CN111072457A - Method for preparing propylene glycol monomethyl ether - Google Patents
Method for preparing propylene glycol monomethyl ether Download PDFInfo
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- CN111072457A CN111072457A CN201811229202.8A CN201811229202A CN111072457A CN 111072457 A CN111072457 A CN 111072457A CN 201811229202 A CN201811229202 A CN 201811229202A CN 111072457 A CN111072457 A CN 111072457A
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- 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
- C07C41/02—Preparation of ethers from oxiranes
- C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/90—Regeneration or reactivation
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Abstract
The invention relates to the field of propylene glycol monomethyl ether production, and discloses a method for preparing propylene glycol monomethyl ether, which comprises the following steps: under the alcoholysis reaction condition, propylene oxide, methanol and a catalyst are contacted in a reaction zone of a moving bed reactor, wherein the catalyst contains a titanium-silicon-aluminum molecular sieve. The method can effectively avoid the problems of temperature runaway of a catalyst bed layer and the like possibly occurring in a fixed bed reactor, can obtain high propylene oxide conversion rate and selectivity of 2-methoxy-1-propanol (MME-2) in propylene glycol monomethyl ether, and can prolong the service life of the catalyst; meanwhile, the catalyst with the activity which cannot meet the requirement can be removed from the reaction zone for regeneration under the condition that the device does not stop.
Description
Technical Field
The invention relates to the field of propylene glycol monomethyl ether production, and in particular relates to a method for preparing propylene glycol monomethyl ether.
Background
Propylene glycol ethers, in particular propylene glycol monomethyl ether, are important chemical products, which have two isomers, 1-methoxy-2-propanol (MME-1) and 2-methoxy-1-propanol (MME-2). Because the chemical structure of the compound has two groups with strong dissolving capacity, namely ether bond and hydroxyl, the former belongs to hydrophobic property and can dissolve hydrophobic compounds; the latter is hydrophilic and can dissolve water soluble matter, so that propylene glycol ether is a universal solvent with excellent performance, also called universal solvent. The propylene glycol monomethyl ether has weak ether smell but no strong pungent smell, so that the application of the propylene glycol monomethyl ether is wider and safer, and the propylene glycol monomethyl ether can be used in various fields. For example, propylene glycol monomethyl ether can be used in styrene-acrylic emulsions, and latex paint systems thereof, and has the characteristics of lowering film-forming temperature, promoting coagulation film-forming, and ensuring good state of the coating film. Besides being used as a solvent of various high-grade coatings, the propylene glycol monomethyl ether is also used as a volatilization speed control and viscosity regulator in printing ink, and can also be used as a viscosity regulator in chemical intermediates and brake fluid formulas. The propylene glycol methyl ether can be mixed with water in any proportion, so that the propylene glycol methyl ether can be applied to a metal cleaning agent formula as a solvent or can be applied to an automobile water tank anti-icing fluid to reduce the freezing point. In addition, propylene glycol monomethyl ether can also be used as a raw material for organic synthesis.
The method for producing the propylene glycol ether basically adopts the epoxypropane as a raw material to be combined with alcohols, but the method has the problems of high reaction temperature (above 100 ℃), high pressure, low catalyst activity (60-90%), poor selectivity (82-90%) and the like. The method for synthesizing propylene glycol monomethyl ether disclosed in CN101550069A adopts ionic liquid as a catalyst, but has strict requirements on raw materials, and if anhydrous methanol is required, the cost is high.
The preparation of propylene glycol monomethyl ether by directly adopting the alcoholysis of propylene oxide catalyzed by a molecular sieve is an environment-friendly process with high atom economy, has great significance in academic research and application, and is newly researched and reported in the aspect of preparing propylene glycol monomethyl ether by alcoholysis of propylene oxide in a moving bed reactor by specially using a titanium-silicon-aluminum molecular sieve as a catalyst.
Disclosure of Invention
The invention aims to overcome the defect that the existing method for preparing propylene glycol monomethyl ether generally needs to be carried out under harsh conditions, and provides a method for preparing propylene glycol monomethyl ether.
The inventor of the invention finds that in the process of preparing propylene glycol monomethyl ether by alcoholysis of propylene oxide, if a titanium-silicon-aluminum molecular sieve is introduced as a catalyst in a reaction system, the conversion rate of the propylene oxide and the selectivity of 2-methoxy-1-propanol (MME-2) in the propylene glycol monomethyl ether can be remarkably improved under relatively mild conditions. In addition, when propylene glycol monomethyl ether is prepared by alcoholysis of propylene oxide catalyzed by a molecular sieve in a fixed bed reactor, the problems of over-high local temperature and temperature runaway in a catalyst bed easily occur in the reaction process, and shutdown is needed when the catalyst is regenerated after being deactivated, so that the working efficiency is low. In order to overcome the defects, the invention provides a method for preparing propylene glycol monomethyl ether, which comprises the following steps: under the alcoholysis reaction condition, propylene oxide, methanol and a catalyst are contacted in a reaction zone of a moving bed reactor, wherein the catalyst contains a titanium-silicon-aluminum molecular sieve.
