the titanium silicalite molecular sieve is a titanium silicalite molecular sieve of MFI structure, such as TS-1 molecular sieve.
In the above preferred embodiment, the weight ratio of the first discharging agent, the titanium source, the aluminum source, the organic acid, the alkali source and the water may be 100: (0.1-10): (0.1-10): (0.005-50): (0.5-50): (20-1000), preferably 100: (0.5-10): (0.5-10): (1-15): (1-20): (100-800), more preferably the weight ratio of the first discharging agent to the organic acid is 100: (2-8), wherein the first discharging agent is SiO 2The organic acid is counted as H+The alkali source is counted as N when containing nitrogen element, and the alkali source is counted as OH when not containing nitrogen element-And (6) counting.
In the above preferred embodiment, the aluminum source is a substance capable of providing aluminum, and preferably the aluminum source is one or more of an aluminum sol, an aluminum salt, aluminum hydroxide and alumina, and the aluminum sol is preferably contained in an amount of 10 to 50 wt% based on the alumina. The aluminum salt may be an inorganic aluminum salt, which may be, for example, one or more of aluminum sulfate, sodium metaaluminate, aluminum chloride, and aluminum nitrate, and/or an organic aluminum salt, which is preferably a C1-C10 organic aluminum salt.
In the above preferred embodiment, the preferred step (2) may be performed as follows: mixing the aluminum source and the alkali source in the presence of a water-containing solvent to obtain a mixed solution, mixing the mixed solution with the first solid and the titanium source, and then carrying out the second heat treatment. Thus, the activity of the titanium-silicon-aluminum molecular sieve can be further improved.
The above preferred embodiment may further comprise a step of recovering the product from the second heat-treated material of step (2), wherein the step of recovering the product is a conventional method and familiar to those skilled in the art, and is not particularly required, and generally refers to a process of filtering, washing, drying and calcining the product. Wherein, the drying process can be carried out at the temperature of between 20 and 200 ℃, and the roasting process can be carried out at the temperature of between 300 and 800 ℃ in a nitrogen atmosphere for 0.5 to 6 hours and then in an air atmosphere for 3 to 12 hours.
Alternatively, according to another preferred embodiment of the present disclosure, the step of preparing the titanium silicalite molecular sieve comprises:
a. mixing a second discharging agent and an organic acid solution, pulping, carrying out third heat treatment on the obtained slurry, and separating to obtain a second solid, wherein the second discharging agent is a discharging agent of a reaction device using a silicon-aluminum molecular sieve as an active component of a catalyst, and the conditions of the third heat treatment are as follows: the temperature is 50-150 ℃, and the time is 0.5-40h, preferably 1-24h, and more preferably 10-20 h;
b. mixing the second solid, a titanium source and an alkali source in the presence of an aqueous solvent, and then carrying out fourth heat treatment, wherein the conditions of the fourth heat treatment are as follows: the temperature is 100-200 ℃, preferably 120-180 ℃, more preferably 140-170 ℃ and the time is 0.5-25h, preferably 2-24h, more preferably 5-20 h.
In the above preferred embodiment, the relative crystallinity of the second solid obtained after the third heat treatment may be 50 to 70%. The second discharging agent can be processed into a second solid with specific relative crystallinity under specific third heat treatment conditions, and then the second solid is subjected to fourth heat treatment, so that the titanium-silicon-aluminum molecular sieve with excellent catalytic performance can be obtained, and the titanium-silicon-aluminum molecular sieve can be used in the reaction of the disclosure to further improve the selectivity of propylene glycol. The relative crystallinity is determined as described above.
In the preferred embodiment described above, the particular definitions of the discharging agent are as described above, except that the titanium silicalite is replaced with a silicoaluminophosphate. The discharging agent of the reaction device using the aluminosilicate molecular sieve as the catalyst active component may be a discharging agent discharged from various devices using the aluminosilicate molecular sieve as the catalyst active component, for example, a discharging agent discharged from a synthesis reaction device using the aluminosilicate molecular sieve as the catalyst active component (such as a discharging agent of a synthesis reaction device of hydrogen sulfide and methanol), or a discharging agent discharged from a catalytic cracking reaction device using the aluminosilicate molecular sieve as the catalyst active component. Preferably, the discharging agent is a catalyst deactivated in reaction under an alkaline environment, and therefore, for the purposes of the present disclosure, the second discharging agent is preferably a discharging agent (such as deactivated silicon-aluminum molecular sieve ZSM-5, powdery, and the particle size is 100-500nm) of a synthesis reaction device of hydrogen sulfide and methanol.
As mentioned above, the activity of the second discharging agent is preferably 50% or less of the activity of the aluminosilicate molecular sieve in the fresh state.
In the preferred embodiment, the activity is measured by taking as an example the discharging agent of the apparatus for the synthesis reaction of hydrogen sulfide and methanol:
ZSM-5 molecular sieve (prepared by the method described in example 1 of CN 1715185A) is treated with water vapor at 200 deg.C for 10h, then tableted, sieved, and 20-40 mesh particles are loaded into a tubular reaction tube with diameter of 0.8cm and length of 55cm, and the bed volume of catalyst particles is 2.0cm3. The reaction temperature is 300 ℃, the reaction pressure is 1atm, the feeding molar ratio of hydrogen sulfide and methanol is 1:2, and the total gas volume space velocity is 700h-1Under the conditions of (1), a catalytic reaction for synthesizing dimethyl sulfide is carried out. And analyzing the product obtained after the catalytic reaction is carried out for 3 hours by using gas chromatography, calculating the conversion rate of the methanol according to the analysis result, and taking the conversion rate as the activity of the silicon-aluminum molecular sieve. Conversion of methanol [ (molar amount of methanol added-molar amount of unreacted methanol)/molar amount of methanol added]X 100%. The result of 1h was used as the initial activity.
