CN115974656A - Method for separating cresol isomer by membrane - Google Patents
Method for separating cresol isomer by membrane Download PDFInfo
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- CN115974656A CN115974656A CN202211590267.1A CN202211590267A CN115974656A CN 115974656 A CN115974656 A CN 115974656A CN 202211590267 A CN202211590267 A CN 202211590267A CN 115974656 A CN115974656 A CN 115974656A
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a novel process for separating cresol isomers by a membrane method, wherein a membrane separation process is applied to separation of the cresol isomers, different purified products are respectively obtained on two sides of a membrane, and efficient separation and effective utilization of the cresol isomers are further realized. The process comprises the steps of firstly, pretreating a cresol isomer mixture obtained in production to remove impurities, then, feeding the mixture into a membrane separation unit, and obtaining a product rich in p-cresol on the permeation side of a membrane; the retentate side is purified to obtain m-cresol or o-cresol products. The new membrane separation process has the advantages of no need of introducing a third component, simple application, easy operation, low energy consumption and the like, effectively solves the problems of introducing catalysts, adsorbents and the like in the existing technologies such as an alkylation method, an adsorption method and the like, and obviously reduces the separation cost and energy consumption of the system.
Description
Technical Field
The invention relates to a method for separating cresol isomers by an inorganic membrane, in particular to a separation process of mixed cresol isomers, belonging to the field of petrochemical production.
Background
Cresol isomers are important intermediate materials, and include three isomers of p-cresol, m-cresol and o-cresol, and cresol with different structures has different purposes: para-cresol is a particularly important disinfectant or fumigant composition useful in the production of toluic acid, dyes and organic intermediates; m-cresol is widely used in the production of synthetic resins, explosives and organic chemicals as a disinfectant, fumigant, mineral chemical, paint and varnish remover; the o-cresol is mainly used as synthetic resin, and can also be used for preparing pesticides dimethyltetrachloro herbicide, medicinal disinfectants, spices, chemical reagents, antioxidants and the like. Therefore, the cresol isomer mixture obtained by production is separated and purified to make the best use of the cresol isomer mixture, and the development of corresponding technology is very important.
Cresol several isomers have very close boiling points, and the separation processes disclosed so far mainly include the following: 1) An alkylation method, also called an alkylation separation method, is the most mature industrial scheme for separating m/p mixed phenol at present, and is characterized in that an alkylation reagent such as isobutene reacts with m-cresol and p-cresol under the action of an acid catalyst to convert the m-cresol and p-cresol into two substances 4, 6-di-tert-butyl-m-cresol and 2, 6-di-tert-butyl-p-cresol with large boiling point difference, the two substances have the boiling point difference of 20 ℃, the two substances are easily separated by a rectification method, and the rectified product is subjected to tert-butylation removal under the action of the catalyst to obtain the m-cresol and the p-cresol. But the process running cost is increased due to the lack of the efficient and stable environment-friendly dealkylation catalyst. 2) The adsorption method is characterized in that according to different adsorption performances of different adsorbents, isomers of p-cresol are selectively adsorbed and separated, then the isomers are dissolved by a desorption agent under certain conditions, and then the p-cresol with high purity can be obtained. 3) The complex method adopts isopropyl ether, n-butyl ether or isoamyl ether as a solvent, and the extractant is piperazine hexahydrate. Dissolving the precipitate generated by the reaction of p-cresol and extractant in water to dissolve complex, and in the dissolving process, because the extractant is soluble in water, but the p-cresol is not, extracting and separating the p-cresol by using water and organic solvent, and then separating the p-cresol by a rectification mode. The method can generate a large amount of waste water and has the problem of environmental pollution caused by organic solvents.
In view of the above, there is a lack in the art of a process for the efficient, economical direct separation of cresol isomers. Therefore, the technical scheme of simple operation, continuous operation, low separation energy consumption and high product yield is urgently needed to be developed in the field.
Disclosure of Invention
The technical problems to be actually solved by the invention are as follows: the p-cresol and the m-cresol in the p-cresol isomers are separated, because the boiling points of the p-cresol and the m-cresol are similar, various separation methods cannot have good selective separation performance easily, and meanwhile, the alkylation method and other methods also have the problems of high equipment investment, complex operation, high energy consumption and the like.
The invention discovers that the separation of the p-cresol and the m-cresol can be effectively realized by adopting the MFI molecular sieve membrane, and the invention has the advantages of good production continuity and high separation factor.
The technical scheme is as follows:
a method for separating cresol isomers by a membrane, which comprises the following steps: sending the mixture containing p-cresol and m-cresol into an MFI molecular sieve membrane for separation, so that a product rich in p-cresol is obtained on the permeation side of the membrane; the retentate side is purified m-cresol and/or o-cresol products.