In particular, the present inventors have unexpectedly found that the use of a titanium-silicon-aluminum catalyst obtained by treating a discharging agent to a specific crystallinity and then heat-treating it together with other raw materials in the reaction of the present invention can further improve the propylene oxide conversion rate and the selectivity of 2-methoxy-1-propanol (MME-2) in propylene glycol monomethyl ether under relatively mild conditions.
According to the method, the problems of temperature runaway and the like of a catalyst bed layer possibly occurring in a fixed bed reactor can be effectively avoided, and under the relatively mild condition, the high propylene oxide conversion rate and the selectivity of 2-methoxy-1-propanol (MME-2) in propylene glycol monomethyl ether can be obtained, and the service life of the catalyst can be prolonged; meanwhile, the catalyst with the activity which cannot meet the requirement can be removed from the reaction zone for regeneration under the condition that the device does not stop.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for preparing propylene glycol monomethyl ether, which comprises the following steps:
under the alcoholysis reaction condition, propylene oxide, methanol and a catalyst are contacted in a reaction zone of a moving bed reactor, wherein the catalyst contains a titanium-silicon-aluminum molecular sieve.
According to one embodiment of the invention, the catalyst moves in the reaction zone in the axial direction of the reactor.
According to the method of the present invention, during the contacting, the catalyst moves in the reaction zone along the axial direction of the reactor (i.e., the reaction zone), which can effectively avoid the problem that local temperature in the catalyst bed is too high during the reaction when the catalyst bed is fixed in the reactor. In the present invention, the "reaction zone" refers to a zone in which propylene oxide and methanol are brought into contact with a catalyst to effect a reaction.
The catalyst may be fed from the upper part (generally the top) of the reaction zone, and the propylene oxide and methanol may be fed from the lower part or the upper part of the reaction zone respectively, so as to contact and react with the propylene oxide and methanol during the falling of the catalyst. Preferably, the catalyst, methanol and optionally solvent are fed separately into the reaction zone from the upper part of the reaction zone and propylene oxide is fed into the reaction zone from the lower part (typically the bottom) of the reaction zone, with the propylene oxide forming a mixture with methanol and reacting in contact with the catalyst during the movement. The specific feed locations for the catalyst, propylene oxide and methanol may be selected according to the specific specifications of the reactor.
According to the process of the present invention, the catalyst can be moved out of the reaction zone after the reaction, and the catalyst moved out of the reaction zone can be recycled into the reaction zone. When the activity of the catalyst moving out of the reaction zone can not meet the use requirement, the titanium-silicon-aluminum molecular sieve moving out of the reaction zone can be regenerated and then sent into the reaction zone again. The regeneration conditions of the present invention are not particularly limited, and can be carried out by a method conventionally used in the art, for example: solvent soaking and/or high temperature roasting. The regeneration may be carried out in a regenerator outside the reactor; or a regeneration zone can be arranged in the reactor, and the titanium-silicon-aluminum molecular sieve moving out of the reaction zone is sent into the regeneration zone for regeneration and then sent into the reaction zone again.
When the catalyst moved out of the reaction zone is sent into a regeneration zone or a regenerator for regeneration, the catalyst with the activity meeting the requirement can be correspondingly fed into the reaction zone in a supplementing way. The amount of the replenished catalyst may be selected according to the activity of the replenished catalyst so as to allow the reaction in the reaction zone to proceed smoothly.
According to the process of the present invention, the moving speeds of the catalyst, propylene oxide and methanol in the reaction zone may be appropriately selected depending on the treating ability of the reaction zone. In general, in small laboratory scale practice, the propylene oxide feed rate may be in the range of 5 to 100mL/min, preferably 10 to 80mL/min, more preferably 20 to 60 mL/min. The moving speed of the catalyst and methanol in the reaction zone may be appropriately selected according to the ratio of propylene oxide to the catalyst and methanol, which will be described later.
According to the process of the present invention, preferably, said contacting is carried out in the presence of at least one solvent. In general, the solvent may be selected from C2-C8Ether of (C)3-C8Ketone and C2-C8At least one of the nitriles of (1). Specific examples of the solvent may include, but are not limited to: at least one of ethyl ether, methyl tert-butyl ether, acetone, butanone and acetonitrile.
The amount of the solvent used in the present invention is not particularly limited, and may be selected according to the amounts of propylene oxide and methanol. Generally, the weight ratio of the solvent to the propylene oxide may be from 0.1 to 100: 1, preferably 0.2 to 80: 1.
according to the process of the present invention, the alcoholysis reaction conditions can be selected based on the desired target product. Specifically, the alcoholysis reaction conditions include: the temperature is 10-140 ℃, preferably 20-120 ℃, and more preferably 50-65 ℃; the pressure in the reaction zone of the reactor is 0 to 2.5MPa, preferably 0.1 to 1.5MPa, and more preferably 1 to 1.5MPa in terms of gauge pressure.
