CN114249633B - Method for separating and purifying 1, 3-propylene glycol - Google Patents
Method for separating and purifying 1, 3-propylene glycol Download PDFInfo
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- CN114249633B CN114249633B CN202210005636.XA CN202210005636A CN114249633B CN 114249633 B CN114249633 B CN 114249633B CN 202210005636 A CN202210005636 A CN 202210005636A CN 114249633 B CN114249633 B CN 114249633B
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- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 238000000034 method Methods 0.000 title claims abstract description 76
- 239000012528 membrane Substances 0.000 claims abstract description 171
- 238000000926 separation method Methods 0.000 claims abstract description 116
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 73
- 229940035437 1,3-propanediol Drugs 0.000 claims abstract description 73
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 73
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 75
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 34
- 238000001704 evaporation Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 18
- 230000036571 hydration Effects 0.000 claims description 16
- 238000006703 hydration reaction Methods 0.000 claims description 16
- 238000005984 hydrogenation reaction Methods 0.000 claims description 16
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 claims description 14
- LYTNHFVPHUPKGE-UHFFFAOYSA-N 2-(1,3-dioxan-2-yl)ethanol Chemical compound OCCC1OCCCO1 LYTNHFVPHUPKGE-UHFFFAOYSA-N 0.000 claims description 12
- VFTQJKSRDCKVQA-UHFFFAOYSA-N oxan-3-ylmethanol Chemical compound OCC1CCCOC1 VFTQJKSRDCKVQA-UHFFFAOYSA-N 0.000 claims description 12
- 238000010790 dilution Methods 0.000 claims description 9
- 239000012895 dilution Substances 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 238000001471 micro-filtration Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 58
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 239000006227 byproduct Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000002835 absorbance Methods 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000007865 diluting Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- LXRZVMYMQHNYJB-UNXOBOICSA-N [(1R,2S,4R)-4-[[5-[4-[(1R)-7-chloro-1,2,3,4-tetrahydroisoquinolin-1-yl]-5-methylthiophene-2-carbonyl]pyrimidin-4-yl]amino]-2-hydroxycyclopentyl]methyl sulfamate Chemical compound CC1=C(C=C(S1)C(=O)C1=C(N[C@H]2C[C@H](O)[C@@H](COS(N)(=O)=O)C2)N=CN=C1)[C@@H]1NCCC2=C1C=C(Cl)C=C2 LXRZVMYMQHNYJB-UNXOBOICSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- WQWLQWVLHSPEAR-UHFFFAOYSA-N propane-1,3-diol;terephthalic acid Chemical compound OCCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 WQWLQWVLHSPEAR-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
Abstract
The invention provides a method for separating and purifying 1, 3-propanediol, which comprises the following steps: sequentially performing precise filtration and reverse osmosis membrane separation on the 1, 3-propanediol reaction solution to obtain membrane dilute solution; concentrating the membrane light solution, and performing light removal treatment on the obtained concentrated solution to obtain a light removal kettle material; rectifying the light component removing kettle material to obtain the 1, 3-propylene glycol product. According to the composition of the 1, 3-propanediol reaction liquid, the method of the invention uses the separation characteristic of reverse osmosis to intercept the byproduct with relatively high molecular weight in the reaction liquid, reduces the separation difficulty of the 1, 3-propanediol product, and further purifies the product through concentration, light removal and rectification operation to obtain the high-purity 1, 3-propanediol product, wherein the purity can reach more than 99.98wt%, the total aldehyde content is below 10ppm, the product yield is high, and the waste liquid emission is less; the method is simple to operate, mild in process condition, stable and reliable in treatment effect and easy to implement industrially.
Description
Technical Field
The invention belongs to the technical field of chemical separation, and relates to a method for separating and purifying 1, 3-propanediol.
Background
1, 3-propanediol is used as an important organic chemical raw material, can be applied to the industries of printing ink, paint, cosmetics, pharmacy, antifreezing agent and the like, and is especially used as a main raw material for producing 1, 3-propanediol terephthalate (PTT); when being used as fiber materials, PTT has the characteristics of polyester fibers, has good rebound resilience and pollution resistance of nylon, has wide application in the fields of carpets, engineering plastics, clothing fabrics and the like, and is a hot spot for the development of the synthetic fibers at present.