The MFI molecular sieve membrane has
The average pore diameter of (2).
The MFI molecular sieve membrane is a ZSM-5 molecular sieve membrane.
The weight ratio of the p-cresol to the m-cresol is 1:9-9:1.
in the separation process, the material temperature is 10-450 ℃, preferably 150-220 ℃, and the feeding partial pressure is 0.1-3 MPa, preferably 100-300Pa.
In the separation process, the mixture is fed by adopting a liquid phase or a gas phase.
Gas phase feeds are gaseous mixtures formed by heating or bubbling.
The MFI molecular sieve membranes are installed in a parallel, series or parallel-series mode through modules.
The permeate side is mass transferred by means of sweeping or vacuum suction.
Advantageous effects
1. The invention provides a new process for separating the paracresol and the meta-cresol in the paracresol isomer, the method can efficiently separate the paracresol and the meta-cresol in the paracresol isomer product, and has the advantages of high separation factor and good separation effect in the separation process of the cresol mixture.
2. The cresol isomer separation process adopted by the invention can be used for replacing an alkylation method in the prior art, and the purpose of separating and treating a pretreated cresol mixture directly through a molecular sieve membrane in a gaseous state by utilizing a membrane separation method can be realized, so that the energy consumption is saved, and the problem that the process operation cost is increased due to the lack of an efficient and stable environment-friendly dealkylation catalyst in the method in the prior art is solved.
3. The method can realize the high-precision separation of the p-cresol isomer mixture, and can realize that the purity of both the p-cresol and the m-cresol reaches 98.5 percent; the separated product has high purity, so that p-cresol can be used for producing plasticizer and phenolic resin, which are important raw materials in plastic industry, and m-cresol can be used as an analytical reagent and also is an important raw material of antioxidant, vitamin E, synthetic resin, color film developer and the like.
4. The invention has simple operation, and the coupling membrane separation unit in the production process can realize the separation and concentration of the target product. The operation conditions of the pretreatment working section and the separation working section are consistent, and the operation conditions do not need to be changed. The device has low investment, can realize the separation of the cresol isomers under the conventional production and operation conditions, is energy-saving and environment-friendly, and has remarkable economic benefit. The inorganic membrane separation unit is directly coupled and embedded into the cresol isomer production process, and the continuous separation and production of the p-cresol and the m-cresol are realized without chemical reaction and adsorption desorption, so that the capacity can be remarkably increased, and the economic benefit is improved. In the process of separating the cresol isomers by the membrane method, the purity requirement of the product can be met only by constructing a membrane separation unit and embedding the membrane separation unit into the whole process flow, and addition and re-separation of third components such as an adsorbent, a desorbent and the like are not needed. The pretreatment section of the prior art can be directly used as a raw material, and other operation conditions are not required to be reset; the separation of p-cresol and m-cresol in cresol isomers can be realized through membrane separation, the separation efficiency is improved to a great extent, and the operation cost is reduced.
Drawings
FIG. 1 is a process flow diagram of separating cresol isomers by membrane method.
Wherein 1 and 3 are single-stage membrane separation modules, 2 and 4 are first gas component receiving lines, and 5 is a second gas component receiving line.
FIG. 2 shows the separation performance of MFI molecular sieve membrane on cresol isomer at different operating temperatures.
FIG. 3 shows the separation performance of MFI molecular sieve membrane for p-cresol isomers at different purge gas flow rates.
FIG. 4 shows the separation performance of MFI molecular sieve membrane on cresol isomer under different raw material partial pressures.
FIG. 5 shows the separation performance of the MFI molecular sieve membrane for p-cresol isomers at different feed rates
FIG. 6 shows the results of the long-term operation of the membrane separation of a mixture of cresol isomers.
Detailed Description
The invention is characterized in that: the separated high-purity p-cresol and m-cresol can be obtained from a mixed cresol system production process in a membrane separation mode; in the separation process, the separation effect is not easily interfered by other components, and the obtained separation product has high purity and less loss. Meanwhile, any temperature and pressure changing treatment is not needed, so that the production energy consumption of related products is remarkably reduced, and the production flow is shortened.
In the present invention, the cresol mixture used is a mixture of p-cresol, m-cresol and/or o-cresol.