According to a preferred embodiment of the invention, the weight ratio of propylene oxide to the catalyst is between 0.1 and 100: 1, preferably 0.1 to 20: 1, more preferably 1 to 8: 1.
the amount of methanol may be selected according to the amount of propylene oxide. Preferably, the molar ratio of propylene oxide to methanol is 1: 0.1 to 10, preferably 1: 2-5.
In the present invention, the titanium-silicon-aluminum molecular sieve is 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.
In order to further improve the activity and selectivity of the catalyst, preferably, the titanium-silicon-aluminum molecular sieve is prepared by the following steps:
(1) mixing a catalyst containing a titanium silicalite molecular sieve with a first heat treatment liquid, then carrying out first heat treatment, and separating to obtain a first solid with the relative crystallinity of 50-90%, wherein the first heat treatment liquid is an acid solution with the concentration of more than 0.1 mol/L;
(2) and mixing the first solid, a silicon source, an aluminum source, an optional titanium source, an alkali source and water, and then carrying out second heat treatment, wherein the temperature of the second heat treatment is 100-200 ℃.
According to a preferred embodiment of the present invention, the first solid isolated in step (1) has a relative crystallinity of 70 to 90%. The inventor of the present invention finds that the titanium-silicon-aluminum molecular sieve obtained by the first heat treatment in step (1) to obtain the first solid with the relative crystallinity of 70-90%, and then performing the second heat treatment is more suitable for preparing propylene glycol monomethyl ether.
In the present invention, there is no limitation on the titanium silicalite molecular sieve, and the titanium silicalite molecular sieve can be a 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 present invention, the catalyst containing the titanium silicalite molecular sieve may contain a fresh titanium silicalite molecular sieve, or may contain a titanium silicalite molecular sieve discharging agent, which is not particularly limited in the present invention.
Of course, from the perspective of preparation effect, the method of the present invention may use fresh titanium silicalite as a raw material, but is not suitable from the perspective of cost control, etc., and in order to save cost, the catalyst containing titanium silicalite is preferably a discharging agent of a reaction device using titanium silicalite as a catalyst.
In the present invention, the discharging agent of the reaction apparatus using the titanium silicalite molecular sieve as the catalyst active component may be a discharging agent discharged from various apparatuses using the titanium silicalite molecular sieve as the catalyst active component, for example, a discharging agent discharged from an oxidation reaction apparatus using the titanium silicalite molecular sieve 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 one or more 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, may be one or more 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 in an alkaline environment, and therefore, for the present invention, it is preferable that the 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 100-500 nm).
In the present invention, the discharging agent is a deactivated catalyst whose activity cannot be restored to 50% of the initial activity by a conventional regeneration method such as solvent washing or calcination (the initial activity is the average activity of the catalyst within 1h under the same reaction conditions, for example, in the actual cyclohexanone oximation reaction, the fresh agent activity of the catalyst is generally more than 95%).
The activity of the discharging agent varies depending on its source. Preferably, the activity of the discharging agent is less than 50% of the activity of the titanium silicalite molecular sieve in a fresh state, and more preferably, the activity of the discharging agent can be 10-40% of the activity of the titanium silicalite molecular sieve in a fresh state. The activity of the titanium silicalite molecular sieve freshener is generally more than 90%, and usually more than 95%.
In the present invention, the discharging agent may be derived from an industrial deactivator or a deactivated catalyst after reaction in a laboratory.
In the invention, the discharging agent of each device is respectively measured by adopting the reaction of each device, and the discharging agent is the discharging agent provided that the activity of the discharging agent is lower than that of a fresh catalyst in the same device under the same reaction condition. As mentioned before, the activity of the discharging agent is preferably less than 50% of the activity of the fresh catalyst.
In a preferred embodiment of the present invention, taking the discharging agent of the cyclohexanone ammoximation reaction apparatus as an example, 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 unit under stirring at 5.7mL/hAdding a mixture of water and 30 wt% of hydrogen peroxide at a speed (the volume ratio of the water to the 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 the cyclohexanone to the tert-butyl alcohol is 1: 2.5), adding 36 wt% of ammonia water at a speed of 5.7mL/h, simultaneously adding the three streams, continuously discharging at corresponding speeds, 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, and calculating the conversion rate of the cyclohexanone and using the conversion rate as the activity of the titanium silicalite molecular sieve by using the following formula. 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.
According to the method of the present invention, preferably the method of the present invention further comprises: the discharging agent is roasted before being mixed with the first heat treatment liquid.
In the present invention, the step (2) is preferably carried out as follows: and mixing a silicon source, an aluminum source and an alkali source in the presence of water 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.
