CN110759809B - Propylene oxidation process - Google Patents

Propylene oxidation process Download PDF

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CN110759809B
CN110759809B CN201810846523.6A CN201810846523A CN110759809B CN 110759809 B CN110759809 B CN 110759809B CN 201810846523 A CN201810846523 A CN 201810846523A CN 110759809 B CN110759809 B CN 110759809B
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titanium
molecular sieve
silicon
source
aluminum
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CN110759809A (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
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present disclosure relates to a process for the oxidation of propylene, the process comprising the steps of: s1, carrying out a first reaction on propylene, an oxidant and methanol in the presence of a first catalyst to obtain a first reaction mixture, wherein the first catalyst contains a titanium silicalite molecular sieve; s2, mixing the first reaction mixture with a second catalyst to perform a second reaction, wherein the second catalyst contains a titanium-silicon-aluminum molecular sieve; the ratio of the reaction time of the first reaction to the reaction time of the second reaction is 1: (0.1-50). The method can produce propylene glycol monomethyl ether and propylene glycol under mild conditions.

Description

Propylene oxidation process
Technical Field
The present disclosure relates to a process for the oxidation of propylene.
Background
Propylene glycol monomethyl ether, also known as propylene glycol methyl ether, includes two isomers: 1-methoxy-2-propanol and 2-methoxy-1-propanol. Propylene glycol methyl ether has weak ether smell but no strong pungent smell, so that the application is wider and safer: the emulsion can be used for styrene-acrylic emulsion, acrylic emulsion and emulsion paint systems thereof, and has the characteristics of reducing film forming temperature, promoting condensation and film forming of the emulsion, and ensuring that a coating film has a good state; besides being used as a solvent of various high-grade coatings, the solvent is also used as a regulator for controlling volatilization speed and viscosity in printing ink; can also be used as viscosity regulator in chemical intermediate and brake fluid formula; the propylene glycol methyl ether can be mixed with water in any proportion, so that the propylene glycol methyl ether can be applied to various fields such as a solvent in a metal cleaning agent formula or an anti-icing fluid for an automobile water tank to reduce the freezing point; and can be used as raw material for organic synthesis.
The propylene glycol is colorless viscous liquid in normal state, is almost tasteless, smells slightly sweet, and can be used as raw material of unsaturated polyester resin; can be used as humectant in cosmetics, toothpaste and soap in combination with glycerol or sorbitol; it is used in hair dye as a conditioning agent, a hair conditioner, an antifreeze, a cellophane, a plasticizer and a pharmaceutical industry.
The existing production of propylene glycol ether and propylene glycol basically adopts propylene oxide as a raw material to be synthesized with alcohol or water, and the propylene glycol ether and the propylene glycol are usually produced at high temperature (such as 180-220 ℃). In addition, most of the current world production of propylene oxide adopts a chlorohydrin method and an oxidation method, the chlorohydrin method has serious corrosion pollution, and the oxidation method has large investment and coproduces a large amount of byproducts, so that the production of propylene glycol ether and propylene glycol is restricted from raw materials.
Therefore, aiming at the defects of the prior art, the research of a novel process for preparing propylene glycol monomethyl ether and 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 propylene oxidation process that can produce propylene glycol monomethyl ether and propylene glycol under mild conditions.
In order to achieve the above object, the present disclosure provides a propylene oxidation process comprising the steps of:
s1, carrying out a first reaction on propylene, an oxidant and methanol in the presence of a first catalyst to obtain a first reaction mixture, wherein the first catalyst contains a titanium-silicon molecular sieve;
s2, mixing the first reaction mixture with a second catalyst to perform a second reaction, wherein the second catalyst contains a titanium-silicon-aluminum molecular sieve;
the ratio of the reaction time of the first reaction to the reaction time of the second reaction is 1: (0.1-50).
Optionally, the molar ratio of propylene, oxidant and methanol is 1: (0.1-10): (0.1-10), preferably 1: (0.2-5): (2-5); the weight ratio of the propylene to the first catalyst to the second catalyst is 100: (2-1000): (5-200), preferably 100: (5-500): (10-100);
the oxidant is selected from hydrogen peroxide, tert-butyl hydroperoxide, cumyl peroxide, cyclohexyl hydroperoxide, peroxyacetic acid or peroxypropionic acid.
Optionally, the conditions of the first reaction are: the temperature is 0-80 ℃, and the pressure is 0.1-2.5MPa;
the conditions of the second reaction are as follows: the temperature is 0-80 deg.C, and the pressure is 0.1-2.5MPa.