Since the quality of the 1, 3-propanediol product has a large influence on the characteristics of the PTT fiber, for example, the purity of the product affects its intrinsic viscosity, and the aldehyde content and chromaticity of the product affects the appearance of PTT; therefore, the research on synthesizing the high-purity 1, 3-propanediol is one of the current hot spots, and mainly comprises two major types of chemical methods and biological methods, wherein the acrolein hydration hydrogenation process in the chemical methods has the characteristics of lower technical difficulty, mild process conditions, high atom utilization rate and the like, and is one of the current industrialized routes, but in the method, acrolein and an intermediate product 3-hydroxy propanal are unstable and are extremely easy to generate polycondensation reaction, so that aldehyde byproducts are generated, more byproducts are generated after hydrogenation, the components of a reaction system are complex, the difficulty of separating and purifying the 1, 3-propanediol is increased, and the quality and the yield of the product are influenced.
CN 110790636a discloses a refining method for removing trace aldehyde groups in 1, 3-propylene glycol, which comprises the steps of adding sulfonic acid ionic liquid into 1, 3-propylene glycol dehydration concentrate containing trace aldehyde group impurities, carrying out aldehyde removal reaction by catalyzing aldehyde groups through the ionic liquid, and obtaining a product with low aldehyde content and high purity of 1, 3-propylene glycol through vacuum rectification; although the method can obviously reduce the content of aldehyde impurities, the cost of the ionic liquid is higher, the yield of the product is lower, and the method is not suitable for mass preparation.
CN 112979420a discloses a process for purifying 1, 3-propanediol, which comprises the steps of: the preparation method comprises the steps of adjusting and reacting a raw material containing 1, 3-propylene glycol through pH, wherein the raw material contains aldehyde organic matters to obtain a reaction product; the reaction product is subjected to first rectification and second reduced pressure rectification to obtain crude 1, 3-propanediol; and (3) adsorbing the crude 1, 3-propanediol by resin and performing third rectification to obtain the 1, 3-propanediol. The method utilizes the characteristic of aldehyde substances, adds reactants to convert the aldehyde substances into macromolecular substances, but side reactions can also occur, and the yield of the product is lower although the aldehyde content can be reduced, and resin adsorption operation is also needed, so that the operation is complex and the cost is higher.
In summary, for the separation and purification of the 1, 3-propanediol reaction solution, a proper process and operation are required to be selected, so that the yield of the 1, 3-propanediol product is improved while the aldehyde substances are sufficiently removed, the operation is simplified, and the cost is reduced.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a method for separating and purifying 1, 3-propanediol, which is characterized in that according to the composition of 1, 3-propanediol reaction liquid, the separation characteristic of reverse osmosis is utilized to intercept byproducts with relatively large molecular weight in the reaction liquid, the separation difficulty of a 1, 3-propanediol product is reduced, and the 1, 3-propanediol product with high purity is obtained by further purification through light removal and rectification operation, and the product yield is high; the method is simple to operate, mild in condition, low in cost and easy to implement industrially.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for separating and purifying 1, 3-propylene glycol, which comprises the following steps:
(1) Sequentially performing precise filtration and reverse osmosis membrane separation on the 1, 3-propanediol reaction solution to obtain membrane dilute solution;
(2) Concentrating the membrane dilute solution obtained in the step (1), and performing light removal treatment on the obtained concentrated solution to obtain a light removal kettle material;
(3) Rectifying the light component removing kettle material obtained in the step (2) to obtain a 1, 3-propylene glycol product.
In the invention, for separation and purification after synthesis of 1, 3-propanediol, various byproducts inevitably exist in the product according to the selection of reaction raw materials and specific reaction processes, and according to the difference of particle sizes and molecular weights of various products, a precise filtration and reverse osmosis membrane separation mode is adopted in sequence, wherein the solid particles are mainly separated, and the organic matters with relatively large molecular weight are intercepted by utilizing the separation characteristic of reverse osmosis; the method is simple to operate, mild in process condition, stable and reliable in treatment effect and easy to realize industrial production.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferable technical scheme of the invention, the 1, 3-propanediol reaction liquid in the step (1) is obtained by an acrolein hydration hydrogenation process.
