CN110655454A - Method and system for preparing dipropylene glycol with high selectivity - Google Patents
Method and system for preparing dipropylene glycol with high selectivity Download PDFInfo
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- CN110655454A CN110655454A CN201810696916.3A CN201810696916A CN110655454A CN 110655454 A CN110655454 A CN 110655454A CN 201810696916 A CN201810696916 A CN 201810696916A CN 110655454 A CN110655454 A CN 110655454A
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- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 31
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000002994 raw material Substances 0.000 claims abstract description 70
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 claims abstract description 44
- 238000006482 condensation reaction Methods 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 46
- 239000000872 buffer Substances 0.000 claims description 39
- 238000000746 purification Methods 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 6
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 6
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011831 acidic ionic liquid Substances 0.000 claims description 4
- 229910000856 hastalloy Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 44
- 229960004063 propylene glycol Drugs 0.000 abstract description 44
- 230000035484 reaction time Effects 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 9
- 239000000047 product Substances 0.000 description 53
- 239000012043 crude product Substances 0.000 description 23
- 235000013772 propylene glycol Nutrition 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 9
- 239000012467 final product Substances 0.000 description 7
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 230000014509 gene expression Effects 0.000 description 4
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- 239000000203 mixture Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
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- 238000003556 assay Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
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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
-
- 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
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of dipropylene glycol, which comprises the following steps of mixing propylene oxide and propylene glycol to obtain a mixed raw material; and then carrying out condensation reaction on the mixed raw materials obtained in the step in a microchannel reactor to obtain the dipropylene glycol. The invention starts from the aspect of hydromechanics in the reaction process, particularly adopts the microchannel reactor as a reaction site, and utilizes the characteristic of the diameter of the low channel of the microchannel reactor to ensure that the raw materials are in a laminar flow state in the channel, thereby reducing the back mixing phenomenon, avoiding the contact chance of the dipropylene glycol with the raw materials of 1, 2-propylene glycol and propylene oxide, reducing the occurrence of series reaction and further effectively improving the selectivity of the dipropylene glycol in the product. The preparation method provided by the invention can effectively reduce the reaction time, improve the yield of the dipropylene glycol product, and is simple in process, mild in condition, easy to control and more suitable for industrial mass production.
Description
Technical Field
The invention relates to the technical field of 1, 2-propylene glycol synthesis, relates to a method and a system for preparing dipropylene glycol, and particularly relates to a method and a system for preparing dipropylene glycol with high selectivity.
Background
Dipropylene glycol, also known as Dipropylene glycol, Dipropylene glycol (DPG for short), is a colorless, odorless liquid at normal temperature, has no corrosivity, has little irritation to skin, has low toxicity, and is widely applied. Dipropylene glycol can be classified into LO + grade and industrial grade. The price of the former is high, and the former is mainly applied to the fields requiring high-quality raw materials such as spices, cosmetics, detergents, food additives and the like; the latter is relatively inexpensive and is widely used as a raw material for the production of industrial solvents and unsaturated resins, nitrocellulose varnishes and the like, which do not have high requirements for the quality of DPG.
Dipropylene glycol is mainly derived from dipropylene glycol and tripropylene glycol (also known as tripropylene glycol, abbreviated as TPG) produced in small amounts during the process of hydration of Propylene Oxide (PO) to 1, 2-propanediol (also known as propylene glycol, abbreviated as PG), with a product ratio of about 1.2-propanediol: dipropylene glycol: tripropylene glycol is 100:10: 1. In the prior art, dipropylene glycol is mainly sold as a byproduct, so that the production industry of dipropylene glycol is difficult to form a certain scale, the operating rate is determined by the market demand of 1.2-propylene glycol, the yield is unstable, and the ever-increasing market demand cannot be met.