According to the process of the present invention, the heat treatment is generally carried out under autogenous pressure in the case of sealing, unless otherwise specified.
In the present invention, it is preferable that the temperature of the first heat treatment is 20 to 45 ℃ (e.g., 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃ or any value therebetween).
In the present invention, the time of the first heat treatment can be determined according to the needs, and for the present invention, the time of the first heat treatment is preferably 1 to 30 hours, preferably 1 to 24 hours, and more preferably 10 to 20 hours. The inventor of the present invention finds that under the specific first heat treatment condition, the crystallinity can be more favorably controlled to meet the range, and therefore, the titanium-silicon-aluminum molecular sieve with good catalytic performance can be obtained.
In the present invention, the temperature of the second heat treatment is 100-200 ℃, more preferably 120-180 ℃, and still more preferably 140-170 ℃.
In the present invention, the time of the second heat treatment is preferably determined as needed, and in the present invention, the time of the second heat treatment is preferably 0.5 to 25 hours, preferably 2 to 24 hours, and more preferably 5 to 20 hours.
In the invention A, the concentration of the acid solution is more than 0.1mol/L, preferably more than or equal to 1mol/L, and more preferably 2-15 mol/L. In the invention, the main solvent of the acid solution is water, and other solvent auxiliaries can be added according to the requirement. The titanium-silicon-aluminum molecular sieve prepared in the way has better catalytic performance.
According to the method provided by the invention, preferably, SiO is used2And (3) calculating the molar ratio of the catalyst containing the titanium-silicon molecular sieve in the step (1) to the silicon source in the step (2) to be 100: (1-30), preferably 100: (5-20). By adopting the preferred embodiment of the invention, the prepared titanium-silicon-aluminum molecular sieve has better catalytic performance.
In the present invention, a catalyst containing a titanium silicalite is preferred: a titanium source: an aluminum source: acid: alkali source: the molar ratio of water is 100: (0.1-10): (0.1-10): (0.005-50): (0.5-50): (20-1000), more preferably 100: (0.5-10): (0.5-10): (1-15): (1-20): (100-800), most preferably 100: (1-5): (0.5-2): (3-13): (5-15): (150-250), the catalyst containing titanium-silicon molecular sieve is SiO2Measured as H, acid+The alkali source is N or OH-And (6) counting. More preferably, the molar ratio of discharging agent to acid is 100: (3-13).
According to the process of the present invention, the acid may be selected from a wide variety of acids, which may be organic and/or inorganic acids, preferably organic acids. Wherein, the inorganic acid can be one or more of HCl, sulfuric acid, perchloric acid, nitric acid and phosphoric acid, and is preferably phosphoric acid; the organic acid can be C1-C10 organic carboxylic acid, preferably one or more of formic acid, acetic acid, propionic acid, naphthenic acid peroxyacetic acid and peroxypropionic acid, and further preferably one or more of naphthenic acid, peroxyacetic acid and peroxypropionic acid. The inventor of the invention finds that the use of specific types and dosage of organic acid can be more beneficial to controlling the crystallinity to meet the range, thereby obtaining the titanium-silicon-aluminum molecular sieve with good catalytic performance.
The silicon source is not particularly limited in the present invention, and may be any substance capable of providing silicon element in the art, for example, the silicon source may be an organic silicon source and/or an inorganic silicon source.
Specifically, the organic silicon source may be, for example, one or more selected from silicon-containing compounds represented by formula I,
in the formula I, R1、R2、R3And R4Each is C1-C4Alkyl of (2) including C1-C4Straight chain alkyl of (2) and C3-C4Branched alkyl groups of (a), for example: r1、R2、R3And R4Each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
Specifically, the organic silicon source may be one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate, and tetra-n-butyl orthosilicate. Tetraethyl orthosilicate or methyl orthosilicate are used as examples in the specific embodiments of the invention, but do not limit the scope of the invention accordingly.
According to the method of the present invention, the optional range of the types of the inorganic silicon source is wide, and for the present invention, the inorganic silicon source is preferably silica sol and/or silica gel, and the silica gel or silica sol in the present invention may be silica gel or silica sol obtained by various production methods in various forms.
In the present invention, the titanium source may 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 TiCl4、Ti(SO4)2、TiOCl2One or more of titanium hydroxide, titanium oxide, titanium nitrate, titanium phosphate and the like, and the organic titanium source can be one or more of fatty titanium alkoxide and organic titanate. The titanium source is preferably an organic titanium source, and more preferably an organic titanate. The organic titanic acidThe ester 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 one or more 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 tetran-propyl titanate), tetrabutyl titanate (various isomers of tetrabutyl titanate, such as tetran-butyl titanate), and tetraethyl titanate.
In the present invention, the kind of the alkali source is wide in selectable range, and it may be an organic alkali source and/or an inorganic alkali source, wherein the inorganic alkali source may 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, and the like, and the organic alkali source may be one or more of urea, an aliphatic amine compound, an aliphatic alcohol amine compound, and a quaternary ammonium alkali compound.