Preferably, the composition of the 1, 3-propanediol reaction liquid in the step (1) comprises 1, 3-propanediol, 3-hydroxypropanal, 3-hydroxymethyl tetrahydropyran, 1, 3-dioxane-2-ethanol, 4-hetero-oxo-heptanediol and water.
Preferably, the composition of the 1, 3-propanediol reaction solution in step (1) comprises, in terms of mass concentration, 1, 3-propanediol.ltoreq.20.0 wt%, such as 20.0wt%, 18.0wt%, 15.0wt%, 12.0wt%, 10.0wt%, 8.0wt%, or 5.0wt%, etc., 3-hydroxypropanal.ltoreq.0.1 wt%, such as 0.1wt%, 0.05wt%, 0.01wt%, or 0.005wt%, etc., 3-hydroxymethyl tetrahydropyran.ltoreq.0.1 wt%, such as 0.1wt%, 0.05wt%, 0.01wt%, or 0.005wt%, etc., 1, 3-dioxane-2-ethanol.ltoreq.0.1 wt%, such as 0.1wt%, 0.05wt%, 0.01wt%, or 0.005wt%, etc., 4-hetero oxyheptanediol.1 wt%, such as 0.0.0.0.05 wt%, 0.01wt%, or 0.005wt%, etc., 0.1wt%, such as 0.0.05 wt%, 0.01wt%, or 0.0.5 wt%, or 0.5wt%, etc., 0.80 wt%, 0.1wt%, or 0.0.0.0 wt%, or 0.5wt%, etc., 0.0.0 wt%, or less than 0.0wt%, based on the mass%; however, the present invention is not limited to the above-mentioned values, and other values not mentioned in the respective numerical ranges are equally applicable.
Preferably, the metal content of the 1, 3-propanediol reaction solution in step (1) is less than or equal to 200ppm, such as 200ppm, 180ppm, 150ppm, 120ppm, 100ppm, 50ppm, etc., turbidity is less than or equal to 50NTU, such as 50NTU, 45NTU, 40NTU, 35NTU, 30NTU, etc., but is not limited to the recited values, and other non-recited values within the respective numerical ranges are equally applicable.
In the invention, 3-hydroxy-propanal is prepared by hydration of acrolein, 1, 3-propanediol is obtained by catalytic hydrogenation of 3-hydroxy-propanal, and meanwhile, a broken catalyst exists in a reaction liquid.
Since the 1, 3-propanediol reaction solution contains various aldehyde byproducts, the aldehyde byproducts can obviously influence the product performance, and thus the total aldehyde content of the product is usually determined so as to represent the purity of the product, and the total aldehyde content is measured by taking formaldehyde as a reference.
As a preferred embodiment of the present invention, the fine filtration in the step (1) is performed in a fine filter.
Preferably, the pore size of the precision filter is not greater than 450nm, such as 450nm, 300nm, 200nm, 100nm, 50nm or 30nm, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
As a preferable technical scheme of the invention, the reverse osmosis membrane separation in the step (1) is performed by adopting a disc type reverse osmosis membrane element.
In the invention, a disc type reverse osmosis membrane element is adopted in reverse osmosis membrane separation, and compared with a roll type reverse osmosis membrane element, the membrane has better tolerance to organic matters in reaction liquid so as to ensure the stability of a separation membrane in the reverse osmosis process.
Preferably, the molecular weight cut-off of the reverse osmosis membrane separation is not less than 100Da.
According to the preferred technical scheme, the reverse osmosis membrane separation in the step (1) comprises primary membrane separation and secondary membrane separation, primary membrane thin solution and primary membrane thick solution are obtained through the primary membrane separation, the secondary membrane separation is carried out after the primary membrane thick solution is diluted, secondary membrane thin solution is obtained, and the two membrane thin solutions are combined and treated together.