In recent years, some manufacturing enterprises begin to synthesize a dipropylene glycol product by a ring-opening condensation reaction using Propylene Oxide (PO) and 1, 2-Propanediol (PG) as raw materials in the presence of a catalyst by a batch or continuous method, but the side reaction of the ring-opening condensation reaction is severe, and the intended product dipropylene glycol continues to be condensed with 1, 2-propanediol or propylene oxide to obtain a propylene glycol polymer having a high degree of condensation of tripropylene glycol, tetrapropylene glycol (also known as tetrapropylene glycol), and a byproduct tripropylene glycol is mainly used. And the tandem reaction causes low selectivity of dipropylene glycol in the product, and the target product is difficult to be efficiently obtained through the reaction. The by-products of tripropylene glycol, tetrapropylene glycol and propylene glycol high polymer with higher condensation degree belong to high boiling point substances, the separation and purification are difficult and the required energy consumption is high; meanwhile, the reaction of the propylene oxide and the 1, 2-propylene glycol is exothermic, so that the temperature is not easy to control in the reaction process, the reaction time is long, and the energy consumption of the device is increased. For example, patent TW201343617A discloses a method for producing dipropylene glycol and/or tripropylene glycol by reacting 1, 2-propanediol: propylene oxide reaction, and dipropylene glycol and tripropylene glycol are prepared with high selectivity without using catalysis. Although the selectivity of DPG and TPG reaches more than 80%, DPG production with high selectivity cannot be realized. Patent CN 203382693 uses propylene oxide and 1, 2-propylene glycol as raw materials to synthesize a crude dipropylene glycol product, and then the crude dipropylene glycol product is refined and separated to obtain high-quality dipropylene glycol, but the reaction is an intermittent reaction, the utilization rate of equipment is not high, and it is not suitable to realize automatic control. In patents CN203393068 and CN201981142, propylene oxide and 1, 2-propylene glycol are also used as raw materials, and a continuous reaction process is used to solve the defects of complex operation, high energy consumption and the like of the synthesis process, but the series reaction is serious, a large amount of by-products are generated, and the tripropylene glycol needs to be refined and recovered. For another example, patent CN101665414A synthesizes dipropylene glycol from propylene oxide and 1, 2-propanediol without catalyst, but has the disadvantages of long reaction time, high energy consumption, etc. Therefore, most of the existing production enterprises can only sell the crude product with the content of 50-80%, the price of the crude product is low, and the economic benefit of the whole set of equipment is also reduced.
Therefore, how to find a more suitable independent dipropylene glycol preparation method, which is continuous in operation, short in reaction time and high in selectivity, is very important for large-scale industrial production of dipropylene glycol, and becomes one of the problems to be solved by a plurality of production enterprises and front-line research and development staff in the industry.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing dipropylene glycol, and in particular, to a method for preparing dipropylene glycol with high selectivity, which can effectively reduce the reaction time, greatly improve the yield and selectivity of dipropylene glycol products, and has a simple process, and is suitable for industrial mass production.
The invention provides a preparation method of dipropylene glycol, which comprises the following steps:
1) mixing propylene oxide and propylene glycol to obtain a mixed raw material;
2) and (3) carrying out condensation reaction on the mixed raw materials obtained in the step in a microchannel reactor to obtain dipropylene glycol.
Preferably, the mixing comprises mixing in a microchannel mixer;
the molar ratio of the propylene glycol to the propylene oxide is (1-10): 1;
the temperature of the condensation reaction is 100-180 ℃;
the pressure of the condensation reaction is 0.1-1 MPa;
the time of the condensation reaction is 1-10 min.
Preferably, a preheating step is further included before the condensation reaction;
the preheating temperature is 60-160 ℃;
the material of the microchannel reactor comprises one or more of stainless steel, hastelloy and silicon carbide;
the diameter of the channel of the microchannel reactor is 0.1-3 mm;
the condensation reaction also includes a separation step.
Preferably, the separation step comprises rectification dehydrogenation and rectification purification;
the vacuum degree of the rectification dehydrogenation is less than or equal to 5 KPa;
the tower top temperature of the rectification dehydrogenation is 120-140 ℃;
the temperature of a tower kettle for rectifying dehydrogenation is 150-170 ℃;
the vacuum degree of the rectification purification is less than or equal to 5 KPa;
the tower top temperature of the rectification and purification is 130-160 ℃;
the temperature of a tower kettle for rectification and purification is 170-190 ℃;
recovering the light components after rectification dehydrogenation into the mixed raw material;
the extraction mode after rectification and purification is measuring line extraction.
Preferably, the step 1) is specifically:
mixing propylene oxide, propylene glycol and a catalyst to obtain a mixed raw material;
the catalyst comprises an acidic liquid catalyst or a basic liquid catalyst.
Preferably, the acidic liquid catalyst comprises one or more of sulfuric acid, hydrochloric acid, nitric acid, benzenesulfonic acid and acidic ionic liquid;
the alkaline liquid catalyst comprises one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium methoxide;
the mass ratio of the catalyst to the propylene oxide is (0.001-0.1): 1.
the invention provides a system for preparing dipropylene glycol, which comprises:
a microchannel mixer;
a microchannel reactor connected to the microchannel mixer outlet;
a dehydrogenation unit connected with the outlet of the microchannel reactor;
and the purifying device is connected with the outlet of the dehydrogenation device.
Preferably, the diameter of the channel of the micro-channel mixer is 0.05-4 mm;
the system further comprises a preheater;
the outlet of the micro-channel mixer is connected with the inlet of the preheater, and the outlet of the preheater is connected with the inlet of the micro-channel mixer.