Optionally, the titanium silicalite molecular sieve is 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 or an MRE-type titanium silicalite molecular sieve;
the titanium-silicon-aluminum molecular sieve is a titanium-silicon-aluminum molecular sieve with an MFI structure, a titanium-silicon-aluminum molecular sieve with an MEL structure, 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 or a titanium-silicon-aluminum molecular sieve with a two-dimensional hexagonal structure.
Optionally, 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;
(2) Mixing the first solid, a silicon source, 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 ℃, and the time is 0.5-25h;
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 0.5-40h;
b. mixing the second solid, a silicon source, 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 deg.C, and the time is 0.5-25h.
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 SiO 2 The 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; with SiO 2 The silicon source is calculated by TiO 2 The molar ratio of the titanium source is (5-20): 1; the concentration of the organic acid solution is more than 0.1mol/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 less than 50% of the activity of the titanium silicalite molecular sieve in a fresh state;
preferably, in the step (2), the aluminum source and the alkali source are mixed in the presence of the 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.
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 SiO 2 The 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; with SiO 2 The silicon source is calculated by TiO 2 The molar ratio of the titanium source is (5-20): 1; the concentration of the organic acid solution is more than 0.1mol/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 naphthenic acid, peracetic acid, or propionic acid; the alkali source is ammonia, aliphatic amine, aliphatic alcohol amine or quaternary ammonium base; the aluminum source is aluminum sol, aluminum salt, aluminum hydroxide or aluminum oxide; the titanium source is inorganic titanium salt and/or organic titanate; the silicon source is organic silicate ester.
By adopting the technical scheme, in the propylene oxidation process, different catalysts are sequentially used, so that the reaction temperature can be effectively reduced, and the conversion rate of propylene and the selectivity of propylene glycol monomethyl ether and propylene glycol can be obviously improved. In addition, in the method disclosed by the invention, the catalyst is easy to recycle, the whole process is environment-friendly, simple and easy to control, no special equipment requirement exists, and the method is beneficial to industrial production and application.
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 steps of:
s1, carrying out a first reaction on propylene, an oxidant and methanol in the presence of a first catalyst to obtain a first reaction mixture, wherein the first catalyst contains a titanium silicalite molecular sieve;
s2, mixing the first reaction mixture with a second catalyst to perform a second reaction, wherein the second catalyst contains a titanium-silicon-aluminum molecular sieve;
the ratio of the reaction time of the first reaction to the reaction time of the second reaction is 1: (0.1-50).
The inventor of the invention unexpectedly finds that in the process of preparing propylene glycol monomethyl ether and propylene glycol from propylene, different catalysts are sequentially used, particularly a catalyst containing a titanium-silicon-aluminum molecular sieve is introduced later, so that the reaction temperature can be effectively reduced, and the conversion rate of propylene and the selectivity of propylene glycol monomethyl ether and propylene glycol can be obviously improved.
In order to obtain the desired reaction effect, the molar ratio of the propylene, the oxidant and the methanol may be 1: (0.1-10): (0.1-10), preferably 1: (0.2-5): (2-5). The ratio of the reaction time of the first reaction to the reaction time of the second reaction is preferably 1: (0.1-10), more preferably 1: (0.2-5).
According to the process of the present disclosure, the oxidizing agent may be selected from hydrogen peroxide, tert-butyl hydroperoxide, cumene peroxide, cyclohexyl hydroperoxide, peroxyacetic acid or peroxypropionic acid. The oxidizing agent is preferably provided in the form of an aqueous solution.
According to the present disclosure, the first catalyst and the second catalyst are used in amounts that enable a catalytic function. For example, the weight ratio of propylene, first catalyst, and second catalyst may be 100: (2-1000): (5-200), preferably 100: (5-500): (10-100).
In the process of the present disclosure, propylene oxidation can be carried out under milder conditions. The conditions of the first reaction may be: the temperature is 0-80 ℃, preferably 30-60 ℃; the pressure is 0.1-2.5MPa, preferably 1-1.5MPa. The conditions of the second reaction may be: the temperature is 0-80 ℃, preferably 30-60 ℃; the pressure is 0.1-2.5MPa, preferably 1-1.5MPa.