Preferably, the operation pressure of the primary membrane separation is 6.0 to 9.0MPa, for example, 6.0MPa, 6.5MPa, 7.0MPa, 7.5MPa, 8.0MPa, 8.5MPa, 9.0MPa, or the like, but is not limited to the recited values, and other non-recited values within the range are equally applicable; the operating temperature is 5 to 45 ℃, for example 5 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 45 ℃ or the like, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the dilution factor of the primary film dope is 1.0 to 3.0 times, for example, 1.0 times, 1.5 times, 1.7 times, 1.9 times, 2.0 times, 2.5 times, or 3.0 times, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the operating pressure of the secondary membrane separation is 6.0 to 9.0MPa, for example, 6.0MPa, 6.5MPa, 7.0MPa, 7.5MPa, 8.0MPa, 8.5MPa, 9.0MPa, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable; the operating temperature is 5 to 45 ℃, for example 5 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 45 ℃ or the like, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
As a preferred embodiment of the present invention, the concentrating in step (2) includes evaporating and concentrating.
Preferably, the above-mentioned evaporation concentration has a pot temperature of 133 to 190 ℃, for example 133 ℃, 140 ℃, 155 ℃, 163 ℃, 170 ℃, 180 ℃, 190 ℃ or the like, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are applicable as well.
Preferably, the absolute pressure of the evaporation concentration is 5 to 50kPa, for example, 5kPa, 10kPa, 15kPa, 25kPa, 35kPa, 45kPa, 50kPa, or the like, but is not limited to the values listed, and other values not listed in the range of the values are equally applicable.
Preferably, the water content of the concentrate of step (2) is not more than 0.05wt%, e.g. 0.05wt%, 0.04wt%, 0.03wt%, 0.02wt% or 0.01wt%, etc., but is not limited to the values recited, other non-recited values within the range of values being equally applicable.
As a preferable technical scheme of the invention, the light component removing treatment in the step (2) is performed by adopting a light component removing tower.
Preferably, the theoretical plate number of the light ends column is not more than 40, such as 40, 35, 30, 25 or 20, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the absolute pressure of the light component removal treatment in the step (2) is 0.1 to 5.0kPa, for example, 0.1kPa, 0.5kPa, 1.0kPa, 2.0kPa, 3.0kPa, 4.0kPa, or 5.0kPa, etc., but the present invention is not limited to the enumerated values, and other non-enumerated values within the numerical range are equally applicable.
Preferably, the top temperature of the light component removal treatment in the step (2) is 65 to 133 ℃, for example 65 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 133 ℃ or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are equally applicable.
Preferably, the reflux ratio of the light component removal treatment in step (2) is not more than 10, for example 10, 9, 8, 7, 6 or 5, but is not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferable technical scheme of the invention, the rectification in the step (3) is performed by adopting a rectifying tower.
Preferably, the theoretical plate number of the rectifying column is not more than 30, for example, 30, 25, 20, 15 or 10, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the absolute pressure of the rectification in step (3) is 0.1 to 5.0kPa, for example, 0.1kPa, 0.5kPa, 1.0kPa, 2.0kPa, 3.0kPa, 4.0kPa, or 5.0kPa, etc., but is not limited to the enumerated values, and other non-enumerated values within the numerical range are equally applicable.
Preferably, the column top temperature of the rectification in the step (3) is 67 to 135 ℃, for example 67 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 135 ℃ or the like, but not limited to the values listed, and other values not listed in the range of the values are equally applicable.