In the above preferred embodiment, the silicon-aluminum molecular sieve may be a common silicon-aluminum molecular sieve having various topologies, and preferably, the silicon-aluminum molecular sieve is selected from at least one of a silicon-aluminum molecular sieve of MFI structure, a silicon-aluminum molecular sieve of FAU structure, a silicon-aluminum molecular sieve of MWW structure, a silicon-aluminum molecular sieve of MEL structure, and a silicon-aluminum molecular sieve of BEA structure. More preferably, the silicoaluminophosphate molecular sieve is at least one of a silicoaluminophosphate molecular sieve of an MFI structure, a silicoaluminophosphate molecular sieve of a BEA structure, and a silicoaluminophosphate molecular sieve of an MWW structure.
In the above preferred embodiment, the weight ratio of the second discharging agent, the titanium source, the organic acid, the alkali source and the water is 100: (0.1-10): (0.005-50): (0.5-50): (20-1000), preferably 100: (0.5-10): (1-15): (1-20): (100-800), more preferably the weight ratio of the second discharging agent to the organic acid is 100: (2-8), wherein the second discharging agent is SiO2The organic acid is counted as H+When the alkali source contains nitrogen element, the amount is counted as N, and the alkali sourceOH when no nitrogen element is contained-And (6) counting.
In the above preferred embodiment, the step (b) is preferably performed as follows: and mixing the aqueous solution of the alkali source with the second solid and the titanium source, and then performing the fourth heat treatment.
In a preferred embodiment of the above two titanium-silicon-aluminum molecular sieves, the pulping is preferably performed at normal temperature and normal pressure. Unless otherwise specified, the heat treatment is generally carried out under autogenous pressure in the case of sealing.
In the above two preferred embodiments of the titanium silicalite molecular sieves, the organic acid is not particularly required, and may be a C1-C10 organic carboxylic acid, preferably at least one of naphthenic acid, peroxyacetic acid and peroxypropionic acid. The concentration of the organic acid solution is preferably >0.1mol/L, more preferably ≧ 1mol/L, further preferably 2-15 mol/L. In the present disclosure, the main solvent of the acid solution is water, and other solvent additives may also be added as needed. The titanium-silicon-aluminum molecular sieve prepared in the way has better catalytic performance.
In a preferred embodiment of the above two titanium-silicon-aluminum molecular sieves, the titanium source can be an organic titanium source (e.g., organic titanate) and/or an inorganic titanium source (e.g., inorganic titanium salt). Wherein the inorganic titanium source can be TiCl4、Ti(SO4)2、TiOCl2Titanium hydroxide, titanium oxide, titanium nitrate, titanium phosphate and the like, and the organic titanium source may be at least one of fatty titanium alkoxide and organic titanate. The titanium source is preferably an organic titanium source, and more preferably an organic titanate. The organic titanate is preferably of the formula M4TiO4Wherein M is preferably an alkyl group having 1 to 4 carbon atoms, and 4M's may be the same or different, preferably the organotitanate is selected from at least one of isopropyl titanate, n-propyl titanate, tetrabutyl titanate and tetraethyl titanate. Specific examples of the titanium source may be, but are not limited to: TiOCl2Titanium tetrachloride, titanium sulfate, tetrapropyl titanate (including various isomers of tetrapropyl titanate, such as tetraisopropyl titanate and tetra-n-propyl titanate), tetrabutyl titanate (each of tetrabutyl titanate)One isomer, such as tetra-n-butyl titanate) and tetraethyl titanate.
In a preferred embodiment of the above two titanium silicalite molecular sieves, the type of the alkali source can be selected from a wide range, and can be an organic alkali source and/or an inorganic alkali source, wherein the inorganic alkali source can be ammonia, or an alkali whose cation is an alkali metal or an alkaline earth metal, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium hydroxide, etc., and the organic alkali source can be one or more of urea, aliphatic amine, aliphatic alcohol amine, and quaternary ammonium alkali compound. The quaternary ammonium base can be various organic quaternary ammonium bases, and the aliphatic amine can be various NH 3In which at least one hydrogen is substituted with an aliphatic hydrocarbon group (preferably an alkyl group), which may be a variety of NH3Wherein at least one hydrogen is substituted with a hydroxyl-containing aliphatic hydrocarbon group (preferably an alkyl group).
Specifically, the quaternary ammonium base may be a quaternary ammonium base represented by formula II, the aliphatic amine may be an aliphatic amine represented by formula III, and the aliphatic alcohol amine may be an aliphatic alcohol amine represented by formula IV:
Figure BDA0001259272780000131
in the formula II, R5、R6、R7And R8Each is C1-C4Alkyl of (2) including C1-C4Straight chain alkyl of (2) and C3-C4Branched alkyl groups of (a), for example: r5、R6、R7And R8Each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
R9(NH2)nFormula III
In the formula III, n is an integer of 1 or 2. When n is 1, R9Is C1～C6Alkyl of (2) including C1～C6Straight chain alkyl of (2) and C3-C6Branched alkyl of (2)Such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl and n-hexyl. When n is 2, R9Is C1-C6Alkylene of (2) including C1～C6Linear alkylene of (A) and (C)3～C6Such as methylene, ethylene, n-propylene, n-butylene, n-pentylene or n-hexylene. More preferably, the aliphatic amine compound is one or more of ethylamine, n-butylamine, butanediamine and hexamethylenediamine
(HOR10)mNH(3-m)Formula IV
In the formula IV, m are R10Are the same or different and are each C1-C4Alkylene of (2) including C1-C4Linear alkylene of (A) and (C)3-C4Branched alkylene groups of (a), such as methylene, ethylene, n-propylene and n-butylene; m is 1, 2 or 3. More preferably, the aliphatic alcohol amine compound is one or more of monoethanolamine, diethanolamine and triethanolamine.