According to the present disclosure, the titanium silicalite molecular sieve may be an MFI type titanium silicalite molecular sieve, an MEL type titanium silicalite molecular sieve, an MWW type titanium silicalite molecular sieve, a hexagonal titanium silicalite molecular sieve or an MRE type titanium silicalite molecular sieve, and is more preferably 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 or a Ti-ZSM-48 molecular sieve. The titanium silicalite molecular sieves can be prepared according to the prior art or can 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 silicalite molecular sieve, the titanium silicalite molecular sieve can be a common titanium silicalite molecular sieve with various topologies, such as: the titanium-silicon-aluminum molecular sieve can be 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 or a titanium-silicon-aluminum molecular sieve with a two-dimensional hexagonal structure. The titanium-silicon-aluminum molecular sieve is preferably a titanium-silicon-aluminum molecular sieve with an MFI structure, a titanium-silicon-aluminum molecular sieve with an MEL structure or a titanium-silicon-aluminum molecular sieve with a BEA structure, and more preferably a titanium-silicon-aluminum molecular sieve with an MFI structure.
According to the present disclosure, the titanium-silicon-aluminum molecular sieve is used as a catalyst in step S2, but the inventors of the present disclosure found in research that the titanium-silicon-aluminum molecular sieve prepared by a specific method is particularly beneficial to improve the selectivity of propylene glycol monomethyl ether and 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 10-20h;
(2) Mixing the first solid, a silicon source, 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 deg.C, preferably 120-180 deg.C, more preferably 140-170 deg.C, and the time is 0.5-25 hr, preferably 2-24 hr, more preferably 5-20 hr.
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 good catalytic performance can be obtained, and the selectivity of propylene glycol monomethyl ether 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 catalyst active component 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 present invention, it is preferable that the first discharging agent is a discharging agent of a cyclohexanone ammoximation reaction apparatus (such as deactivated titanium silicalite TS-1, powdery, and having a particle size of 100 to 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 50% or less of the activity of the titanium silicalite molecular sieve when fresh, and more preferably, the activity of the first discharging agent may be 10 to 40% of the activity of the titanium silicalite molecular sieve when fresh. 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 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 above, 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:
the TS-1 molecular sieves (prepared as described in Zeolite, 1992, vol.12 2 2.1%) was placed in a 100mL slurry bed reactor with continuous feed and membrane separation, and a mixture of water and 30wt% 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 36wt% ammonia water is added at the speed of 5.7mL/h, the three material flows are added simultaneously, and are discharged continuously at the corresponding speed, the reaction temperature is maintained at 80 ℃, after the reaction is stable, the product is sampled every 1h, the composition of the liquid phase is analyzed by using a gas chromatography, the conversion rate of cyclohexanone is calculated by adopting the following formula, and the cyclohexanone is used as the activity of the titanium-silicon molecular sieve. Conversion of cyclohexanone = [ (molar amount of cyclohexanone charged-not reacted)Molar amount of cyclohexanone) added]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 2 The 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. With SiO 2 The silicon source is calculated by TiO 2 The molar ratio of the titanium source may be (5-20): 1.
in the above preferred embodiment, the aluminum source is a substance capable of providing aluminum, and preferably the aluminum source is an aluminum sol, an aluminum salt, aluminum hydroxide or alumina, and the aluminum sol is preferably contained in an amount of 10 to 50% by weight in terms of alumina. The aluminium salt may be an inorganic aluminium salt, preferably a C1-C10 organic aluminium salt, and/or an organic aluminium salt, for example aluminium sulphate, sodium metaaluminate, aluminium chloride or aluminium nitrate.
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, the silicon source 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 20-200 ℃, and the roasting process can be carried out at the temperature of 300-800 ℃ in a nitrogen atmosphere for 0.5-6h and then in an air atmosphere for 3-12 h.
Alternatively, according to another preferred embodiment of the present disclosure, the step of preparing the titanium silicalite molecular sieve comprises:
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 0.5-40h, preferably 1-24h, more preferably 10-20h;
b. mixing the second solid, a silicon source, 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 deg.C, preferably 120-180 deg.C, more preferably 140-170 deg.C, and the time is 0.5-25 hr, preferably 2-24 hr, more preferably 5-20 hr.
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 good 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 monomethyl ether. 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 100-500 nm) of a synthesis reaction device for 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 described above, 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 granules are packed in a tubular reaction tube with diameter of 0.8cm and length of 55cm, and the volume of catalyst granule bed is 2.0cm 3 . At the reaction temperature of 300 ℃, the reaction pressure of 1atm, the feeding molar ratio of hydrogen sulfide and methanol of 1 -1 Under the conditions of (3), 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]X100%. Wherein the result of 1h is taken 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 SiO 2 The 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. With SiO 2 The silicon source is calculated by TiO 2 The molar ratio of the titanium source may be (5-20): 1.
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, the silicon source and the titanium source, and then performing the fourth heat treatment.
