CN107324977B - Acetal membrane filtration purification method - Google Patents
Acetal membrane filtration purification method Download PDFInfo
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- CN107324977B CN107324977B CN201710622741.7A CN201710622741A CN107324977B CN 107324977 B CN107324977 B CN 107324977B CN 201710622741 A CN201710622741 A CN 201710622741A CN 107324977 B CN107324977 B CN 107324977B
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- Prior art keywords
- acetal
- molecular sieve
- inorganic membrane
- membrane
- acetaldehyde
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000000746 purification Methods 0.000 title claims abstract description 19
- 238000005374 membrane filtration Methods 0.000 title claims abstract description 13
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 title claims abstract 9
- 239000012528 membrane Substances 0.000 claims abstract description 57
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002808 molecular sieve Substances 0.000 claims abstract description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000047 product Substances 0.000 claims abstract description 27
- 230000008016 vaporization Effects 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 10
- 238000005373 pervaporation Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000012466 permeate Substances 0.000 claims abstract description 6
- 238000009834 vaporization Methods 0.000 claims description 18
- 238000012856 packing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 21
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000003883 substance clean up Methods 0.000 abstract description 2
- 150000001241 acetals Chemical class 0.000 description 54
- 239000000203 mixture Substances 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940126601 medicinal product Drugs 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/58—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of compound purification, in particular to an acetal membrane filtration purification method, which comprises the steps of vaporizing a product produced by the catalytic reaction of acetaldehyde and ethanol to produce acetal, carrying out pervaporation through a molecular sieve inorganic membrane component with the pore diameter of 3.5-4A under the vacuum negative pressure condition of 50-100 pa, and collecting a substance intercepted on the outer side of the molecular sieve inorganic membrane, namely purified acetal; recovering the water, acetaldehyde and ethanol that permeate through the molecular sieve inorganic membrane. The method adopts the pervaporation membrane separation technology, has simple flow, mild operation conditions, high automation degree and safe and simple operation, does not need to add any other auxiliary conditions and auxiliary agents, reduces secondary separation and product pollution in the separation process, greatly improves the product purity, and can realize continuous production.
Description
Technical Field
The invention relates to the technical field of compound purification, in particular to an acetal membrane filtration and purification method.
Background
Acetal, also called acetaldehyde diethyl acetal, is colorless transparent liquid, is volatile and aromatic, can be used as an alcoholic liquor additive, can also be used as an intermediate for synthesizing high-end medicinal products, is a food additive allowed to be used in China GB2760-96, and can reach the specified use amount of more than 200ppm as a flavoring spice.
The main method for producing acetal at present is to take ethanol and acetaldehyde as raw materials, carry out condensation reaction in a batch reaction kettle under the condition of taking inorganic acid or Lewis acid (calcium chloride, ferric chloride and the like) as a catalyst, and then obtain the product after subsequent multiple separation. Because the reaction process is limited by thermodynamics, a large amount of water is generated in the reaction aggregate, and acetal, ethanol, acetaldehyde and water form azeotrope, so that the separation is difficult, and a plurality of unsolvable problems are formed for the separation and purification of products. In order to improve the purity of the acetal, the traditional method adopts a rectification mode, for example, in chinese patent CN103058837A, the purification production of the acetal is realized by designing rectification equipment, but the mode of distillation separation by a rectification tower has high equipment investment cost, complex operation, low efficiency and high energy consumption; on the other hand, the requirement of high-quality products on high purity of acetal cannot be met. Therefore, an acetal purification method which is efficient and rapid and is suitable for industrial popularization and application is sought, and the method has great significance for meeting the requirement of the market on high-quality products.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an acetal membrane filtration purification method, which can purify the acetal produced by the reaction of ethanol and acetaldehyde rapidly, efficiently and with high purity.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a membrane filtration purification method for acetal comprises the steps of vaporizing a product produced by the catalytic reaction of acetaldehyde and ethanol to produce acetal, carrying out pervaporation through a molecular sieve inorganic membrane component with the pore diameter of 3.5-4A under the vacuum negative pressure condition of 50-100 Pa, and collecting a substance intercepted on the outer side of the molecular sieve inorganic membrane to obtain the purified acetal; recovering the water, acetaldehyde and ethanol that permeate through the molecular sieve inorganic membrane.
Optionally, the specific method of vaporization is to pressurize and heat the vapor to vaporize the vapor at 190 Kpa-200 Kpa and 83-122 ℃.
Optionally, the vaporization rate of the product is 40 kg/h-100 kg/h.