According to a preferred embodiment of the present invention, the alkali source is one or more of ammonia, an aliphatic amine, an aliphatic alcohol amine and a quaternary ammonium base.
In the invention, the quaternary ammonium base can be various organic quaternary ammonium bases, and the aliphatic amine can be various NH3In 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:
in the formula II，R1、R2、R3And R4Each is C1-C4Alkyl of (2) including C1-C4Straight chain alkyl of (2) and C3-C4Branched alkyl groups of (a), for example: r1、R2、R3And R4Each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
R7(NH2)n(formula III)
In the formula III, n is an integer of 1 or 2. When n is 1, R7Is C1～C6Alkyl of (2) including C1～C6Straight chain alkyl of (2) and C3-C6Such 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, R7Is 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
(HOR8)mNH(3-m)(formula IV)
In the formula IV, m are R8Are 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 one or more of sodium hydroxide, ammonia, ethylenediamine, n-butylamine, butanediamine, hexamethylenediamine, monoethanolamine, diethanolamine, triethanolamine, tetraethylammonium hydroxide, and tetrapropylammonium hydroxide.
Wherein, when the alkali source contains ammonia waterWhen the molar ratio of the alkali source is in the range including NH in molecular form3And NH in ionic form4 +The presence of ammonia.
In the present invention, the alkali source contains both N and OH-When, without particular reference, the alkali source is OH-And (6) counting.
In the present invention, preferably the alkali source is provided in the form of an alkali solution, more preferably an alkali solution having a pH > 9.
In the present invention, the aluminum source is a substance capable of providing aluminum, and preferably the aluminum source is one or more of aluminum sol, 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.
In the present invention, the aluminum salt may be an inorganic aluminum salt, which may be one or more of aluminum sulfate, sodium metaaluminate, aluminum chloride and aluminum nitrate, and/or an organic aluminum salt, which is preferably an organic aluminum salt having C1-C10.
In the present invention, it is preferable that the method of the present invention further comprises a step of recovering a product from the heat-treated material of step (2), the step of recovering the product being a conventional method familiar to those skilled in the art, and generally means a process of filtering, washing, drying and calcining the product without particular requirement. 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.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples, the reagents used were all commercially available chemically pure reagents.
In the following examples and comparative examples, the pressures were gauge pressures unless otherwise specified.
In the following examples and comparative examples, the composition of each component in the obtained reaction liquid was measured by gas chromatography, and quantified by the normalized normalization method, and on the basis of this, the propylene oxide conversion and propylene glycol monomethyl ether selectivity were calculated by using the following formulas, respectively:
propylene oxide conversion (%) × 100% (moles of propylene oxide participating in the reaction/moles of propylene oxide added);
selectivity of 1-methoxy-2-propanol (MME-1) ═ mole of 1-methoxy-2-propanol/mole of propylene oxide consumed by the reaction) × 100%;
selectivity of 2-methoxy-1-propanol (MME-2) ═ mole of (2-methoxy-1-propanol/mole of propylene oxide consumed by the reaction) × 100%.
Preparation example 1
Preparation of titanium-silicon-aluminum molecular sieve
(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% 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%. The cyclohexanone conversion, measured for the first time, i.e. 1h, was its initial activity, which was 99.5%. After a period of time of about 168 hours, the conversion rate of cyclohexanone is reduced from initial 99.5% to 50%, the catalyst is separated out and regenerated by roasting in a roasting regeneration mode (roasting at 570 ℃ for 4 hours in an air atmosphere), then the catalyst is continuously used in cyclohexanone ammoximation reaction, the step is repeatedly carried out until the activity after regeneration is lower than 50% of the initial activity, the inactivated ammoximation catalyst sample is used as the discharging agent of the invention, and the discharging agents SH-1 (the activity is 40%) and SH-2 (the activity is 25%) are sequentially obtained according to the method) SH-3 (activity 10%).