In the preferred embodiment of the above two titanium-silicon-aluminum molecular sieves, the beating 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 preferred embodiment of the above two titanium silicalite molecular sieves, the organic acid is not particularly required, and may be a C1-C10 organic carboxylic acid, preferably naphthenic acid, peroxyacetic acid or peroxypropionic acid. The concentration of the organic acid solution is preferably >0.1mol/L, more preferably ≥ 1mol/L, still more preferably 2-15mol/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 silicon source may be an inorganic silicon source and/or an organic silicon source. The inorganic silicon source can be silicate, silica sol or silica gel. The organic silicon source may be an organic silicate selected from the group consisting of formula I:
Figure BDA0001746737040000121
in the formula I, R 1 、R 2 、R 3 And R 4 Each is C 1 -C 4 Alkyl of (2) including C 1 -C 4 Straight chain alkyl of (2) and C 3 ～C 4 Branched alkyl groups such as: r 1 、R 2 、R 3 And R 4 Each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. Preferably, the silicon source is an organic silicate, such as methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, or butyl orthosilicate.
In a preferred embodiment of the above two titanium silicalite molecular sieves, the titanium source can be an organic titanium source (e.g., an organic titanate) and/or an inorganic titanium source (e.g., an inorganic titanium salt). Wherein the inorganic titanium source can be TiCl 4 、Ti(SO 4 ) 2 、TiOCl 2 Titanium hydroxide, titanium oxide, titanium nitrate or titanium phosphate, and the organic titanium source may be fatty titanium alkoxide and/or 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 M 4 TiO 4 Wherein 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 isopropyl titanate, n-propyl titanate, tetrabutyl titanate, or tetraethyl titanate. Specific examples of the titanium source may be, but are not limited to: tiOCl 2 Titanium tetrachloride, titanium sulfate, tetrapropyl titanate (including various isomers of tetrapropyl titanate, such as tetraisopropyl titanate and tetra-n-propyl titanate), tetrabutyl titanate (various isomers of tetrabutyl titanate, such as titaniumTetra-n-butyl titanate), tetraethyl titanate, and the like.
In a preferred embodiment of the above two titanium-silicon-aluminum molecular sieves, the type of the alkali source can be selected from a wide range, and the alkali source 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 urea, an aliphatic amine, an aliphatic alcohol amine, or a quaternary ammonium base compound. The quaternary ammonium base can be various organic quaternary ammonium bases, and the aliphatic amine can be various NH 3 In which at least one hydrogen is substituted with an aliphatic hydrocarbon group (preferably an alkyl group), which may be a variety of NH 3 Wherein 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 BDA0001746737040000131
in the formula II, R 5 、R 6 、R 7 And R 8 Each is C 1 -C 4 Alkyl of (2) including C 1 -C 4 Straight chain alkyl of (1) and C 3 -C 4 Branched alkyl groups of (a), for example: r 5 、R 6 、R 7 And R 8 Each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
R 9 (NH 2 ) n (formula III)
In the formula III, n is an integer of 1 or 2. When n is 1, R 9 Is C 1 ～C 6 Alkyl of (2) including C 1 ～C 6 Straight chain alkyl of (2) and C 3 -C 6 Branched alkyl radicals of (2), e.g. methyl, ethyl, n-propyl, isopropyl, n-butylAlkyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl and n-hexyl. When n is 2, R 9 Is C 1 -C 6 Alkylene of (2) including C 1 ～C 6 Linear alkylene of (A) and (C) 3 ～C 6 Such as methylene, ethylene, n-propylene, n-butylene, n-pentylene or n-hexylene. More preferably, the aliphatic amine compound is ethylamine, n-butylamine, butanediamine or hexamethylenediamine.
(HOR 10 ) m NH (3-m) (formula IV)
In the formula IV, m are R 10 Are the same or different and are each C 1 -C 4 Alkylene of (2) including C 1 -C 4 Linear alkylene of (A) and (C) 3 -C 4 Branched 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 monoethanolamine, diethanolamine or triethanolamine.
Most preferably, the alkali source is sodium hydroxide, aqueous ammonia, ethylenediamine, n-butylamine, butanediamine, hexamethylenediamine, monoethanolamine, diethanolamine, triethanolamine, tetraethylammonium hydroxide, or tetrapropylammonium hydroxide. Wherein, when the alkali source contains ammonia water, the mol ratio of the alkali source includes NH in molecular form 3 And NH in ionic form 4 + On the basis of the ammonia present.
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 disclosed by the disclosure, after the second reaction is completed, the reaction product can be subjected to a common distillation or rectification method, 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 present disclosure will be further illustrated by the following examples, but is not 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, all reagents used were commercially available, chemically pure reagents. The titanium silicalite TS-1 used was prepared as described in Zeolite, 1992, vol.12, pages 943 to 950 of the prior art. The silicoaluminophosphate molecular sieve ZSM-5 used was prepared according to the method of example 1 of Chinese patent CN 1715185A.