The invention discovers that the MFI molecular sieve membrane is adopted when the separation operation is carried out, and the separation of the paracresol and the metacresol can be exactly realized due to the special pore channel structure of the MFI molecular sieve membrane. The MFI molecular sieve membrane is a compact membrane material formed by the interactive growth of MFI type molecular sieves, the channel structure of the MFI molecular sieve membrane is formed by the cross-linking of a 10-membered ring-shaped straight channel and a 10-membered elliptical sinusoidal channel, and the average pore diameter of the MFI molecular sieve membrane is
The separation of components is realized by utilizing regular pore channels of the molecular sieve. The following examples are exemplified by MFI molecular sieve membranes. The preparation of MFI molecular sieve membranes may be carried out with reference to the prior art, for example: shu X, wang X, kong Q, et al, high-Flux MFI Zeolite Membrane Supported on YSZ Hollow Fiber for Separation of Ethanol/Water [ J].INDUSTRIAL&ENGINEERING CHEMISTRY RESEARCH,2012,51(37):12073-12080。
The pore channels have obvious separation selectivity on p-cresol and m-cresol, thereby showing excellent separation performance. On the other hand, the operation conditions of the separation process can be well matched with the front-stage pretreatment working section, so that the integrated design and production are realized.
In the examples which follow, the constituents of the cresol mixture to be separated which are used are 33.3% p-cresol and 66.7% m-cresol.
Fig. 1 shows that the raw material gas is pretreated by the pretreatment unit, so that parameters such as pressure and temperature of the raw material gas meet requirements. The pretreatment unit used in the present invention is not particularly limited, and may include a pressurizing device or a heating device, and the cresol liquid phase raw material is pretreated before entering the membrane separation assembly to meet the corresponding gas phase state requirement. The treated raw material gas enters the retentate side of the membrane separation unit in sequence under proper feeding conditions and positions through the adjustment of the partial pressure of the raw material, and a product rich in p-cresol is obtained on the permeate side and a product rich in m-cresol is obtained on the retentate side after membrane separation and is removed in time. The first-stage membrane component adopted in the invention comprises a shell and an internal MFI molecular sieve membrane, wherein the shell is made of stainless steel or nylon, the shell and the MFI molecular sieve membrane divide the space in the component into a permeation side and a retentate side, the configuration of the shell and the MFI molecular sieve membrane is tubular, and a separation layer is selected to be positioned outside the hollow fiber membrane. The outlet of the permeation side obtains a product rich in p-cresol, and the residual side obtains a product rich in m-cresol.
In the process of feeding the raw materials of the single-stage membrane component, the pressure range is controlled to be 0.01-1 MPa.
Example 1
The separation of p-cresol and m-cresol from the mixture of cresol isomers was carried out according to the procedure described above. The raw material composition and physical properties are shown in table 1.
TABLE 1 simulation of cresol composition and physical Properties
The cresol raw material is heated to 170 ℃ in the raw material pretreatment unit, and then is fed in a gas phase mode in a bubbling gas bubbling mode, and is diluted by the bubbling gas until the raw material partial pressure is 1.4kPa, and then enters the membrane separation assembly. The separation membrane adopts a ZSM-5 molecular sieve membrane, the silica-alumina ratio is 300, the sweep gas adopts helium, the separation pressure is normal pressure, and the separation temperature is 200 ℃. After the single-stage membrane separation component separation, the separation selectivity of p-cresol and m-cresol at the outlet of the permeation side is 5.88, and the content of p-cresol is 73.5% (mol). The product on the permeation side is cooled to room temperature in a liquefying device. The change in the content of each component throughout the separation process is shown in table 2.
TABLE 2 variation of the content of each component in the membrane separation unit
Example 2
In this example, the influence of different purge gas flow rates on the separation performance was examined, the molecular sieve membrane material used was Silicalite-1, the feed gas was the same as in example 1, the purge gas flow rate was changed to measure the separation performance of the long membrane at an operating temperature of 230 ℃, a bubbling gas flow rate of 5mL/min, and a diluting gas flow rate of 10mL/min, and the cresol isomer feed used was the same as in the above example. The cresol raw material is heated in the raw material pretreatment unit and then is fed in a gas phase mode through bubbling of the bubbling gas, the cresol raw material is diluted by the bubbling gas until the raw material partial pressure is 100Pa, and then the cresol raw material enters the membrane separation assembly, other parameters are the same as those in example 1, the test result is shown in figure 2, and the separation factor can reach 32-33 when the amount of the purging gas is 30 mL/min.
Example 3
In this example, the effect of partial pressure of raw material on separation performance was examined, the raw material gas and molecular sieve membrane material used were the same as in example 2, the feed pressure was changed by changing the flow rates of the bubbling gas and the diluting gas at an operating temperature of 230 ℃ and a purge gas of 15mL/min, the cresol raw material used was the same as in the previous example, other parameters were the same as in example 2, and the results of the separation performance test are shown in fig. 3, and a separation factor of about 32 was achieved at a feed pressure of 100 Pa.