(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, and then mixing and stirring the mixed slurry for 12 hours at 35 ℃; after solid-liquid separation, mixing the solid (the relative crystallinity is 72 percent), silicon source ethyl 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 treating for 12 hours at the temperature of 140 ℃, wherein the molar composition of the materials is an inactivated cyclohexanone oximation catalyst: silicon source: a titanium source: an aluminum source: acid: alkali: 100 parts of water: 5: 1: 1: 3: 5: 250, deactivated cyclohexanone oximation catalyst and silicon source are SiO2Measured 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 the inactivated cyclohexanone oximation catalyst SH-2 and 5mol/L peroxyacetic acid solution at normal temperature and normal pressure, and then mixing and stirring the mixed pulp at 25 ℃ for 18 hours; after solid-liquid separation, mixing solid (relative crystallinity is 90%), silicon source ethyl orthosilicate, aluminum source aluminum sol (content is 20 wt%), 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 treating for 20 hours at 170 ℃, wherein the molar composition of the materials is an inactivated cyclohexanone oximation catalyst: silicon source: a titanium source: an aluminum source: acid: alkali: 100 parts of water: 10: 2: 0.5: 13: 15: 200 deactivated cyclohexanone oximation catalyst and silicon source 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 pressure, mixing and pulping the inactivated cyclohexanone oximation catalyst SH-3 and 8mol/L aqueous solution of peroxypropionic acid, and then mixing and stirring the mixed slurry at 32 ℃ for 10 hours; after solid-liquid separation, the solid is (relatively crystallized)The degree is 84 percent), silicon source ethyl orthosilicate, aluminum source aluminum hydroxide, titanium source titanium tetrachloride and ethylenediamine aqueous solution (pH is 11) are mixed, the mixed solution is put into a stainless steel sealed reaction kettle, and hydrothermal treatment is carried out for 5 hours at 150 ℃, wherein the molar composition of the materials is inactivated cyclohexanone oximation catalyst: silicon source: a titanium source: an aluminum source: acid: alkali: 100 parts of water: 20: 5: 2: 8: 9: 150 deactivated cyclohexanone oximation catalyst and silicon source with SiO2Measured 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 formic acid is replaced by the peroxopropionic acid aqueous solution, the relative crystallinity of the solid after solid-liquid separation is 61%, 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 mixed slurry is mixed at 150 ℃, the peroxypropionic acid aqueous solution is replaced by acetic acid, and the inactivated cyclohexanone oximation catalyst: acid 100: 12, the relative crystallinity of the solid after solid-liquid separation is 56 percent, and an XRD crystal phase diagram shows that the titanium-silicon-aluminum molecular sieve (TS-E) with an MFI structure is obtained.
(7) Preparing a titanium-silicon-aluminum molecular sieve according to the method in the step (2), wherein the molar ratio of the deactivated cyclohexanone oximation catalyst to the silicon source is 100: 2, XRD crystal phase diagram shows that titanium-silicon-aluminum molecular sieve (TS-F) with MFI structure is obtained.
(8) Preparing a titanium-silicon-aluminum molecular sieve according to the method in the step (2), wherein the molar ratio of the deactivated cyclohexanone oximation catalyst to the silicon source is 100: the XRD crystallographic phase diagram shows that a titanium-silicon-aluminum molecular sieve (TS-G) with an MFI structure is obtained.
Wherein the X-ray diffraction (XRD) phase diagram of the sample is determined on a Siemens D5005 type X-ray diffractometer, and the crystallinity of the sample relative to a reference sample is expressed by the ratio of the sum of diffraction intensities (peak heights) of five finger diffraction characteristic peaks of the sample and the reference sample at the 2 theta of 22.5-25.0 degrees, wherein the crystallinity is 100 percent by taking a fresh TS-1 molecular sieve sample as the reference sample.
Example 1
Propylene oxide, methanol, acetone as A solvent and the molecular sieve TS-A prepared in preparation example 1 as A catalyst were continuously fed into A moving bed reactor, respectively, to be subjected to A contact reaction. Wherein propylene oxide is fed from a lower feed inlet of the reactor, and a mixture of methanol and a solvent and a catalyst are fed into the reactor from a liquid-phase feed inlet and a solid-phase feed inlet located at the top of the reactor, respectively. Wherein the feeding rate of the propylene oxide is 50mL/min, and the molar ratio of the propylene oxide to the methanol is 1: 2, the weight ratio of the solvent to the propylene oxide is 10: 1, the weight ratio of the propylene oxide to the catalyst is 8: 1, the temperature in the reactor is 65 ℃, and the pressure in the reactor is 1.0 MPa. In the operation process, the catalyst output from the bottom of the reactor is directly recycled without regeneration. The reaction mixtures obtained 1h and 12h after the start of the reaction were subjected to gas chromatography analysis, and the propylene oxide conversion and the propylene glycol monomethyl ether selectivity were calculated. The results are listed in table 1.
Comparative example 1
The molecular sieve TS-A obtained in preparation example 1 was pelletized into 10-20 mesh particles, and charged into A catalyst bed of A stainless steel fixed bed microreactor (A reactor containing A layer of catalyst, A loading amount of 10mL, and A reactor height-diameter ratio of 15), and under conditions of A temperature of 65 ℃ and A pressure of 1.0mpA, propylene oxide, methanol, and acetone as A solvent were fed into the reactor from the bottom of the reactor to contact the catalyst bed, and A reaction mixture was obtained from the top of the reactor. Wherein the molar ratio of the propylene oxide to the methanol is 1: 2, the weight ratio of the agent to the propylene oxide is 10: 1, the liquid hourly weight space velocity of the propylene oxide is 8h-1. The reaction mixtures obtained 1h and 12h after the start of the reaction were subjected to gas chromatography analysis, and the propylene oxide conversion and the propylene glycol monomethyl ether selectivity were calculated. The results are listed in table 1.