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 injection amount of 0.5 μ L, and sample injection port 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 3min. FID detector, detector temperature 200 ℃.
In each of the examples and comparative examples:
when the molar ratio of the propylene to the oxidant is less than or equal to 1, the relative conversion rate of the propylene (%) = (the molar amount of the propylene in the feed-the molar amount of the unreacted propylene)/the molar amount of the propylene in the feed x 100%;
when the molar ratio of propylene to oxidant > 1, the relative conversion of propylene (%) = (molar amount of propylene in charge-molar amount of unreacted propylene)/molar amount of propylene in charge x molar amount of propylene in charge/molar amount of oxidant in charge x 100%;
propylene glycol monomethyl ether selectivity (%) = molar amount of propylene glycol monomethyl ether in product/molar amount of propylene total conversion x 100%.
Propylene glycol (%) = molar amount of propylene glycol in product/molar amount of propylene total conversion x 100%.
Preparation example 1
(1) The TS-1 molecular sieves (prepared as described in Zeolite, 1992, vol.12 2 2.1%) was placed in a 100mL slurry-bed reactor with continuous feed and membrane separation unit under stirring at 5.7The method comprises the following steps of adding a mixture of water and 30wt% of hydrogen peroxide at a speed of mL/h (the volume ratio of water to hydrogen peroxide is 10: 9), adding a mixture of cyclohexanone and tert-butyl alcohol at a speed of 10.5mL/h (the volume ratio of cyclohexanone to tert-butyl alcohol is 1: 2.5), adding 36wt% of ammonia water at a speed of 5.7mL/h, adding the three streams simultaneously, continuously discharging at corresponding speeds, maintaining the reaction temperature at 80 ℃, sampling products at intervals of 1h after the reaction is stabilized, analyzing the composition of a liquid phase by using a gas chromatography, and calculating the conversion rate of cyclohexanone and using the formula as the activity of the titanium silicalite molecular sieve. Conversion of cyclohexanone = [ (molar amount of cyclohexanone added-not) molar amount of cyclohexanone reacted)/molar amount of cyclohexanone added]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 (0.1 MPa, 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 the solid (the relative crystallinity is 71%), silicon source methyl orthosilicate, aluminum source aluminum sulfate, titanium source titanium sulfate and sodium hydroxide aqueous solution (the pH is 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 the inactivated cyclohexanone oximation catalyst: a titanium source: an aluminum source: acid: alkali: water =100:1:1:2:5:250, deactivated cyclohexanone oximation catalyst with SiO 2 Measured as H, acid + Calculated as OH, base - Measured as SiO 2 Silicon source and calculated as TiO 2 The molar ratio of the titanium source is calculated as10:1. 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 pulp at 20 ℃, and carrying out first heat treatment for 20 hours; after solid-liquid separation, mixing solid (the relative crystallinity is 89%), silicon source ethyl orthosilicate, aluminum source aluminum sol (the content is 20 weight%), titanium source tetrabutyl titanate and tetrapropyl ammonium hydroxide aqueous solution (the 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 material composition by mass is an inactivated cyclohexanone oximation catalyst: a titanium source: an aluminum source: acid: alkali: water =100:2:0.5:8:15:200 deactivated cyclohexanone oximation catalyst with SiO 2 Measured as H, acid + Calculated as OH, base - Measured as SiO 2 Silicon source and based on TiO 2 The molar ratio of the titanium source is 20:1. 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 of peroxypropionic acid aqueous solution, 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%), silicon source propyl orthosilicate, aluminum source aluminum hydroxide, titanium source titanium tetrachloride and ethylenediamine aqueous solution (the pH value 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 quality composition is the inactivated cyclohexanone oximation catalyst: a titanium source: an aluminum source: acid: alkali: water =100:5:2:5:5:150, deactivated Cyclohexanone oximation catalyst with SiO 2 Measured as H, acid + Alkali is calculated as N and SiO 2 Silicon source and based on TiO 2 The molar ratio of the titanium source is 15:1. then recovering the product according to the method of the step (2) to obtain the titanium-silicon-aluminum molecular sieve, wherein the XRD crystal phase diagram of the titanium-silicon-aluminum molecular sieve shows that the titanium-silicon-aluminum molecular sieve has the structureTitanium silicalite molecular sieve of MFI structure (TS-C).