Optionally, the molecular sieve inorganic membrane component is an inorganic membrane component formed by sequentially connecting eight groups of inorganic membrane components, and each group of inorganic membrane component comprises 7 tubular membranes; the total packing area of the eight groups of inorganic membranes is 1.6m2。
The specific method for producing the acetal by the acetaldehyde and the ethanol through the catalytic reaction takes the acetaldehyde and the ethanol as raw materials, takes the super-strong solid acid as a catalyst and takes
The molecular sieve is used as a carrier and reacts to generate acetal.
The invention relates to an acetal membrane filtration and purification method, which adopts a pervaporation membrane separation technology, and creatively selects a molecular sieve inorganic membrane with a proper pore diameter and a vacuum negative pressure permeation condition, so that after a vaporized acetal product passes through the molecular sieve inorganic membrane, acetal is retained outside the membrane, small molecular water, ethanol and acetaldehyde can smoothly pass through the molecular sieve inorganic membrane, the separation and purification of the acetal are realized, the flow is simple, the operation condition is mild, the automation degree is high, the operation is safe and simple, no other auxiliary conditions or auxiliary medicaments are required to be added, the secondary separation and product pollution in the separation process are reduced, the product purity is greatly improved, and the continuous production can be realized.
Furthermore, the vapor pressure, the vaporization temperature and the vaporization rate of the vaporization of the product with separation are creatively selected, the stability of the separation and purification of the product is ensured, and the high purity of the acetal obtained by separation is ensured.
Detailed Description
The technical solution of the present invention will be described in detail by specific examples.
The specific method for producing acetal by the catalytic reaction of acetaldehyde and ethanol in the following examples is to take acetaldehyde and ethanol as raw materials, take super-strong solid acid as a catalyst and take
The molecular sieve is used as a carrier and reacts to generate acetal.
In the following examples, an NBS-AH type full-automatic electric heating steam generator was used to generate steam; A2X-T rotary vane oil pump is adopted to generate a vacuum negative pressure condition.
In the following embodiments, the molecular sieve inorganic membrane component is an inorganic membrane component formed by connecting eight groups of inorganic membrane components in sequence, each group of inorganic membrane component comprises 7 tubular membranes, and the total packing area of the eight groups of inorganic membranes is 1.6m2。
Example 1
A membrane filtration purification method of acetal comprises that the product of acetaldehyde and ethanol catalytic reaction for producing acetal is vaporized by steam under 195Kpa pressure, 100 ℃, 80kg/h vaporization rate and 80Pa vacuum negative pressure, and passes through a molecular sieve inorganic membrane component with 4A pore diameter for pervaporation, and the material trapped at the outer side of the molecular sieve inorganic membrane is the purified acetal; the outer side of the molecular sieve inorganic membrane component is connected with a dehydration tank, and water, acetaldehyde and ethanol which permeate through the molecular sieve inorganic membrane enter the dehydration tank for recycling under the action of negative pressure.
The purified acetal was collected and the purity was checked to be 99.9%.
Example 2
A membrane filtration purification method of acetal comprises that the product of acetaldehyde and ethanol catalytic reaction for producing acetal is vaporized by steam under 190Kpa pressure and 122 ℃ at a vaporization rate of 40kg/h and under a vacuum negative pressure condition of 50pa, and passes through a molecular sieve inorganic membrane component with a pore diameter of 3.5A for pervaporation, and the material trapped at the outer side of the molecular sieve inorganic membrane is the purified acetal; the outer side of the molecular sieve inorganic membrane component is connected with a dehydration tank, and water, acetaldehyde and ethanol which permeate through the molecular sieve inorganic membrane enter the dehydration tank for recycling under the action of negative pressure.
The purified acetal was collected and the purity was checked to be 99.9%.
Example 3
A membrane filtration purification method of acetal comprises that the product of acetaldehyde and ethanol catalytic reaction for producing acetal is vaporized by steam under 200Kpa pressure, 83 ℃, 100kg/h vaporization rate and 100Pa vacuum negative pressure, and passes through a molecular sieve inorganic membrane component with 4A pore diameter for pervaporation, and the material trapped at the outer side of the molecular sieve inorganic membrane is the purified acetal; the outer side of the molecular sieve inorganic membrane component is connected with a dehydration tank, and water, acetaldehyde and ethanol which permeate through the molecular sieve inorganic membrane enter the dehydration tank for recycling under the action of negative pressure.
The purified acetal was collected and the purity was checked to be 99.9%.
Comparative example 1
Acetal with a purity of 99.9% was mixed with ethanol with a purity of 99.9%, and the mixture of acetal and ethanol was separated in the same manner as in example 1.
The product trapped on the outer side of the inorganic membrane was taken, and the analysis and detection result showed that the material trapped on the outer side of the inorganic membrane was still a mixture of acetal and ethanol, and the volume content of acetal was 98.5%, indicating that the same method as in example 1 could not separate the mixture of acetal and ethanol well.