Most preferably, the alkali source is at least one selected from the group consisting of sodium hydroxide, aqueous ammonia, ethylenediamine, n-butylamine, butanediamine, hexamethylenediamine, monoethanolamine, diethanolamine, triethanolamine, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide. Wherein, when the alkali source contains ammonia water, the mol ratio of the alkali source includes NH in molecular form3And NH in ionic form4 +The presence of ammonia.
In a preferred embodiment of the above two titanium silicalite molecular sieves, the source of alkalinity is preferably provided in the form of an alkaline solution, more preferably the alkaline solution has a pH > 9.
In a preferred embodiment of the above two titanium-silicon-aluminum molecular sieves, the aqueous solvent is substantially water, and a cosolvent may be added as needed, in the embodiment of the present disclosure, the aqueous solvent is water.
According to the method of the present disclosure, the oxidizing agent may be at least one selected from the group consisting of hydrogen peroxide, t-butyl hydroperoxide, cumene peroxide, cyclohexyl hydroperoxide, peracetic acid, and peroxypropionic acid, and the oxidizing agent is preferably provided in the form of an aqueous solution.
According to the method disclosed by the invention, the existence of the solvent can further improve the mixing degree of reactants in the reaction system, enhance the diffusion and more conveniently regulate the intensity of the reaction. The kind of the optional solvent is not particularly limited, and may be an organic solvent other than alcohol. In particular, when the titanium-silicon-aluminum molecular sieve prepared by the preferred embodiment of the present disclosure is used as a catalyst to perform a reaction, the addition of the solvent in the reaction is more beneficial to obtain a high selectivity to propylene glycol than the titanium-silicon-aluminum molecular sieve prepared by the second preferred embodiment. Preferably, the solvent may be at least one selected from the group consisting of acetone, butanone, acetonitrile, propionitrile, phenylacetonitrile, acetic acid, and propionic acid, preferably acetone and/or acetonitrile. The amount of solvent used may vary widely, for example, the weight ratio of solvent to catalyst may be (1-200): 1.
according to the method of the present disclosure, the reaction conditions may be: the temperature is 40-150 ℃, preferably 60-120 ℃; the pressure is 0.1-3MPa, preferably 0.2-2 MPa; the time is 1-1000min, preferably 2-500 min.
According to the method disclosed by the invention, the reaction product can be subjected to ordinary distillation or rectification, and after the target product is separated, unreacted propylene and the like can be directly returned to the reaction device for continuous reaction without separation and purification.
The invention will now be further illustrated by the following examples, without thereby being limited thereto.
In the preparation examples, the X-ray diffraction (XRD) phase diagram of the sample was measured on a Siemens D5005 type X-ray diffractometer.
In the examples and comparative examples, the reagents used were all commercially available, chemically pure reagents. The titanium silicalite molecular sieve TS-1 is prepared by the method described in Zeolite, 1992, Vol.12, pages 943-950 in the prior art, the Ti-SBA-15 molecular sieve is prepared by the method of example 1 in Chinese patent CN104649287A, and the Ti-MCM-22 molecular sieve is prepared by the method of example 1 in Chinese patent CN 1686795A. The silicoaluminophosphate molecular sieve ZSM-5 used was prepared according to the method of example 1 in Chinese patent CN1715185A, and the beta molecular sieve was prepared according to the method of example 1 in Chinese patent CN 103449465A.
The composition of the reaction product is analyzed by gas chromatography, and the analysis result is quantified by a correction normalization method. Wherein, the chromatographic analysis conditions are as follows: Agilent-6890N type chromatograph, FFAP capillary chromatographic column, sample amount of 0.5 μ L, and sample inlet temperature of 180 deg.C. The column temperature was maintained at 100 ℃ for 2min, then ramped up to 200 ℃ at a rate of 15 ℃/min and maintained for 3 min. FID detector, detector temperature 200 ℃.
In each of the examples and comparative examples:
when the molar ratio of propylene to oxidant is less than or equal to 1, the relative conversion (%) of propylene is (the molar amount of propylene in the charge-the molar amount of unreacted propylene)/the molar amount of propylene in the charge x 100%;
when the molar ratio of propylene to oxidant > 1, the relative conversion (%) of propylene is (molar amount of propylene in the charge-molar amount of unreacted propylene)/molar amount of propylene in the charge x molar amount of propylene in the charge/molar amount of oxidant in the charge x 100%;
propylene glycol selectivity (%) -, mol of propylene glycol in the product/mol of propylene total conversion x 100%.