Preferably, the system further comprises a buffer device and/or a buffer device;
the outlet of the micro-channel mixer is connected with the inlet of the buffer device, and the outlet of the buffer device is connected with the inlet of the preheater;
the outlet of the micro-channel mixer is connected with the inlet of the cache device, and the outlet of the cache device is connected with the inlet of the dehydrogenation device.
Preferably, the dehydrogenation device comprises one or more of a plate rectifying tower, a packed rectifying tower and a rectifying still;
the purification device comprises one or more of a plate-type rectifying tower, a filler rectifying tower and a rectifying still;
the outlet of the tower top of the dehydrogenation device is connected with the inlet of the buffer device;
and the outlet of the tower kettle of the dehydrogenation device is connected with the inlet of the purification device.
The invention provides a preparation method of dipropylene glycol, which comprises the following steps of mixing propylene oxide and propylene glycol to obtain a mixed raw material; and then carrying out condensation reaction on the mixed raw materials obtained in the step in a microchannel reactor to obtain the dipropylene glycol. Compared with the prior art, the invention provides an independent preparation method of dipropylene glycol with high selectivity aiming at the problems of poor independence and unstable start-up of the conventional dipropylene glycol as a byproduct of propylene glycol. Aiming at the existing independent ring-opening condensation reaction, the side reaction is serious, the selectivity is low, and the target product is difficult to be efficiently obtained through the reaction; the separation and purification are difficult, and the energy consumption is high; and the defects of uncontrollable temperature, long reaction time, increased energy consumption and the like exist.
The invention creatively starts from the fluid mechanics angle of the reaction process, abandons the characteristic of the prior mixed flow state reaction, changes the reaction into the ordered laminar flow, is more beneficial to the proceeding of the reaction and the improvement of the selectivity, particularly adopts the microchannel reactor as the reaction place, utilizes the characteristic of the diameter of the low channel of the microchannel reactor to lead the raw material to be in the laminar flow state in the channel, reduces the back mixing phenomenon, effectively avoids the contact opportunity of the dipropylene glycol with the raw material 1.2-propylene glycol and the propylene oxide, reduces the occurrence of the series reaction, thereby effectively improving the selectivity of the dipropylene glycol in the product. The preparation method provided by the invention can effectively reduce the reaction time, greatly improve the yield of the dipropylene glycol product, and is simple in process, mild in condition, easy to control and more suitable for industrial mass production.
Experimental results show that the preparation method provided by the invention can improve the selectivity of dipropylene glycol from 50-80% to 90-98%, and reduce the reaction time from 1-3 h to 1-10 min, thereby effectively improving the yield of target products, the aging cost and the energy consumption.
Drawings
FIG. 1 is a schematic flow chart of a system for preparing dipropylene glycol with high selectivity provided by the present invention;
FIG. 2 is a gas chromatography of the crude product after reaction in example 1 of the present invention;
fig. 3 is a gas chromatography spectrum of dipropylene glycol product prepared according to example 1 of the present invention.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs industrial purity or purity which is conventional in the art of dipropylene glycol production.
All the noun expressions and acronyms of the invention belong to the conventional noun expressions and acronyms in the field, each noun expression and acronym is clearly and definitely clear in the relevant application field, and a person skilled in the art can clearly, exactly and uniquely understand the noun expressions and acronyms.
The invention provides a preparation method of dipropylene glycol, which comprises the following steps:
1) mixing propylene oxide and propylene glycol to obtain a mixed raw material;
2) and (3) carrying out condensation reaction on the mixed raw materials obtained in the step in a microchannel reactor to obtain dipropylene glycol.
According to the invention, firstly, the propylene oxide and the propylene glycol are mixed to obtain a mixed raw material.
The adding proportion of the propylene oxide and the propylene glycol is not particularly limited, and can be selected and adjusted by the skilled in the art according to the actual production situation, the raw material situation and the product requirement, and the molar ratio of the propylene glycol to the propylene oxide is preferably (1-10): 1, more preferably (3-9): 1, more preferably (3-5): 1.
the mixing mode is not particularly limited by the invention, and the mixing mode known by the technicians in the field can be selected and adjusted by the technicians in the field according to the actual production condition, the raw material condition and the product requirement, and the mixing mode is particularly preferably used for mixing in a microchannel mixer in order to improve the mixing effect and further improve the mass transfer effect of the later reaction and match with the microchannel reactor for reaction.
The mixing parameters are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the mixing time in the present invention is preferably 1-5 min, more preferably 1.5-4.5 min, and more preferably 2-4 min. The diameter of the micro-channel mixer channel is preferably 0.05-4 mm, more preferably 0.1-3.5 mm, more preferably 0.5-3 mm, more preferably 1-2.5 mm, and more preferably 1.5-2 mm.
The invention then carries out condensation reaction on the mixed raw material obtained in the step in a microchannel reactor to obtain the dipropylene glycol.