Comparative example 2
Acetal with a purity of 99.9% and acetaldehyde with a purity of 99.9% were mixed, and the mixture of acetal and acetaldehyde was separated in the same manner as in example 1.
The product trapped on the outer side of the inorganic membrane was taken, and the analysis and detection result showed that the substance trapped on the outer side of the inorganic membrane was still a mixture of acetal and acetaldehyde, and the volume content of acetal was 97.8%, indicating that the same method as in example 1 could not separate the mixture of acetal and acetaldehyde well.
Comparative example 3
Acetal of 99.9% purity was mixed with water, and the mixture of acetal and water was separated in the same manner as in example 1.
The product trapped on the outer side of the inorganic membrane was taken, and the analysis and detection results showed that the material trapped on the outer side of the inorganic membrane was still a mixture of acetal and water, and the volume content of acetal was 97.5%, indicating that the mixture of acetal and water could not be separated well by the same method as in example 1.
According to the detection results of comparative examples 1 to 3, in the process of separating and purifying the acetal by adopting a pervaporation membrane separation mode, the molecular weight of the substance to be separated is not only related to, but also related to the composition of the substance to be separated, and the boiling point, the conductivity, the intermolecular force, the molecular distance, the molecular size and the like of the substance to be separated after blending are related to each other, and the high-quality separation and purification of the substance can be realized only by selecting proper negative pressure conditions, steam conditions, vaporization temperature conditions, vaporization rate conditions and membrane pore diameters according to the substance to be separated. However, when the existing method is used for separating and purifying the acetal product produced by the catalytic reaction of acetaldehyde and glycolic acid, the membrane separation technology is not used, and the prior art also does not disclose which rule to select pressure, vaporization rate, vaporization temperature and membrane pore size when the membrane separation technology is used for separating and purifying the product, so that the invention pays creative labor, adopts a proper analysis sieve inorganic membrane component, a proper vaporization condition, a proper vaporization rate and a negative pressure permeation condition, separates and purifies the acetal product generated by the catalytic reaction of acetaldehyde and glycolic acid to ensure that the purity of the obtained acetal reaches 99.9 percent, has simple separation process, mild operation condition, high automation degree and safe and simple operation, does not need to add any other auxiliary conditions and auxiliary agents, and reduces secondary separation and product pollution in the separation process, greatly improves the product purity and can realize continuous production.
Claims (3)
1. A membrane filtration purification method for acetal is characterized by comprising the steps of vaporizing a product produced by the catalytic reaction of acetaldehyde and ethanol to produce acetal, performing pervaporation through a molecular sieve inorganic membrane component with the pore diameter of 3.5-4A under the vacuum negative pressure condition of 50-100 Pa, and collecting a substance intercepted on the outer side of the molecular sieve inorganic membrane, namely purified acetal; recovering water, acetaldehyde and ethanol that permeate through the molecular sieve inorganic membrane; the specific method of vaporization is that steam is adopted for pressurization and heating vaporization, the steam pressure is 190 Kpa-200 Kpa, and the vaporization temperature is 83-122 ℃.
2. The membrane filtration purification method of acetal according to claim 1, wherein the vaporization rate of the product is 40kg/h to 100 kg/h.
3. The acetal membrane filtration purification method according to claim 1, wherein the molecular sieve inorganic membrane components are inorganic membrane components that are sequentially connected by eight groups of inorganic membrane components, and each group of inorganic membrane components comprises 7 tubular membranes; the total packing area of the eight groups of inorganic membranes is 1.6m2。
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| CN201710622741.7A CN107324977B (en) | 2017-07-27 | 2017-07-27 | Acetal membrane filtration purification method |
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| CN201710622741.7A CN107324977B (en) | 2017-07-27 | 2017-07-27 | Acetal membrane filtration purification method |
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| CN107324977B true CN107324977B (en) | 2020-09-01 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2418009A1 (en) * | 2009-04-08 | 2012-02-15 | Universidade Do Porto | Simulated moving bed membrane reactor, new hybrid separation process and uses thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| PT103123A (en) * | 2004-05-19 | 2005-11-30 | Univ Do Porto | INDUSTRIAL PROCESS OF ACETAL PRODUCTION IN AN ADSORPTIVE REACTOR OF SIMULATED MOVEL MOBILE |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2418009A1 (en) * | 2009-04-08 | 2012-02-15 | Universidade Do Porto | Simulated moving bed membrane reactor, new hybrid separation process and uses thereof |
Non-Patent Citations (1)
| Title |
|---|
| 森头汽化膜反应器;周荣飞等;《膜科学与技术》;20060228;第26卷(第1期);第61-67页 * |
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