Example 2
Propylene oxide, methanol, acetone as a solvent and the molecular sieve TS-B prepared in preparation example 1 as a catalyst were continuously fed into a moving bed reactor, respectively, to be subjected to a contact reaction. Wherein propylene oxide is fed from a lower feed inlet of the reactor, and a mixture of methanol and a solvent and a catalyst are fed into the reactor from a liquid-phase feed inlet and a solid-phase feed inlet located at the top of the reactor, respectively. Wherein the feeding rate of the propylene oxide is 40mL/min, and the molar ratio of the propylene oxide to the methanol is 1: 5, the weight ratio of the solvent to the propylene oxide is 1: 1, the weight ratio of the propylene oxide to the catalyst is 1: 1, the temperature in the reactor is 50 ℃, and the pressure in the reactor is 1.5 MPa. In the operation process, the catalyst output from the bottom of the reactor is directly recycled without regeneration. The reaction mixtures obtained 1h and 12h after the start of the reaction were subjected to gas chromatography analysis, and the propylene oxide conversion and the propylene glycol monomethyl ether selectivity were calculated. The results are listed in table 1.
Example 3
Propylene oxide, methanol, acetone as a solvent and the molecular sieve TS-C prepared in preparation example 1 as a catalyst were continuously fed into a moving bed reactor, respectively, to be subjected to a contact reaction. Wherein propylene oxide is fed from a lower feed inlet of the reactor, and a mixture of methanol and a solvent and a catalyst are fed into the reactor from a liquid-phase feed inlet and a solid-phase feed inlet located at the top of the reactor, respectively. Wherein the feeding rate of the propylene oxide is 30mL/min, and the molar ratio of the propylene oxide to the methanol is 1: 3, the weight ratio of the solvent to the propylene oxide is 10: 1, the weight ratio of the propylene oxide to the catalyst is 3: 1, the temperature in the reactor is 60 ℃, and the pressure in the reactor is 1.0 MPa. In the operation process, the catalyst output from the bottom of the reactor is directly recycled without regeneration. The reaction mixtures obtained 1h and 12h after the start of the reaction were subjected to gas chromatography analysis, and the propylene oxide conversion and the propylene glycol monomethyl ether selectivity were calculated. The results are listed in table 1.
Examples 4 to 7
Propylene glycol monomethyl ether was prepared by alcoholysis of propylene oxide by the method of example 1, except that the molecular sieve TS-A from preparation 1 was replaced with the titanium silicalite molecular sieves TS-D, TS-E, TS-F and TS-G, respectively, of equivalent mass as prepared in preparation 1. The reaction mixtures obtained 1h and 12h after the start of the reaction were subjected to gas chromatography analysis, and the propylene oxide conversion and the propylene glycol monomethyl ether selectivity were calculated. The results are listed in table 1.
Comparative example 2
Propylene glycol monomethyl ether was prepared by alcoholysis of propylene oxide according to the procedure of example 1, except that the molecular sieve TS-A prepared in preparation example 1 was replaced with titanium silicalite molecular sieve TS-1 of equal mass (degree of crystallinity 100%).
The reaction mixtures obtained 1h and 12h after the start of the reaction were subjected to gas chromatography analysis, and the propylene oxide conversion and the propylene glycol monomethyl ether selectivity were calculated. The results are listed in table 1.
Comparative example 3
Propylene glycol monomethyl ether was prepared by alcoholysis of propylene oxide according to the procedure described in example 1, except that the molecular sieve TS-A prepared in preparation example 1 was replaced with an equivalent mass of the aluminosilicate molecular sieve ZSM-5 (prepared as described in comparative example 1 of CN 1235875A).
The reaction mixtures obtained 1h and 12h after the start of the reaction were subjected to gas chromatography analysis, and the propylene oxide conversion and the propylene glycol monomethyl ether selectivity were calculated. The results are listed in table 1.
TABLE 1
From the results in table 1, it can be seen that the method for preparing propylene glycol monomethyl ether provided by the invention can improve the conversion rate of propylene oxide, the selectivity of 2-methoxy-1-propanol (MME-2) in propylene glycol monomethyl ether and the stability of the catalyst under relatively mild conditions. In addition, the optimized titanium-silicon-aluminum molecular sieve can further improve the conversion rate of propylene oxide, the selectivity of 2-methoxy-1-propanol (MME-2) in propylene glycol monomethyl ether and the stability of the catalyst.
From the results of example 1 and examples 4 and 5, it can be seen that the titanium-silicon-aluminum catalyst obtained by treating the discharging agent to a specific crystallinity according to the preferred embodiment and then heat-treating with other raw materials can further improve the propylene oxide conversion rate, the selectivity of 2-methoxy-1-propanol (MME-2) in propylene glycol monomethyl ether, and the catalyst stability.