Preparation example 1
(1) Taking a TS-1 molecular sieve (prepared by the method described in Zeolite, 1992, Vol.12: 943-950), TiO22.1%) was placed in a 100mL slurry bed reactor with continuous feed and membrane separation means, and a mixture of water and 30 wt% of hydrogen peroxide (the volume ratio of water to hydrogen peroxide was 10: 9) a mixture of cyclohexanone and tert-butanol was added at a rate of 10.5mL/h (the volume ratio of cyclohexanone to tert-butanol was 1: 2.5) adding 36 wt% ammonia water at the speed of 5.7mL/h, simultaneously adding the three material flows, continuously discharging at the corresponding speed, keeping the reaction temperature at 80 ℃, and producing the product every 1h after the reaction is stable Sampling the material, analyzing the composition of the liquid phase by using a gas chromatography, calculating the conversion rate of cyclohexanone by using the following formula, and taking the conversion rate as the activity of the titanium silicalite molecular sieve. Conversion of cyclohexanone [ (molar amount of cyclohexanone charged-molar amount of unreacted cyclohexanone)/molar amount of cyclohexanone charged]X 100%. The cyclohexanone conversion, measured for the first time, i.e. 1h, was its initial activity, which was 99.5%. After a period of about 168 hours, the cyclohexanone conversion rate is reduced from the initial 99.5% to 50%, the catalyst is separated and regenerated by roasting (roasting at 570 ℃ for 4 hours in an air atmosphere), and then the catalyst is continuously used in the cyclohexanone ammoximation reaction, and the step is repeatedly carried out until the activity after regeneration is lower than 50% of the initial activity, at which time, the inactivated ammoximation catalyst sample is used as the discharging agent of the preparation example, and discharging agents SH-1 (the activity is 40%), SH-2 (the activity is 25%) and SH-3 (the activity is 10%) are sequentially obtained according to the method.
(2) Under normal temperature (20 ℃, the same below) and normal pressure (0.1MPa, the same below), firstly mixing and pulping the inactivated cyclohexanone oximation catalyst SH-1 and 1mol/L naphthenic acid aqueous solution, then mixing and stirring the mixed slurry at 45 ℃, and carrying out first heat treatment for 12 hours; after solid-liquid separation, mixing a solid (with a relative crystallinity of 71 percent), aluminum source aluminum sulfate, titanium source titanium sulfate and a sodium hydroxide aqueous solution (with a pH value of 12), putting the mixed solution into a stainless steel sealed reaction kettle, and carrying out second heat treatment for 12 hours at 170 ℃, wherein the material composition by mass is an inactivated cyclohexanone oximation catalyst: a titanium source: an aluminum source: acid: alkali: 100 parts of water: 1: 1: 2: 5: 250, deactivated cyclohexanone oximation catalyst with SiO 2Measured as H, acid+Calculated as OH, base-And (6) counting. And filtering the obtained product, washing with water, drying at 110 ℃ for 120min, and then roasting at 550 ℃ for 3h to obtain the molecular sieve, wherein an XRD (X-ray diffraction) crystal phase diagram of the molecular sieve shows that the titanium-silicon-aluminum molecular sieve (TS-A) with an MFI structure is obtained.
(3) Firstly, mixing and pulping deactivated cyclohexanone oximation catalyst SH-2 and 5mol/L peroxyacetic acid solution at normal temperature and normal pressure, then mixing and stirring the mixed slurry at 20 ℃, and carrying out first heat treatment for 20 hours; after solid-liquid separation, solid (relative crystallinity is 89%), aluminum source aluminum sol (containingThe amount is 20 weight percent), mixing titanium source tetrabutyl titanate and tetrapropyl ammonium hydroxide aqueous solution (pH is 10), putting the mixed solution into a stainless steel sealed reaction kettle, and carrying out second heat treatment for 20 hours at 150 ℃, wherein the mass composition of the materials is inactivated cyclohexanone oximation catalyst: a titanium source: an aluminum source: acid: alkali: 100 parts of water: 2: 0.5: 8: 15: 200 deactivated cyclohexanone oximation catalyst with SiO2Measured as H, acid+Calculated as OH, base-And (6) counting. And (3) recovering the product according to the method in the step (2) to obtain the titanium-silicon-aluminum molecular sieve, wherein an XRD crystal phase diagram of the titanium-silicon-aluminum molecular sieve shows that the titanium-silicon-aluminum molecular sieve (TS-B) with an MFI structure is obtained.
(4) Under normal temperature and normal pressure, mixing and pulping the inactivated cyclohexanone oximation catalyst SH-3 and 8mol/L aqueous solution of peroxypropionic acid, then mixing and stirring the mixed slurry at 30 ℃, and carrying out first heat treatment for 10 hours; after solid-liquid separation, mixing the solid (the relative crystallinity is 80%), aluminum source aluminum hydroxide, titanium tetrachloride and ethylenediamine aqueous solution (the pH is 11), putting the mixed solution into a stainless steel sealed reaction kettle, and carrying out second heat treatment for 5 hours at the temperature of 140 ℃, wherein the material composition by mass is an inactivated cyclohexanone oximation catalyst: a titanium source: an aluminum source: acid: alkali: 100 parts of water: 5: 2: 5: 5: 150 deactivated cyclohexanone oximation catalyst with SiO 2Measured as H, acid+The base is calculated as N. And (3) recovering the product according to the method in the step (2) to obtain the titanium-silicon-aluminum molecular sieve, wherein an XRD crystal phase diagram of the titanium-silicon-aluminum molecular sieve shows that the titanium-silicon-aluminum molecular sieve (TS-C) with an MFI structure is obtained.