(5) Preparing the titanium-silicon-aluminum molecular sieve according to the method of 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%), silicon source propyl orthosilicate, aluminum source aluminum hydroxide, titanium source titanium tetrachloride and ethylenediamine 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 granules are packed in a tubular reaction tube with diameter of 0.8cm and length of 55cm, and the volume of catalyst granule bed is 2.0cm 3 . At the reaction temperature of 300 ℃, the reaction pressure of 1atm, the feeding molar ratio of hydrogen sulfide and methanol of 1 -1 Under the conditions of (1), a catalytic reaction for synthesizing dimethyl sulfide is carried out. Obtained after 3 hours of gas chromatography analysis of the catalytic reactionAnd (4) calculating the conversion rate of the methanol according to the analysis result and using the methanol as the activity of the silicon-aluminum molecular sieve. Conversion of methanol = [ (molar amount of methanol added-not) molar amount of methanol reacted)/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 the discharging agents SH-I (the activity is 45%), SH-II (the activity is 35%) and SH-III (the activity is 15%) are obtained in sequence according to the method.
(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 (0.1 MPa, 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), silicon source methyl orthosilicate, titanium source titanium sulfate and sodium hydroxide aqueous solution (the pH is 12), putting the mixed solution into a stainless steel sealed reaction kettle, and carrying out fourth heat treatment for 12 hours at the temperature of 170 ℃, wherein the material comprises the following components in mass: a titanium source: acid: alkali: water =100:1:2:5:250, deactivated catalyst is SiO 2 Measured as H, acid + Calculated as OH as base - Measured as SiO 2 Silicon source and calculated as TiO 2 The molar ratio of the titanium source is 10:1. 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 percent), silicon source ethyl orthosilicate, titanium source tetrabutyl titanate and tetrapropyl ammonium 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 the temperature of 150 ℃, wherein the mass composition of the materials is that the deactivated catalyst: a titanium source: acid: alkali: water =100:2:8:15:200 deactivated cyclohexanone oximation catalyst with SiO 2 Acid is calculated as H + Calculated as OH as base - Measured as SiO 2 Silicon source and based on TiO 2 The molar ratio of the titanium source is 20:1. 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), silicon source propyl orthosilicate, titanium source titanium tetrachloride and 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 material comprises the following components in mass: a titanium source: acid: alkali: water =100:5:5:5:150, deactivated catalyst with SiO 2 Measured as H, acid + Alkali is calculated as N, and SiO is calculated as 2 Silicon source and based on TiO 2 The molar ratio of the titanium source is 15:1. 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
Propylene, methanol, 12 wt% hydrogen peroxide and a first catalyst (titanium silicalite TS-1) are mixed according to a molar ratio of propylene to hydrogen peroxide to methanol of 1:1:5, the weight ratio of the propylene to the first catalyst is 100:15, putting the mixture into se:Sup>A reaction kettle, carrying out se:Sup>A first reaction for 1h at the temperature of 60 ℃ and the pressure of 1.5 MPse:Sup>A, and then adding se:Sup>A second catalyst (TS-A), wherein the weight ratio of propylene to the second catalyst is 100:30, the second reaction was continued at a temperature of 60 ℃ and a pressure of 1.5MPa for 5 hours, the results of which are shown in Table 1.
Example 2
Propylene, methanol, 12 wt% hydrogen peroxide and a first catalyst (titanium silicalite TS-1) are mixed according to a molar ratio of propylene to hydrogen peroxide to methanol of 1:0.5:2, the weight ratio of the propylene to the first catalyst is 100:5, putting the mixture into se:Sup>A reaction kettle, carrying out se:Sup>A first reaction for 1h at the temperature of 60 ℃ and the pressure of 1.5 MPse:Sup>A, and then adding se:Sup>A second catalyst (TS-A), wherein the weight ratio of propylene to the second catalyst is 100:15, the second reaction was continued at a temperature of 60 ℃ and a pressure of 1.5MPa for 3 hours, the results of which are shown in Table 1.
Example 3
Propylene, methanol, 12 wt% hydrogen peroxide and a first catalyst (titanium silicalite TS-1) are mixed according to a molar ratio of propylene to hydrogen peroxide to methanol of 1:10:10, the weight ratio of propylene to the first catalyst is 100:2, putting the mixture into se:Sup>A reaction kettle, carrying out se:Sup>A first reaction for 1h at the temperature of 60 ℃ and the pressure of 1.5 MPse:Sup>A, and then adding se:Sup>A second catalyst (TS-A), wherein the weight ratio of propylene to the second catalyst is 100:5, the second reaction was continued at a temperature of 60 ℃ and a pressure of 1.5MPa for 5 hours, the results of which are shown in Table 1.