From the results of example 1 and examples 6 and 7, it can be seen that the molar ratio of the catalyst preferably containing titanium silicalite to the silicon source can further improve the propylene oxide conversion, the selectivity of 2-methoxy-1-propanol (MME-2) in propylene glycol monomethyl ether, and the catalyst stability.
In addition, the titanium-silicon-aluminum molecular sieve is adopted to react in a moving bed, the conversion rate of propylene oxide, the selectivity of 2-methoxy-1-propanol (MME-2) in propylene glycol monomethyl ether and the stability of the catalyst can be further improved under relatively mild conditions, and the problems of temperature runaway of a catalyst bed layer and the like which may occur in a fixed bed reactor are effectively avoided.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A process for the preparation of propylene glycol monomethyl ether, the process comprising:
under the alcoholysis reaction condition, propylene oxide, methanol and a catalyst are contacted in a reaction zone of a moving bed reactor, wherein the catalyst contains a titanium-silicon-aluminum molecular sieve.
2. The method of claim 1, wherein the contacting is performed in the presence of at least one solvent; the solvent is selected from C2-C8Ether of (C)3-C8Ketone and C2-C8At least one of the nitriles of (a);
preferably, the weight ratio of the solvent to propylene oxide is from 0.1 to 100: 1.
3. the process according to claim 1 or 2, wherein the molar ratio of propylene oxide to methanol is 1: 0.1 to 10, preferably 1: 2-5;
preferably, the weight ratio of propylene oxide to the catalyst is from 0.1 to 100: 1, preferably 0.1 to 20: 1.
4. the process of any one of claims 1-3, wherein the alcoholysis reaction conditions comprise: the temperature is 10-140 ℃, and the pressure in the reaction zone of the reactor is 0-2.5MPa in gauge pressure;
preferably, at least part of the catalyst removed from the reaction zone is recycled to the reaction zone, optionally after regeneration.
5. The method of any one of claims 1 to 4, wherein the titanium silicalite molecular sieve is prepared by:
(1) mixing a catalyst containing a titanium silicalite molecular sieve with a first heat treatment liquid, then carrying out first heat treatment, and separating to obtain a first solid with the relative crystallinity of 50-90%, wherein the first heat treatment liquid is an acid solution with the concentration of more than 0.1 mol/L;
(2) and mixing the first solid, a silicon source, an aluminum source, an optional titanium source, an alkali source and water, and then carrying out second heat treatment, wherein the temperature of the second heat treatment is 100-200 ℃.
6. The process of claim 5, wherein the first solid isolated in step (1) has a relative crystallinity of from 70 to 90%.
7. The method according to claim 5 or 6, wherein the catalyst containing the titanium silicalite molecular sieve in the step (1) is a discharging agent of a reaction device using the titanium silicalite molecular sieve as the catalyst, preferably a discharging agent of an ammoximation reaction device;
preferably, the titanium silicalite molecular sieve is of an MFI structure, and the activity of the discharging agent is less than 50% of the activity of the titanium silicalite molecular sieve in a fresh state;
preferably, the discharging agent is calcined before being mixed with the first heat treatment liquid.
8. The method according to any one of claims 5-7, wherein step (2) is performed as follows: mixing a silicon source, an aluminum source and an alkali source in the presence of water 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;
preferably, the temperature of the first heat treatment is 20-45 ℃, and the time of the first heat treatment is 1-30 h;
preferably, the temperature of the second heat treatment is 120-180 ℃, and the time of the second heat treatment is 0.5-25 h.
9. The method according to any one of claims 5-8, wherein SiO is used2And (3) calculating the molar ratio of the catalyst containing the titanium-silicon molecular sieve in the step (1) to the silicon source in the step (2) to be 100: (1-30), preferably 100: (5-20);
preferably, the catalyst containing titanium silicalite: a titanium source: an aluminum source: acid: alkali source: the molar ratio of water is 100: (0.1-10): (0.1-10): (0.005-50): (0.5-50): (20-1000) catalyst containing titanium-silicon molecular sieve is SiO2Measured as H, acid+The alkali source is calculated by N or OH.
10. The method according to any one of claims 5-9,
the acid is organic acid, preferably one or more of naphthenic acid, peracetic acid and propionic acid; the alkali source is one or more of ammonia, aliphatic amine, aliphatic alcohol amine and quaternary ammonium hydroxide; the aluminum source is one or more of aluminum sol, aluminum salt, aluminum hydroxide and aluminum oxide; the titanium source is selected from organic titanate and/or inorganic titanium salt; the silicon source is an organic silicon source and/or an inorganic silicon source, preferably an organic silicon source, and more preferably one or more selected from silicon-containing compounds shown in formula I,
in the formula I, R1、R2、R3And R4Each independently is C1-C4Alkyl group of (1).
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