Preferably, the reflux ratio of the rectification in step (3) is not more than 5, such as 5, 4, 3, 2 or 1, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the weight ratio of the light component at the top of the column in the light treatment in the step (2) is 1.0 to 10.0wt%, for example, 1.0wt%, 2.0wt%, 3.0wt%, 4.0wt%, 5.0wt%, 6.0wt%, 7.0wt%, 8.0wt%, 9.0wt% or 10.0wt%, etc., but not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Preferably, the rectification in step (3) is carried out with the 1, 3-propanediol product being taken overhead, and the mass proportion of the 1, 3-propanediol product in the light ends removal kettle is 95.0-99.0 wt%, such as 95.0wt%, 95.5wt%, 96.0wt%, 97.0wt%, 98.0wt% or 99.0wt%, etc., but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
As a preferred technical solution of the present invention, the method comprises the steps of:
(1) Sequentially carrying out precise filtration and reverse osmosis membrane separation on 1, 3-propylene glycol reaction liquid, wherein the 1, 3-propylene glycol reaction liquid is obtained by an acrolein hydration hydrogenation process, and the composition of the 1, 3-propylene glycol reaction liquid comprises less than or equal to 20.0wt% of 1, 3-hydroxy propanal less than or equal to 0.1wt%, 3-hydroxymethyl tetrahydropyran less than or equal to 0.1wt% of 1, 3-dioxane-2-ethanol less than or equal to 0.1wt%, 4-hetero-oxo-heptanediol less than or equal to 10.0wt%, water more than or equal to 70.0wt%, wherein the metal content is less than or equal to 200ppm, and the turbidity is less than or equal to 50NTU; the precise filtration is carried out in a precise filter, and the pore diameter of the precise filter is not more than 450nm; the reverse osmosis membrane separation is carried out by adopting a disc type reverse osmosis membrane element, and the molecular weight cut-off is not less than 100Da;
the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, wherein primary membrane thin solution and primary membrane thick solution are obtained through the primary membrane separation, the operation pressure of the primary membrane separation is 6.0-9.0 MPa, the operation temperature is 5-45 ℃, the secondary membrane separation is carried out after the primary membrane thick solution is diluted, the dilution multiple is 1.0-3.0 times, the operation pressure of the secondary membrane separation is 6.0-9.0 MPa, the operation temperature is 5-45 ℃, secondary membrane thin solution is obtained, and the two membrane thin solutions are combined and treated together;
(2) Evaporating and concentrating the membrane thin solution obtained in the step (1), wherein the kettle temperature of the evaporating and concentrating is 133-190 ℃, the absolute pressure is 5-50 kPa, so as to obtain concentrated solution, the water content of the concentrated solution is not more than 0.05wt%, the concentrated solution is subjected to light removal treatment, the light removal treatment is performed by adopting a light removal tower, the theoretical plate number of the light removal tower is not more than 40, the absolute pressure of the light removal treatment is 0.1-5.0 kPa, the tower top temperature is 65-133 ℃, the reflux ratio is not more than 10, and the light removal kettle material is obtained, wherein the mass ratio of light components extracted from the tower top is 1.0-10.0 wt%;
(3) Rectifying the light component removing kettle material obtained in the step (2), wherein the rectification is carried out by adopting a rectifying tower, the theoretical plate number of the rectifying tower is not more than 30, the absolute pressure of the rectification is 0.1-5.0 kPa, the temperature is 67-135 ℃, the reflux ratio is not more than 5, and the 1, 3-propylene glycol product is extracted from the top of the rectifying tower and accounts for 95.0-99.0wt% of the light component removing kettle material.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the composition of the 1, 3-propanediol reaction liquid, the method of the invention uses the separation characteristic of reverse osmosis to intercept the byproduct with relatively high molecular weight in the reaction liquid, reduces the separation difficulty of the 1, 3-propanediol product, and further purifies the product through concentration, light removal and rectification operation to obtain the high-purity 1, 3-propanediol product, wherein the purity can reach more than 99.98wt%, the total aldehyde content is below 10ppm, the product yield is high, and the waste liquid emission is less;
(2) The method disclosed by the invention is simple to operate, mild in process condition, stable and reliable in treatment effect and easy to implement industrially.
Drawings
FIG. 1 is a process flow chart of a method for separating and purifying a 1, 3-propanediol reaction solution according to example 1 of the present invention.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
The invention provides a method for separating and purifying 1, 3-propanediol in the detailed description, which comprises the following steps:
(1) Sequentially performing precise filtration and reverse osmosis membrane separation on the 1, 3-propanediol reaction solution to obtain membrane dilute solution;
(2) Concentrating the membrane dilute solution obtained in the step (1), and performing light removal treatment on the obtained concentrated solution to obtain a light removal kettle material;
(3) Rectifying the light component removing kettle material obtained in the step (2) to obtain a 1, 3-propylene glycol product.