Example 4
Propylene, methanol, 12 wt% hydrogen peroxide and a first catalyst (titanium silicalite TS-1) are mixed according to a molar ratio of propylene to hydrogen peroxide to methanol of 1:0.1:1, the weight ratio of propylene to the first catalyst is 100:100, putting into se:Sup>A reaction kettle, carrying out se:Sup>A first reaction for 1h at the temperature of 60 ℃ and the pressure of 1.5 MPse:Sup>A, and then adding se:Sup>A second catalyst (TS-A), wherein the weight ratio of propylene to the second catalyst is 100:150 and the second reaction was continued at a temperature of 60 ℃ and a pressure of 1.5MPa for 5h, the results of which are shown in Table 1.
Example 5
Propylene, methanol, 12 wt% hydrogen peroxide and a first catalyst (titanium silicalite TS-1) are mixed according to a molar ratio of propylene to hydrogen peroxide to methanol of 1:1:5, the weight ratio of the propylene to the first catalyst is 100:15, putting the mixture into se:Sup>A reaction kettle, carrying out se:Sup>A first reaction for 1h at the temperature of 60 ℃ and the pressure of 1.5 MPse:Sup>A, and then adding se:Sup>A second catalyst (TS-A), wherein the weight ratio of propylene to the second catalyst is 100:30, the second reaction was continued at a temperature of 60 ℃ and a pressure of 1.5MPa for 10 hours, and the results are shown in Table 1.
Example 6
Propylene, methanol, 12 wt% hydrogen peroxide and a first catalyst (titanium silicalite TS-1) are mixed according to a molar ratio of propylene to hydrogen peroxide to methanol of 1:1:5, the weight ratio of the propylene to the first catalyst is 100:15, putting the mixture into se:Sup>A reaction kettle, carrying out se:Sup>A first reaction for 1h at the temperature of 60 ℃ and the pressure of 1.5 MPse:Sup>A, and then adding se:Sup>A second catalyst (TS-A), wherein the weight ratio of propylene to the second catalyst is 100:30, the second reaction was continued at a temperature of 60 ℃ and a pressure of 1.5MPa for 0.1h, the results of which are shown in Table 1.
Examples 7 to 13
Propylene glycol monomethyl ether and propylene glycol were prepared according to the method of example 1, except that the catalysts were replaced with TS-B, TS-C, TS-D, TS-E, TS-F, TS-G and TS-H, respectively, and the reaction results are shown in Table 1.
Examples 14 to 21
Propylene glycol monomethyl ether and propylene glycol were prepared according to the method of example 1, except that the catalysts were replaced with SA-A, SA-B, SA-C, SA-D, SA-E, SA-F, SA-G and SA-H, respectively, and the reaction results were as shown in Table 1.
Example 22
Propylene glycol monomethyl ether and propylene glycol were prepared according to the method of example 1, except that in the second reaction, the same amount of titanium silicalite molecular sieve prepared according to example 1 of CN102616805A was used instead of the second catalyst (TS-se:Sup>A), and the reaction results are shown in table 1.
Comparative example 1
Propylene glycol monomethyl ether and propylene glycol were prepared according to the method of example 1, except that the second reaction, i.e., only the first reaction, was carried out without using the catalyst (TS-se:Sup>A). The results are shown in Table 1.
Comparative example 2
Propylene glycol monomethyl ether and propylene glycol were prepared according to the method of example 1, except that in the second reaction, the same amount of titanium silicalite TS-1 was used instead of the second catalyst (TS-se:Sup>A). The results are shown in Table 1.
Comparative example 3
Propylene glycol monomethyl ether and propylene glycol were prepared according to the method of example 1, except that in the second reaction, the same amount of the silicoaluminophosphate molecular sieve ZSM-5 was used in place of the second catalyst (TS-se:Sup>A). The results are shown in Table 1.
Comparative example 4
Propylene glycol monomethyl ether and propylene glycol were prepared according to the method of comparative example 1, except that the reaction temperature was 80 ℃. The results are shown in Table 1.
TABLE 1
Figure BDA0001746737040000221
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Figure BDA0001746737040000231
The results prove that the propylene can be oxidized by adopting the method disclosed by the invention, the higher propylene conversion rate can be obtained, the selectivity of propylene glycol monomethyl ether and 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 1-4, the disclosed method can significantly improve the relative conversion of propylene and the selectivity of propylene glycol monomethyl ether and propylene glycol compared to when no second reaction is performed, or when no catalyst containing a titanium silicalite molecular sieve is used for the second reaction. As can be seen from a comparison of example 1 and example 5, when the ratio of the reaction time of the first reaction to the reaction time of the second reaction is 1: (0.2 to 5), the relative conversion of propylene and the selectivity of propylene glycol monomethyl ether and propylene glycol can be further improved. As can be seen from the comparison of examples 1, 7-13 and 14-22, the titanium silicalite molecular sieve prepared by the specific method is beneficial to obtaining higher propylene relative conversion rate and selectivity of propylene glycol monomethyl ether and propylene glycol when used for reaction.