(5) Preparing the titanium-silicon-aluminum molecular sieve according to the method in the step (4), except that the temperature of the first heat treatment is 60 ℃, the relative crystallinity of the solid after solid-liquid separation is 65%, and an XRD crystal phase diagram shows that the titanium-silicon-aluminum molecular sieve (TS-D) with an MFI structure is obtained.
(6) Preparing the titanium-silicon-aluminum molecular sieve according to the method in the step (4), except that the temperature of the first heat treatment is 180 ℃, the relative crystallinity of the solid after solid-liquid separation is 95%, and an XRD crystal phase diagram shows that the titanium-silicon-aluminum molecular sieve (TS-E) with an MFI structure is obtained.
(7) Preparing the titanium-silicon-aluminum molecular sieve according to the method in the step (4), except that formic acid is replaced by the peroxopropionic acid aqueous solution, the relative crystallinity of the solid after solid-liquid separation is 60%, and an XRD crystal phase diagram shows that the titanium-silicon-aluminum molecular sieve (TS-F) with an MFI structure is obtained.
(8) Preparing a titanium-silicon-aluminum molecular sieve according to the method in the step (4), except that the deactivated cyclohexanone oximation catalyst: acid 100: 15, the relative crystallinity of the solid after solid-liquid separation is 62%, and an XRD crystal phase diagram shows that the titanium-silicon-aluminum molecular sieve (TS-G) with an MFI structure is obtained.
(9) Preparing the titanium-silicon-aluminum molecular sieve according to the method in the step (4), except that the TS-1 molecular sieve (the relative crystallinity is 100%), aluminum source aluminum hydroxide, titanium source titanium tetrachloride and ethylene diamine aqueous solution are directly mixed for second heat treatment, and an XRD crystal phase diagram shows that the titanium-silicon-aluminum molecular sieve (TS-H) with an MFI structure is obtained.
Preparation example 2
(1) ZSM-5 molecular sieve (prepared by the method described in example 1 of CN 1715185A) is treated with water vapor at 200 deg.C for 10h, then tableted, sieved, and 20-40 mesh particles are loaded into a tubular reaction tube with diameter of 0.8cm and length of 55cm, and the bed volume of catalyst particles is 2.0cm3. The reaction temperature is 300 ℃, the reaction pressure is 1atm, the feeding molar ratio of hydrogen sulfide and methanol is 1:2, and the total gas volume space velocity is 700h-1Under the conditions of (1), a catalytic reaction for synthesizing dimethyl sulfide is carried out. And analyzing the product obtained after the catalytic reaction is carried out for 3 hours by using gas chromatography, calculating the conversion rate of the methanol according to the analysis result, and taking the conversion rate as the activity of the silicon-aluminum molecular sieve. Conversion of methanol [ (molar amount of methanol added-molar amount of unreacted methanol)/molar amount of methanol added]X 100%. Wherein the initial activity was 99% as the result of 1 h. After a period of about 180 hours, the conversion rate of methanol is reduced from the initial 99% to 50%, the catalyst is separated and regenerated by roasting (roasting at 570 ℃ for 4 hours in air atmosphere), then the catalyst is continuously used in the synthetic reaction of hydrogen sulfide and methanol, the step is repeatedly carried out until the activity after regeneration is lower than 50% of the initial activity, the inactivated catalyst sample is used as the discharging agent of the invention, and then the discharging agents SH-I (the activity is 45%), SH-II (the activity is 35%), SH-III (the activity is 45%) are sequentially obtained according to the method Sex 15%).
(2) Mixing and pulping the inactivated catalyst SH-I and 1mol/L naphthenic acid aqueous solution at normal temperature (20 ℃, the same below) and normal pressure (0.1MPa, the same below), mixing and stirring the mixed pulp at 50 ℃, and carrying out third heat treatment for 12 hours; after solid-liquid separation, mixing the solid (the relative crystallinity is 70 percent), titanium sulfate as a titanium source and an aqueous solution of sodium hydroxide (the pH value is 12), putting the mixed solution into a stainless steel sealed reaction kettle, and carrying out fourth heat treatment for 12 hours at 170 ℃, wherein the material comprises the following components in percentage by mass: a titanium source: acid: alkali: 100 parts of water: 1: 2: 5: 250, deactivated catalyst is SiO2Acid is calculated as H+Calculated as OH, base-And (6) counting. And filtering the obtained product, washing with water, drying at 110 ℃ for 120min, and then roasting at 550 ℃ for 3h to obtain the molecular sieve, wherein an XRD (X-ray diffraction) crystal phase diagram of the molecular sieve shows that the titanium-silicon-aluminum molecular sieve (SA-A) with an MFI structure is obtained.
(3) Mixing and pulping the inactivated catalyst SH-II and 5mol/L peroxyacetic acid solution at normal temperature and normal pressure, mixing and stirring the mixed pulp at 150 ℃, and carrying out third heat treatment for 20 hours; after solid-liquid separation, mixing the solid (the relative crystallinity is 53%), tetrabutyl titanate derived from titanium and tetrapropylammonium hydroxide aqueous solution (the pH is 10), putting the mixed solution into a stainless steel sealed reaction kettle, and carrying out fourth heat treatment for 20 hours at 150 ℃, wherein the material comprises the following components in percentage by mass: a titanium source: acid: alkali: 100 parts of water: 2: 8: 15: 200 deactivated cyclohexanone oximation catalyst with SiO 2Measured as H, acid+Calculated as OH, base-And (6) counting. And (3) recovering the product according to the method in the step (2) to obtain the titanium-silicon-aluminum molecular sieve, wherein an XRD crystal phase diagram of the titanium-silicon-aluminum molecular sieve shows that the titanium-silicon-aluminum molecular sieve (SA-B) with an MFI structure is obtained.