Example 4
In this example, the influence of the feed flow rate on the separation performance was examined, the feed gas and the molecular sieve membrane material used were the same as in example 2, the separation performance was examined at an operating temperature of 230 ℃, a purge gas of 15mL/min and a feed partial pressure of 200Pa, the cresol feed components used were the same as in the previous example, the other parameters were the same as in example 2, and the separation performance test results are shown in fig. 4, where the separation factor reached about 24 at a feed flow rate of 20 mL/min.
Example 5
In this example, the influence of the separation temperature on the separation performance was examined, the influence of the operation temperature on the system separation was examined when the feed gas and the molecular sieve membrane material used were the same as in example 2, the sweep gas was 15mL/min, the feed partial pressure was 200Pa, the bubbling gas flow rate was 5mL/min, and the diluting gas flow rate was 10mL/min, the cresol feed components used were the same as in the foregoing example, the other parameters were the same as in example 2, and the separation performance test results are shown in fig. 5, and the separation factor at the operation temperature of 200 ℃ could be 300 or more.
Example 6
This example considers the stability of the separation process for a long time, and when the operation temperature is 200 ℃, the purge gas flow is 15mL/min, the bubbling gas flow is 5mL/min, and the diluting gas flow is 10mL/min, the cresol raw material components are the same as the previous example, other parameters are the same as example 2, and the operation result is shown in fig. 6, which shows that the membrane separation section in the process can keep stable operation for a long time under the production operation condition.
Claims (10)
1. A method for separating cresol isomers by a membrane is characterized by comprising the following steps: sending the mixture containing p-cresol and m-cresol into an MFI molecular sieve membrane for separation, so that a product rich in p-cresol is obtained on the permeation side of the membrane; the retentate side is subjected to filtration to obtain purified m-cresol and/or o-cresol products.
2. The membrane separation method of cresol isomers according to claim 1, wherein the MFI molecular sieve membrane has
The average pore diameter of (a).
3. The method for separating cresol isomers by using membranes as claimed in claim 1, wherein the MFI molecular sieve membranes are ZSM-5 molecular sieve membranes and Silicalite-1 molecular sieve membranes.
4. The method for membrane separation of cresol isomers according to claim 1, wherein the weight ratio of p-cresol and m-cresol is 1:9-9:1.
5. the process for the membrane separation of cresol isomers according to claim 1, characterized in that the separation is carried out at a mass temperature of 10 to 450 ℃, preferably 150 to 220 ℃.
6. The membrane separation process of cresol isomers according to claim 1, characterized in that the separation is carried out with a feed pressure of 0.1MPa to 3MPa, preferably 100 to 300Pa.
7. The process for membrane separation of cresol isomers according to claim 1, wherein the separation is carried out with a mixture fed in liquid or gas phase.
8. The process for separating cresol isomers by membrane separation according to claim 1, wherein the membrane separation device uses a molecular sieve membrane, and the configuration of the molecular sieve membrane can be flat plate type, tubular type, multichannel type or hollow fiber type.
9. The process for membrane separation of cresol isomers according to claim 1, characterized in that the gas phase feed is formed by heating or bubbling a gaseous mixture.
10. The method for membrane separation of cresol isomers according to claim 1, wherein the membrane separation device is a single-stage or multi-stage membrane separation device, and the MFI molecular sieve membranes are installed in parallel, series or series-parallel mode by modules; the permeate side is mass transferred by means of sweeping or vacuum suction.
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Citations (4)
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|---|---|---|---|---|
| US20030215953A1 (en) * | 2000-09-29 | 2003-11-20 | Solvay Pharmaceuticals Gmbh | Separation of cresol from mares' urine |
| JP2007137787A (en) * | 2005-11-15 | 2007-06-07 | Honshu Chem Ind Co Ltd | Method for separating p-cresol |
| CN107445806A (en) * | 2017-07-17 | 2017-12-08 | 天津大学 | Complexation-crystallization method separating-purifying metacresol and paracresol method |
| CN107879900A (en) * | 2017-12-22 | 2018-04-06 | 中触媒新材料股份有限公司 | A kind of process of cresols mixed isomers separating-purifying |
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| US20030215953A1 (en) * | 2000-09-29 | 2003-11-20 | Solvay Pharmaceuticals Gmbh | Separation of cresol from mares' urine |
| JP2007137787A (en) * | 2005-11-15 | 2007-06-07 | Honshu Chem Ind Co Ltd | Method for separating p-cresol |
| CN107445806A (en) * | 2017-07-17 | 2017-12-08 | 天津大学 | Complexation-crystallization method separating-purifying metacresol and paracresol method |
| CN107879900A (en) * | 2017-12-22 | 2018-04-06 | 中触媒新材料股份有限公司 | A kind of process of cresols mixed isomers separating-purifying |
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