In order to further improve the effect of the subsequent condensation reaction and ensure the quality of the final product, the invention preferably further comprises a preheating step before the condensation reaction. The preheating temperature is preferably 60-160 ℃, more preferably 80-140 ℃, and more preferably 100-120 ℃ in order to improve the condensation reaction effect and ensure the product performance.
The microchannel reactor is not particularly limited, and the microchannel reactor known by the skilled in the art can be selected and adjusted by the skilled in the art according to the actual production condition, the raw material condition and the product requirement, and in order to improve the condensation reaction effect and the mass transfer effect of the condensation reaction, the diameter of the channel of the microchannel reactor is preferably 0.1-3 mm, more preferably 0.5-2.5 mm, and more preferably 1-2 mm. The material of the microchannel reactor preferably comprises one or more of stainless steel, hastelloy and silicon carbide, and more preferably the stainless steel, hastelloy or silicon carbide.
The parameters of the condensation reaction are not particularly limited, and conventional parameters of the reaction well known to those skilled in the art can be used, and the those skilled in the art can select and adjust the parameters according to actual production conditions, raw material conditions and product requirements, and in order to improve the condensation reaction effect and ensure the performance of the product, the preheating temperature is preferably 100-180 ℃, more preferably 110-170 ℃, more preferably 120-160 ℃, and more preferably 130-150 ℃. The pressure of the condensation reaction is preferably 0.1-1 MPa, more preferably 0.3-0.8 MPa, and more preferably 0.5-0.6 MPa. The time of the condensation reaction is preferably 1-10 min, more preferably 3-8 min, and more preferably 5-6 min.
In order to further ensure the quality of the final product, complete and refine the whole preparation process, the method preferably further comprises a separation step after the condensation reaction. The specific steps and parameters of the separation are not particularly limited by the invention, and the separation can be carried out by common separation steps and parameters which are well known to those skilled in the art, and in order to adapt to industrial production and achieve reasonable recycling of raw materials, the separation steps preferably comprise rectification dehydrogenation and rectification purification.
The vacuum degree of the rectification dehydrogenation in the invention is preferably not more than 5KPa, more preferably not more than 3KPa, and still more preferably not more than 1 KPa. The tower top temperature of the rectification dehydrogenation is preferably 120-140 ℃, more preferably 122-138 ℃, and more preferably 125-135 ℃. The temperature of the tower kettle for rectification dehydrogenation is preferably 150-170 ℃, more preferably 152-168 ℃, and more preferably 155-165 ℃.
The vacuum degree of the rectification purification of the invention is preferably not more than 5KPa, more preferably not more than 3KPa, and still more preferably not more than 1 KPa. The tower top temperature of the rectification and purification is preferably 130-160 ℃, more preferably 135-155 ℃, and more preferably 140-150 ℃. The temperature of the rectifying and purifying tower kettle is preferably 170-180 ℃, more preferably 172-188 ℃, and more preferably 175-185 ℃.
After rectification dehydrogenation, the unreacted propylene oxide and light 1, 2-propylene glycol components are removed, and the light propylene oxide and light 1, 2-propylene glycol components are recycled into the mixed raw material for recycling. The extraction mode after rectification and purification is preferably measurement line extraction.
In the process of preparing dipropylene glycol according to the present invention, a catalyst may not be needed, or a catalyst may be used, the present invention is not particularly limited, and the essence of the technical solution of the present invention is not affected, and for a better complete preparation process, when a catalyst is used, the step 1) according to the present invention is specifically preferably:
mixing the propylene oxide, the propylene glycol and the catalyst to obtain a mixed raw material.
The selection and amount of the catalyst are not particularly limited in the present invention, and may be conventional catalysts and amounts thereof for the reaction, which are well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the catalyst of the present invention may be an acidic liquid catalyst or a basic liquid catalyst. Wherein, the acidic liquid catalyst preferably comprises one or more of sulfuric acid, hydrochloric acid, nitric acid, benzenesulfonic acid and acidic ionic liquid, and more preferably comprises sulfuric acid, hydrochloric acid, nitric acid, benzenesulfonic acid or acidic ionic liquid. The basic liquid catalyst of the present invention preferably comprises one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium methoxide, more preferably sodium hydroxide, potassium hydroxide, sodium bicarbonate or sodium methoxide. The mass ratio of the catalyst to the propylene oxide is preferably (0.001-0.1): 1, more preferably (0.005 to 0.08): 1, more preferably (0.01 to 0.06): 1, more preferably (0.02 to 0.05): 1.