(4) Mixing and pulping the inactivated catalyst SH-III and 8mol/L aqueous solution of peroxypropionic acid at normal temperature and normal pressure, and then mixing and stirring the mixed pulp at 100 ℃ for 10 hours; after solid-liquid separation, mixing a solid (the relative crystallinity is 61 percent), titanium tetrachloride serving as a titanium source and an ethylenediamine aqueous solution (the pH value is 11), putting the mixed solution into a stainless steel sealed reaction kettle, and carrying out hydrothermal treatment for 5 hours at the temperature of 140 ℃, wherein the mass components of the materials are inactivated catalysts: a titanium source: acid:alkali: 100 parts of water: 5: 5: 5: 150, deactivated catalyst with SiO2Acid is calculated as H+The alkali is counted as N. And (3) recovering the product according to the method in the step (2) to obtain the titanium-silicon-aluminum molecular sieve, wherein an XRD crystal phase diagram of the titanium-silicon-aluminum molecular sieve shows that the titanium-silicon-aluminum molecular sieve (SA-C) with an MFI structure is obtained.
(5) Preparing the titanium-silicon-aluminum molecular sieve according to the method in the step (4), except that the temperature of the third heat treatment is 40 ℃, the relative crystallinity of the solid after solid-liquid separation is 41%, and an XRD crystal phase diagram shows that the titanium-silicon-aluminum molecular sieve (SA-D) with an MFI structure is obtained.
(6) Preparing the titanium-silicon-aluminum molecular sieve according to the method in the step (4), except that the temperature of the third heat treatment is 180 ℃, the relative crystallinity of the solid after solid-liquid separation is 80%, and an XRD crystal phase diagram shows that the titanium-silicon-aluminum molecular sieve (SA-E) with an MFI structure is obtained.
(7) Preparing the titanium-silicon-aluminum molecular sieve according to the method in the step (4), except that formic acid is replaced by the peroxopropionic acid aqueous solution, the relative crystallinity of the solid after solid-liquid separation is 38%, and an XRD crystal phase diagram shows that the titanium-silicon-aluminum molecular sieve (SA-F) with an MFI structure is obtained.
(8) Preparing a titanium-silicon-aluminum molecular sieve according to the method in the step (4), wherein the difference is that the deactivated catalyst: acid 100: 20, the relative crystallinity of the solid after solid-liquid separation is 30 percent, and an XRD crystal phase diagram shows that the titanium-silicon-aluminum molecular sieve (SA-G) with an MFI structure is obtained.
(9) Preparing the titanium-silicon-aluminum molecular sieve according to the method in the step (4), except that a ZSM-5 molecular sieve (the relative crystallinity is 100 percent), titanium tetrachloride serving as a titanium source and an ethylene diamine aqueous solution are directly mixed for fourth heat treatment, and an XRD crystal phase diagram shows that the titanium-silicon-aluminum molecular sieve (SA-H) with an MFI structure is obtained.
Example 1
Putting propylene, 30 wt% aqueous hydrogen peroxide and a catalyst (ZSM-5 molecular sieve and TS-1 molecular sieve in a weight ratio of 1:3) into a reaction kettle, wherein the molar ratio of the propylene to the hydrogen peroxide is 1: and 2, the weight ratio of the propylene to the water to the catalyst is 20: 20: 1, the reaction is carried out at a temperature of 60 ℃ and a pressure of 1.5 MPa. The results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
Example 2
Putting propylene, 30 wt% aqueous hydrogen peroxide and a catalyst (ZSM-5 molecular sieve and TS-1 molecular sieve in a weight ratio of 1:1) into a reaction kettle, wherein the molar ratio of the propylene to the hydrogen peroxide is 1: 5, the weight ratio of the propylene to the water to the catalyst is 40: 100: 1, the reaction is carried out at a temperature of 60 ℃ and a pressure of 1.5 MPa. The results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
Example 3
Putting propylene, 30 wt% aqueous hydrogen peroxide, acetone as a solvent and a catalyst (beta molecular sieve and TS-1 molecular sieve in a weight ratio of 1:0.5) into a reaction kettle, wherein the molar ratio of the propylene to the hydrogen peroxide is 1:0.5, the weight ratio of the propylene to the water to the catalyst is 100: 15: 1, the weight ratio of solvent acetone to catalyst is 50: 1. the reaction was carried out at a temperature of 40 ℃ and a pressure of 0.2 MPa. The results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
Example 4
Putting propylene, 40 wt% of tert-butyl hydroperoxide aqueous solution and a catalyst (beta molecular sieve and Ti-SBA-15 molecular sieve in a weight ratio of 1:0.1) into a reaction kettle, wherein the molar ratio of the propylene to the tert-butyl hydroperoxide is 1: 8, the weight ratio of the propylene to the water to the catalyst is 150: 60: 1, the reaction is carried out at a temperature of 40 ℃ and a pressure of 0.2 MPa. The results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
Example 5
Putting propylene, cumyl peroxide and a catalyst (a ZSM-5 molecular sieve and a Ti-MCM-22 molecular sieve in a weight ratio of 1:6) into a reaction kettle, wherein the molar ratio of the propylene to the cumyl peroxide is 1: 0.1, the weight ratio of propylene to catalyst is 0.5: 1: 1, the reaction is carried out at a temperature of 50 ℃ and a pressure of 0.2 MPa. The results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
Example 6