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 various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (11)

1. A method for preparing propylene glycol monomethyl ether and propylene glycol by propylene oxidation is characterized by comprising the following steps:
s1, carrying out a first reaction on propylene, an oxidant and methanol in the presence of a first catalyst to obtain a first reaction mixture, wherein the first catalyst contains a titanium silicalite molecular sieve;
s2, mixing the first reaction mixture with a second catalyst to perform a second reaction, wherein the second catalyst contains a titanium-silicon-aluminum molecular sieve;
the ratio of the reaction time of the first reaction to the reaction time of the second reaction is 1: (0.2-50);
the mol ratio of the propylene to the oxidant to the methanol is 1: (1-10): (0.1-10);
the weight ratio of the propylene to the first catalyst to the second catalyst is 100: (2-1000): (5-200);
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 1-30h;
(2) Mixing the first solid, a silicon source, 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 ℃, and the time is 0.5-25h;
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 0.5-40h;
b. mixing the second solid, a silicon source, 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 ℃, and the time is 0.5-25h;
the discharging agent of the reaction device taking the titanium silicalite molecular sieve as the active component of the catalyst in the step (1) is at least one selected from the discharging agent of an ammoximation reaction device, the discharging agent of a hydroxylation reaction device and the discharging agent of an epoxidation reaction device;
and c, taking the silicon-aluminum molecular sieve as the discharging agent of the reaction device of the catalyst active component in the step a as the discharging agent of the synthesis reaction device of hydrogen sulfide and methanol.
2. The process of claim 1, wherein the molar ratio of propylene, oxidant and methanol is 1: (0.2-5): (2-5);
the oxidant is selected from hydrogen peroxide, tert-butyl hydroperoxide, cumyl peroxide, cyclohexyl hydroperoxide, peroxyacetic acid or peroxypropionic acid.
3. The process of claim 1, wherein the weight ratio of propylene, first catalyst and second catalyst is 100: (5-500): (10-100).
4. The method of claim 1, wherein the conditions of the first reaction are: the temperature is 0-80 ℃, and the pressure is 0.1-2.5MPa;
the conditions of the second reaction are as follows: the temperature is 0-80 deg.C, and the pressure is 0.1-2.5MPa.
5. The process of claim 1, wherein the titanium silicalite molecular sieve is 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, or an MRE-type titanium silicalite molecular sieve;
the titanium-silicon-aluminum molecular sieve is a titanium-silicon-aluminum molecular sieve with an MFI structure, a titanium-silicon-aluminum molecular sieve with an MEL structure, 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 or a titanium-silicon-aluminum molecular sieve with a two-dimensional hexagonal structure.
6. The method of claim 1, wherein the first discharging agent, the titanium source, the aluminum source, the organic acid, the alkali source, and theThe weight ratio of water is 100: (0.1-10): (0.1-10): (0.005-50): (0.5-50): (20-1000), the first discharging agent is SiO 2 The 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; with SiO 2 The silicon source is calculated by TiO 2 The molar ratio of the titanium source is (5-20): 1; the concentration of the organic acid solution is more than 0.1mol/L.
7. 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.
8. 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.
9. 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 SiO 2 The 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; with SiO 2 The silicon source is calculated by TiO 2 The molar ratio of the titanium source is (5-20): 1; the concentration of the organic acid solution is more than 0.1mol/L.
10. 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.
11. The method of claim 1, wherein the organic acid is naphthenic acid, peracetic acid, or propionic acid; the alkali source is ammonia, aliphatic amine, aliphatic alcohol amine or quaternary ammonium base; the aluminum source is aluminum sol, aluminum salt, aluminum hydroxide or aluminum oxide; the titanium source is inorganic titanium salt and/or organic titanate; the silicon source is organosilicate.
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CN105439826A (en) * 2014-08-25 2016-03-30 中国石油化工股份有限公司 A preparing method of propylene glycol monomethyl ether
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CN1944365A (en) * 2006-09-23 2007-04-11 湖南长岭石化科技开发有限公司 Process for synthesizing propylene glycol ether
CN103012078A (en) * 2011-09-28 2013-04-03 中国石油化工股份有限公司 Method for preparing propylene glycol monomethyl ether by catalyzing propylene oxide
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