in order to further improve the performance of the final product and to complete and optimize the preparation method and the process system, the preparation method specifically comprises the following steps:
the method comprises the steps of injecting propylene oxide, 1.2-propylene glycol and a catalyst into a microchannel mixer through a metering pump according to a certain proportion, mixing multiple strands of raw materials through the microchannel mixer, then feeding the raw materials into a raw material buffer tank, preheating the materials in the raw material buffer tank to 60-160 ℃ through a preheater, starting feeding the materials into the microchannel reactor, controlling the pressure in the microchannel reactor to be 0.1-1 Mpa, the reaction temperature to be 100-180 ℃, keeping the materials for 2-10 min, collecting a crude product at an outlet of the microchannel reactor, condensing the crude product, then feeding the crude product into a separation device, dividing the crude product separation device into two parts, namely a first part light removal device, removing unreacted propylene oxide and 1.2-propylene glycol, returning the unreacted propylene oxide and 1.2-propylene glycol to the raw material buffer tank, and separating the crude product into a second part which is a product purification device to obtain a high-quality dipropylene glycol product.
The purity of the product obtained by the method reaches 99.95 percent, the chroma is less than or equal to 5, and the selectivity of dipropylene glycol in the crude product is more than or equal to 98 percent.
The invention also provides a system for preparing dipropylene glycol, comprising:
a microchannel mixer;
a microchannel reactor connected to the microchannel mixer outlet;
a dehydrogenation unit connected with the outlet of the microchannel reactor;
and the purifying device is connected with the outlet of the dehydrogenation device.
The selection and composition of the required equipment in the above system for preparing dipropylene glycol, and the corresponding preferred principles, and the selection and composition of the equipment corresponding to the above preparation method, and the corresponding preferred principles can all be corresponded, and are not described in detail herein.
The connection mode is not particularly limited by the present invention, and may be a conventional connection mode in the art, which is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual production situation, the raw material situation and the product requirement, and the connection mode is preferably connected by a pipeline, or connected by a pipeline and a pump.
In the invention, the production system comprises a microchannel mixer and a microchannel reactor connected with an outlet of the microchannel mixer, namely, the outlet of the microchannel mixer is connected with an inlet of the microchannel reactor.
In the present invention, the production system further comprises a preheater. The preheater is arranged between the microchannel mixer and the microchannel reactor, namely, the outlet of the microchannel mixer is connected with the inlet of the preheater, and the outlet of the preheater is connected with the inlet of the microchannel mixer. The method has the effects of facilitating the condensation reaction and improving the reaction efficiency. The structure and parameters of the preheater are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, as the structure and parameters of conventional preheaters are well known to those skilled in the art. In other embodiments, other devices having the same function may be included to facilitate the condensation reaction and improve the reaction effect.
In the present invention, the production system further includes a buffer device. The buffer device is arranged between the micro-channel mixer and the preheater, namely the outlet of the micro-channel mixer is connected with the inlet of the buffer device, and the outlet of the buffer device is connected with the inlet of the preheater. The method has the function of ensuring the stability and the continuity of the production process, and is suitable for large-scale production and remote control. The structure and parameters of the buffer device are not particularly limited by the present invention, and can be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, with the structure and parameters of the conventional preheater well known to those skilled in the art, and the buffer device of the present invention is preferably a buffer tank. In other embodiments, other devices may be included to help ensure the stability and continuity of the production process, and mass production and remote control are preferred.
In the present invention, the production system further includes a cache device, i.e., a product cache device. The buffer device is arranged between the microchannel reactor and the dehydrogenation device, namely the outlet of the microchannel mixer is connected with the inlet of the buffer device, and the outlet of the buffer device is connected with the inlet of the dehydrogenation device. The method has the function of ensuring the stability and the continuity of the production process, and is suitable for large-scale production and remote control. The structure and parameters of the buffer device are not particularly limited in the present invention, and may be the structure and parameters of a conventional preheater well known to those skilled in the art, and those skilled in the art may select and adjust the buffer device according to actual production conditions, raw material conditions and product requirements, and the buffer device of the present invention is preferably a buffer tank. In other embodiments, other devices may be included to help ensure the stability and continuity of the production process, and mass production and remote control are preferred.
In the present invention, the production system includes a dehydrogenation unit. The dehydrogenation device is arranged between the microchannel reactor and the purification device, namely the outlet of the microchannel reactor is connected with the inlet of the dehydrogenation device; more preferably, the buffer device is arranged between the buffer device and the purification device, that is, the outlet of the buffer device is connected with the inlet of the purification device, and the outlet of the purification device is connected with the inlet of the purification device. The method has the effects of providing the purity of the final product, ensuring the performance of the product and ensuring the stability and continuity of the production process.
In the present invention, there is no particular limitation on the selection of the dehydrogenation device, and the conventional dehydrogenation device known to those skilled in the art can be used, and those skilled in the art can select and adjust the dehydrogenation device according to the actual production situation, raw material situation and product requirement. In other embodiments, the dehydrogenation device can be other equipment, so as to help ensure the stability and continuity of the production process and improve the dehydrogenation effect, and the preferable scheme is suitable for matching.