Propylene, A30 wt% aqueous hydrogen peroxide solution and A catalyst (TS-A) were charged into A reaction vessel, the molar ratio of propylene to hydrogen peroxide was 1: and 2, the weight ratio of the propylene to the water to the catalyst is 20: 15: 1, the reaction is carried out at a temperature of 60 ℃ and a pressure of 1.5 MPa. The results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
Example 7
Propylene, 30 wt% aqueous hydrogen peroxide, acetone as a solvent, and a catalyst (TS-B) were charged into a reaction vessel, and the molar ratio of propylene to hydrogen peroxide was 1: 5, the weight ratio of the propylene to the water to the catalyst is 60: 40: 1, the weight ratio of solvent acetone to catalyst is 50: 1. the reaction was carried out at a temperature of 30 ℃ and a pressure of 1.5 MPa. The results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
Example 8
Propylene, 30 wt% aqueous hydrogen peroxide, solvent acetonitrile and catalyst (TS-C) were charged to a reaction kettle, the molar ratio of propylene to hydrogen peroxide was 1: 0.5, the weight ratio of the propylene to the water to the catalyst is 80: 10: 1, the weight ratio of the solvent acetonitrile to the catalyst is 100: 1. the reaction was carried out at a temperature of 80 ℃ and a pressure of 1.0 MPa. The results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
Examples 9 to 13
Propylene was oxidized by the method of example 8, except that the catalyst was replaced with TS-D, TS-E, TS-F, TS-G and TS-H, respectively, and the results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
Example 14
Propylene was oxidized by the method of example 6, except that the catalyst was replaced with SA-A, and the results of the reaction for 2 hours and the reaction for 12 hours were shown in Table 1.
Example 15
Propylene was oxidized by the method of example 7, except that the catalyst was replaced with SA-B, and the results of the reaction for 2 hours and the reaction for 12 hours were shown in Table 1.
Example 16
Propylene was oxidized by the method of example 8, except that the catalyst was replaced with SA-C, and the results of the reaction for 2 hours and the reaction for 12 hours were shown in Table 1.
Examples 17 to 21
Propylene was oxidized by the method of example 8, except that the catalyst was replaced with SA-D, SA-E, SA-F, SA-G and SA-H, respectively, and the results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
Example 22
Propylene was oxidized by the method of example 8, except that the titanium silicalite molecular sieve prepared in example 1 according to chinese patent CN102616805A was used as a catalyst, and the results of the reaction for 2 hours and the reaction for 12 hours are shown in table 1.
Example 23
Propylene was oxidized by the method of example 7, except that acetone, a solvent, was not used in this example. The results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
Example 24
Propylene was oxidized by the method of example 15 except that acetone, a solvent, was not used in this example. The results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
Comparative example 1
The reaction was carried out in the same manner as in example 1 except that no catalyst was used in this comparative example. The results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
Comparative example 2
The reaction was carried out as in example 1, except that this comparative example used titanium silicalite TS-1 as the catalyst. The results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
Comparative example 3
The reaction was carried out as in example 1, except that this comparative example used a silicalite ZSM-5 as the catalyst. The results of the reaction for 2 hours and the reaction for 12 hours are shown in Table 1.
TABLE 1
Figure BDA0001259272780000241
Figure BDA0001259272780000251
The results prove that the propylene can be oxidized by the method disclosed by the invention, the higher propylene conversion rate can be obtained, the selectivity of propylene glycol in the product is higher, and the catalytic oxidation activity and the catalytic activity stability of the catalyst are better. As can be seen from a comparison of example 1 and comparative examples 1-3, the method of the present disclosure can greatly improve propylene glycol selectivity compared to the method without using a catalyst and using a titanium silicalite molecular sieve and a silicoaluminophosphate molecular sieve as catalysts, respectively. As can be seen by comparing examples 1-3 with examples 4-5, when the molar ratio of propylene to oxidant is 1: (0.2-5), the weight ratio of the propylene, the solvent and the catalyst is preferably (1-100): (2-150): 1, the relative conversion of propylene and the selectivity to propylene glycol can be further improved. As can be seen from the comparison between examples 6-8 and examples 9-13, and between examples 14-16 and examples 17-24, the titanium silicalite molecular sieves prepared by the specific method are advantageous for obtaining higher propylene relative conversion and propylene glycol selectivity when used in a reaction. As can be seen by comparing example 6 with examples 7-8 and example 14 with examples 15-16, and in particular example 7 with example 23 and example 15 with example 24, the addition of solvent is more beneficial to achieve high propylene glycol selectivity when reacting the titanium silicalite molecular sieves prepared with the first preferred embodiment of the present disclosure as compared to the titanium silicalite molecular sieves prepared with the second preferred embodiment of the present disclosure.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of the various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present invention, as long as the combination does not depart from the spirit of the present disclosure.