In the invention, in order to further form a complete recycling production system and ensure the stability and continuity of the production process, the outlet at the top of the dehydrogenation device is connected with the inlet of the buffer device, namely, the light components after dehydrogenation mainly contain unreacted propylene oxide and 1, 2-propylene glycol, and the light components are returned to the raw material buffer device for recycling. The outlet of the tower kettle of the dehydrogenation device is connected with the inlet of the purification device, namely, the dehydrogenated heavy component, namely the product, enters the subsequent purification device.
In the present invention, the production system includes a purification apparatus. The purification device is arranged after the dehydrogenation device, namely the outlet of the dehydrogenation device is connected with the inlet of the purification device. The method has the effects of providing the purity of the final product, ensuring the performance of the product and ensuring the stability and continuity of the production process.
In the present invention, the selection of the purification device is not particularly limited, and a conventional purification device known to those skilled in the art may be used, and those skilled in the art may select and adjust the purification device according to actual production conditions, raw material conditions, and product requirements. In other embodiments, the purification device can be other equipment, so as to be beneficial to ensuring the stability and continuity of the production process and improving the dehydrogenation effect, and the optimal scheme is adopted.
In the present invention, the final product is withdrawn from the side of the purification apparatus in order to ensure the performance of the final product and the stability and continuity of the production process.
Referring to fig. 1, fig. 1 is a schematic flow chart of a system for preparing dipropylene glycol with high selectivity according to the present invention. The method comprises the following steps of 1-a microchannel mixer, 2-a raw material mixing tank, 3-a raw material preheater, 4-a microchannel reactor, 5-a crude product buffer tank, 6-a dehydrogenation device and 7-a product refining and purifying device.
The preparation method and the system of the dipropylene glycol provided by the steps are a circulating method and a circulating system for preparing the dipropylene glycol with high selectivity. The invention starts from the fluid mechanics angle of the reaction process creatively, abandons the characteristic of the prior mixed flow state reaction, changes the reaction into the ordered laminar flow, and is more beneficial to the reaction and the improvement of the selectivity. And the defects that the 1.2-propylene glycol and the propylene oxide have poor intersolubility, are easy to separate after being mixed by adopting stirring and other modes, and are difficult to achieve sufficient mixing are overcome. The invention particularly adopts the microchannel mixer as a mixing place, the characteristic dimension of the channel in the microchannel mixer reaches micron order, and the raw materials are mixed in molecular level by convection action and molecular diffusion before reaction, thereby improving the mass transfer effect in the reaction process, effectively reducing the reaction time and providing guarantee for the subsequent reaction. The microchannel reactor is used as a reaction site, and by utilizing the characteristics of the diameter of a low channel of the microchannel reactor, the effective mass transfer effect and the sufficient mixing of materials are realized, so that the reaction of 1.2-propylene glycol and propylene oxide is guaranteed, the reaction time is greatly reduced, the raw materials are in a laminar flow state in the channel, the back mixing phenomenon does not exist, the opportunity that the dipropylene glycol is contacted with the raw materials of 1.2-propylene glycol and propylene oxide is effectively avoided, and the occurrence of series reaction is reduced, so that the selectivity of the dipropylene glycol is effectively improved, and the defects of low selectivity, long reaction time, high energy consumption and the like of a series reaction product in the industrial synthesis process of the dipropylene glycol are overcome.
The preparation method provided by the invention can effectively reduce the reaction time, greatly improve the yield of the dipropylene glycol product, and is simple in process, mild in condition, easy to control and more suitable for industrial mass production.
Experimental results show that the preparation method provided by the invention can improve the selectivity of dipropylene glycol from 50-80% to 90-98%, and reduce the reaction time from 1-3 h to 1-10 min, thereby effectively improving the yield of target products, the aging cost and the energy consumption.
For further illustration of the present invention, the following will describe the preparation method and system of dipropylene glycol according to the present invention in detail with reference to the following examples, but it should be understood that these examples are implemented on the premise of the technical scheme of the present invention, and the detailed embodiments and specific procedures are given, only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
Firstly, respectively injecting epoxy propane, 1, 2-propylene glycol and a benzenesulfonic acid catalyst into a microchannel mixer through a metering pump, mixing a plurality of strands of raw materials through the microchannel mixer, then feeding the mixed raw materials into a raw material buffer tank, preheating the materials in the raw material buffer tank to 80 ℃ through a preheater, then feeding the preheated materials into a microchannel reactor for full reaction, controlling the temperature in the microchannel reactor to be 110 ℃, the pressure to be 0.3MPa and the material residence time to be 10min, wherein the feeding amounts of the raw materials are respectively: the feeding amount of the propylene oxide is 58Kg/h, the feeding amount of the 1, 2-propylene glycol is 152Kg/h, and the benzene sulfonic acid is 0.5 Kg/h.
The crude product after the reaction of the example 1 of the invention is detected and analyzed.
Referring to FIG. 2, FIG. 2 is a gas chromatography of the crude product after the reaction of example 1 of the present invention.
Referring to table 1, table 1 shows the specific composition of the crude product after the reaction of example 1 of the present invention.
As shown in fig. 2, the specific composition of the crude product is shown in table 1, wherein the content of dipropylene glycol is 63.536%, and the selectivity of dipropylene glycol in the product is more than 97%.
TABLE 1
| Name (R) | PO | PG | DPG | TPG | Other impurities |
| Content/% | 0.001 | 34.638 | 63.536 | 1.756 | 0.069 |
And then rectifying and separating the crude product, namely firstly removing light by a first rectifying tower, rectifying the light by the first rectifying tower under negative pressure, controlling the temperature of the tower top to be 120-140 ℃, the temperature of a tower kettle to be 150-170 ℃, and returning the unreacted 1.2-propylene glycol, the unreacted propylene oxide and the catalyst on the tower top to a raw material tank for later use after condensation, and feeding the materials in the tower kettle to a second rectifying tower. The second rectifying tower is also used for negative pressure rectification, the vacuum degree is controlled to be less than or equal to 5KPa, the tower top temperature is controlled to be 130-160 ℃, the tower kettle temperature is controlled to be 170-190 ℃, and a dipropylene glycol product is extracted from a measuring line of the rectifying tower.
The product prepared in example 1 of the present invention was subjected to assay analysis.
Referring to fig. 3, fig. 3 is a gas chromatography spectrum of the dipropylene glycol product prepared according to example 1 of the present invention.
As can be seen from FIG. 3, the purity of the dipropylene glycol product prepared by the invention is more than or equal to 99.95%, and the chroma of the product is less than or equal to 5.
Example 2
Firstly, respectively injecting propylene oxide, 1, 2-propylene glycol and a sodium bicarbonate catalyst into a microchannel mixer through a metering pump, mixing a plurality of strands of raw materials through the microchannel mixer, then feeding the mixed raw materials into a raw material buffer tank, preheating the materials in the raw material buffer tank to 50 ℃ through a preheater, then feeding the preheated materials into a microchannel reactor for full reaction, controlling the temperature in the microchannel reactor to be 120 ℃, the pressure to be 0.2MPa and the retention time of the materials to be 2min, wherein the feeding amounts of the raw materials are respectively: the feeding amount of propylene oxide is 58Kg/h, the feeding amount of 1, 2-propylene glycol is 304Kg/h, and the feeding amount of sodium methoxide is 0.5 Kg/h.
The crude product after the reaction of the example 2 of the invention is detected and analyzed, the content of the dipropylene glycol in the crude product is 37%, and the selectivity of the dipropylene glycol in the product is 98%.
And then rectifying and separating the crude product, namely firstly removing light by a first rectifying tower, rectifying the crude product by the first rectifying tower under negative pressure, controlling the temperature of the tower top to be 120-140 ℃, the temperature of a tower kettle to be 150-170 ℃, returning the unreacted 1.2-propylene glycol and the unreacted propylene oxide on the tower top to a raw material tank for later use after condensation, and feeding the materials in the tower kettle to a second rectifying tower. The second rectifying tower is also used for negative pressure rectification, the vacuum degree is controlled to be less than or equal to 5KPa, the tower top temperature is controlled to be 130-160 ℃, the tower kettle temperature is controlled to be 170-190 ℃, and a dipropylene glycol product is extracted from a measuring line of the rectifying tower.
The product prepared in the embodiment 2 of the invention is detected and analyzed, the product purity is more than or equal to 99.95, and the product chroma is less than or equal to 5.
Example 3
Firstly, respectively injecting propylene oxide and 1, 2-propylene glycol into a microchannel mixer through a metering pump, mixing a plurality of strands of raw materials through the microchannel mixer, then feeding the mixed raw materials into a raw material buffer tank, preheating the materials in the raw material buffer tank to 50 ℃ through a preheater, then feeding the preheated materials into a microchannel reactor for full reaction, controlling the temperature in the microchannel reactor to be 150 ℃, the pressure to be 1MPa, and the material residence time to be 10min, wherein the feeding amounts of the raw materials are respectively as follows: the feeding amount of the propylene oxide is 58Kg/h, and the feeding amount of the 1, 2-propylene glycol is 152 Kg/h.
The crude product after the reaction of the embodiment 3 of the invention is detected and analyzed, the content of the dipropylene glycol in the crude product is 60%, and the selectivity of the dipropylene glycol in the product is 97%.