Claims (14)

1. A process for the oxidation of propylene, the process comprising: carrying out contact reaction on propylene, an oxidant and water in the presence of a catalyst, wherein the catalyst contains a titanium-silicon-aluminum molecular sieve; wherein the weight ratio of propylene, catalyst and water is (0.5-150): 1: (1-200); wherein, the preparation steps of the titanium-silicon-aluminum molecular sieve comprise:
(1) Mixing and pulping a first discharging agent and an organic acid solution, carrying out first heat treatment on the obtained slurry, and separating to obtain a first solid, wherein the first discharging agent is a discharging agent of a reaction device which takes a titanium silicalite molecular sieve as a catalyst active component, and the conditions of the first heat treatment are as follows: the temperature is 20-45 ℃ and the time is 1-30 h; wherein the relative crystallinity of the first solid obtained after the first heat treatment is from 70 to 90%;
(2) mixing the first solid, an aluminum source, a titanium source and an alkali source in the presence of an aqueous solvent, and then carrying out second heat treatment, wherein the conditions of the second heat treatment are as follows: the temperature is 100 ℃ and 200 ℃, and the time is 0.5-25 h; or, the preparation steps of the titanium-silicon-aluminum molecular sieve comprise:
a. mixing and pulping a second discharging agent and an organic acid solution, carrying out third heat treatment on the obtained slurry, and separating to obtain a second solid, wherein the second discharging agent is a discharging agent of a reaction device which takes a silicon-aluminum molecular sieve as an active component of a catalyst, and the conditions of the third heat treatment are as follows: the temperature is 50-150 ℃, and the time is 0.5-40 h; wherein the relative crystallinity of the second solid obtained after the third heat treatment is from 50 to 70%;
b. Mixing the second solid, a titanium source and an alkali source in the presence of an aqueous solvent, and then carrying out fourth heat treatment, wherein the conditions of the fourth heat treatment are as follows: the temperature is 100 ℃ and 200 ℃, and the time is 0.5-25 h;
wherein relative crystallinity refers to the crystallinity of a solid relative to fresh agent to which the discharge agent corresponds.
2. The process of claim 1, wherein the molar ratio of propylene to oxidant is 1: (0.1-10); the reaction conditions are as follows: the temperature is 40-150 ℃, and the pressure is 0.1-3 MPa; the oxidant is at least one selected from hydrogen peroxide, tert-butyl hydroperoxide, cumyl peroxide, cyclohexyl hydroperoxide, peroxyacetic acid and peroxypropionic acid.
3. The process of claim 2, wherein the molar ratio of propylene to oxidant is 1: (0.2-5).
4. The process according to claim 2, wherein the weight ratio of propylene, catalyst and water is (1-100): 1: (2-150).
5. The process of claim 1, wherein, when the catalyst contains a titanium silicalite molecular sieve, the titanium silicalite molecular sieve is at least one selected from the group consisting of a titanium silicalite molecular sieve of MFI structure, a titanium silicalite molecular sieve of MEL structure, a titanium silicalite molecular sieve of BEA structure, a titanium silicalite molecular sieve of MWW structure, a titanium silicalite molecular sieve of MOR structure, a titanium silicalite molecular sieve of TUN structure, and a titanium silicalite molecular sieve of two-dimensional hexagonal structure.
6. The method of claim 1, wherein the weight ratio of the first discharging agent, the titanium source, the aluminum source, the organic acid, the alkali source, and the water is 100: (0.1-10): (0.1-10): (0.005-50): (0.5-50): (20-1000), the first discharging agent is SiO2The organic acid is counted as H+The alkali source is counted as N when containing nitrogen element, and the alkali source is counted as OH when not containing nitrogen element-Counting; the concentration of the organic acid solution is more than 0.1 mol/L.
7. The method according to claim 1, wherein the discharging agent of the reaction device using the titanium silicalite molecular sieve as the catalyst active component in the step (1) is at least one selected from the group consisting of a discharging agent of an ammoximation reaction device, a discharging agent of a hydroxylation reaction device and a discharging agent of an epoxidation reaction device.
8. The process of claim 1, wherein the titanium silicalite molecular sieves in step (1) are of the MFI structure and the activity of the first discharge agent is less than 50% of the activity of the titanium silicalite molecular sieves when fresh.
9. The method according to claim 1, wherein in the step (2), the aluminum source and the alkali source are mixed in the presence of an aqueous solvent to obtain a mixed solution, and then the second heat treatment is performed after the mixed solution is mixed with the first solid and the titanium source.
10. The method of claim 1, wherein the weight ratio of the second discharging agent, the titanium source, the organic acid, the alkali source, and the water is 100: (0.1-10): (0.005-50): (0.5-50): (20-1000), the second discharging agent is SiO2The organic acid is calculated as H+The alkali source is counted as N when containing nitrogen element, and the alkali source is counted as OH when not containing nitrogen element-Counting; the concentration of the organic acid solution is more than 0.1 mol/L.
11. The method of claim 1, wherein the discharging agent of the reaction device with the silicon-aluminum molecular sieve as the catalyst active component in the step a is the discharging agent of a synthesis reaction device of hydrogen sulfide and methanol.
12. The process of claim 1, wherein the silicoaluminophosphate molecular sieve in step a is a silicoaluminophosphate molecular sieve of the MFI structure, and the activity of the second discharge agent is less than 50% of the activity of the silicoaluminophosphate molecular sieve when fresh.
13. The method according to claim 1, wherein the organic acid is at least one selected from the group consisting of naphthenic acid, peracetic acid, and propionic acid; the alkali source is at least one selected from ammonia, aliphatic amine, aliphatic alcohol amine and quaternary ammonium base; the aluminum source is at least one selected from aluminum sol, aluminum salt, aluminum hydroxide and aluminum oxide; the titanium source is inorganic titanium salt and/or organic titanate.
14. The method of claim 1, wherein the method further comprises: the reaction is carried out in the presence of a solvent, wherein the solvent is at least one selected from acetone, butanone, acetonitrile, propionitrile, phenylacetonitrile, acetic acid and propionic acid, and the weight ratio of the solvent to the catalyst is (1-200): 1.
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