And then rectifying and separating the crude product, namely firstly removing light by a first rectifying tower, rectifying the crude product by the first rectifying tower under negative pressure, controlling the temperature of the tower top to be 120-140 ℃, the temperature of a tower kettle to be 150-170 ℃, returning the unreacted 1.2-propylene glycol and the unreacted propylene oxide on the tower top to a raw material tank for later use after condensation, and feeding the materials in the tower kettle to a second rectifying tower. The second rectifying tower is also used for negative pressure rectification, the vacuum degree is controlled to be less than or equal to 5KPa, the tower top temperature is controlled to be 130-160 ℃, the tower kettle temperature is controlled to be 170-190 ℃, and a dipropylene glycol product is extracted from a measuring line of the rectifying tower.
The product prepared in the embodiment 3 of the invention is detected and analyzed, the product purity is more than or equal to 99.95, and the product chroma is less than or equal to 5.
The above detailed description of the method and system for highly selective preparation of dipropylene glycol according to the present invention is provided herein with reference to specific examples to illustrate the principles and embodiments of the present invention, which are intended to facilitate the understanding of the method and its core ideas, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any devices or systems and performing any combination thereof. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. The preparation method of dipropylene glycol is characterized by comprising the following steps:
1) mixing propylene oxide and propylene glycol to obtain a mixed raw material;
2) and (3) carrying out condensation reaction on the mixed raw materials obtained in the step in a microchannel reactor to obtain dipropylene glycol.
2. The method of claim 1, wherein the mixing comprises mixing in a microchannel mixer;
the molar ratio of the propylene glycol to the propylene oxide is (1-10): 1;
the temperature of the condensation reaction is 100-180 ℃;
the pressure of the condensation reaction is 0.1-1 MPa;
the time of the condensation reaction is 1-10 min.
3. The method according to claim 1, further comprising a preheating step before the condensation reaction;
the preheating temperature is 60-160 ℃;
the material of the microchannel reactor comprises one or more of stainless steel, hastelloy and silicon carbide;
the diameter of the channel of the microchannel reactor is 0.1-3 mm;
the condensation reaction also includes a separation step.
4. The production method according to claim 3, wherein the separation step includes rectification dehydrogenation and rectification purification;
the vacuum degree of the rectification dehydrogenation is less than or equal to 5 KPa;
the tower top temperature of the rectification dehydrogenation is 120-140 ℃;
the temperature of a tower kettle for rectifying dehydrogenation is 150-170 ℃;
the vacuum degree of the rectification purification is less than or equal to 5 KPa;
the tower top temperature of the rectification and purification is 130-160 ℃;
the temperature of a tower kettle for rectification and purification is 170-190 ℃;
recovering the light components after rectification dehydrogenation into the mixed raw material;
the extraction mode after rectification and purification is measuring line extraction.
5. The preparation method according to any one of claims 1 to 4, wherein the step 1) is specifically:
mixing propylene oxide, propylene glycol and a catalyst to obtain a mixed raw material;
the catalyst comprises an acidic liquid catalyst or a basic liquid catalyst.
6. The method of claim 5, wherein the acidic liquid catalyst comprises one or more of sulfuric acid, hydrochloric acid, nitric acid, benzenesulfonic acid, and acidic ionic liquids;
the alkaline liquid catalyst comprises one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate and sodium methoxide;
the mass ratio of the catalyst to the propylene oxide is (0.001-0.1): 1.
7. a system for producing dipropylene glycol, comprising:
a microchannel mixer;
a microchannel reactor connected to the microchannel mixer outlet;
a dehydrogenation unit connected with the outlet of the microchannel reactor;
and the purifying device is connected with the outlet of the dehydrogenation device.
8. The system of claim 7, wherein the microchannel mixer has a channel diameter of 0.05 to 4 mm;
the system further comprises a preheater;
the outlet of the micro-channel mixer is connected with the inlet of the preheater, and the outlet of the preheater is connected with the inlet of the micro-channel mixer.
9. The system according to claim 8, characterized in that the system further comprises a buffer means and/or a buffer means;
the outlet of the micro-channel mixer is connected with the inlet of the buffer device, and the outlet of the buffer device is connected with the inlet of the preheater;
the outlet of the micro-channel mixer is connected with the inlet of the cache device, and the outlet of the cache device is connected with the inlet of the dehydrogenation device.
10. The system of claim 9, wherein the dehydrogenation device comprises one or more of a plate rectifier, a packed rectifier, and a rectifier kettle;
the purification device comprises one or more of a plate-type rectifying tower, a filler rectifying tower and a rectifying still;
the outlet of the tower top of the dehydrogenation device is connected with the inlet of the buffer device;
and the outlet of the tower kettle of the dehydrogenation device is connected with the inlet of the purification device.
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