The following are exemplary but non-limiting examples of the invention:
example 1:
the embodiment provides a method for separating and purifying 1, 3-propanediol, wherein the process flow chart of the method is shown in fig. 1, and the method comprises the following steps:
(1) Sequentially carrying out precise filtration and reverse osmosis membrane separation on a 1, 3-propylene glycol reaction solution, wherein the 1, 3-propylene glycol reaction solution is obtained by an acrolein hydration hydrogenation process, and the composition of the 1, 3-propylene glycol reaction solution comprises, by mass, 10.9wt% of 1, 3-propylene glycol, 50ppm of 3-hydroxy-propionaldehyde, 80ppm of 3-hydroxymethyl-tetrahydropyran, 70ppm of 1, 3-dioxane-2-ethanol, 20ppm of 4-hetero-oxo-heptanediol, 0.8wt% of 4-hetero-oxo-heptanediol and 88.3wt% of water, wherein the nickel metal content is 75ppm, the turbidity is 10NTU, and the total aldehyde content is 28ppm; the precise filtration is carried out in a precise filter, and the pore diameter of the precise filter is 450nm; the reverse osmosis membrane separation is carried out by adopting a disc type reverse osmosis membrane element, and the molecular weight cut-off is 100Da;
the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, wherein primary membrane separation is carried out to obtain primary membrane light liquor and primary membrane concentrated liquor, the operation pressure of the primary membrane separation is 9.0MPa, the operation temperature is 30 ℃, the primary membrane concentrated liquor is diluted and then subjected to secondary membrane separation, the dilution multiple is 1.0, the operation pressure of the secondary membrane separation is 9.0MPa, the operation temperature is 30 ℃, the secondary membrane light liquor is obtained, and the two membrane light liquors are combined and treated together;
(2) Evaporating and concentrating the membrane thin solution obtained in the step (1), wherein the kettle temperature of the evaporating and concentrating is 133 ℃, the absolute pressure is 5kPa, a concentrated solution is obtained, the water content of the concentrated solution is 0.05wt%, the volatile matters of the evaporating and concentrating are reused in the diluting and acrolein hydration hydrogenation process in the step (1), the concentrated solution is subjected to light removal treatment, the light removal treatment is carried out by a light removal tower, the theoretical plate number of the light removal tower is 40, the absolute pressure of the light removal treatment is 1.0kPa, the temperature is 102 ℃, the reflux ratio is 3, and the light removal kettle material is obtained, wherein the mass ratio of light components extracted from the top of the tower is 3.7wt%;
(3) Rectifying the light component removing kettle material obtained in the step (2), wherein the rectification is carried out by adopting a rectifying tower, the theoretical plate number of the rectifying tower is 30, the absolute pressure of the rectification is 1.0kPa, the temperature is 103 ℃, the reflux ratio is 3, and the 1, 3-propylene glycol product is extracted from the top of the rectifying tower and accounts for 97.6wt% of the light component removing kettle material.
Measuring the mass concentration of 3-hydroxy-propionaldehyde, 1, 3-propylene glycol, 3-hydroxymethyl tetrahydropyran, 1, 3-dioxane-2-ethanol, 4-hetero-oxo-heptanediol and 4-hetero-oxo-heptanediol in each strand of material by adopting a gas chromatography method; detecting the COD value by adopting an oxidation-reduction potentiometric titration method; detecting nickel content by adopting an inductive coupling plasma spectrum generator; ultraviolet absorbance and total aldehyde content were determined by ultraviolet spectrophotometry, and chromaticity was determined by platinum-cobalt colorimetry.
In this example, the membrane separation yield of the treated 1, 3-propanediol from step (1) was 97.0%, the concentration from step (2) was carried out, the evaporated fraction was free of 1, 3-propanediol, the COD value was 58ppm, the mass concentration of 1, 3-propanediol in the concentrate was 98.5% by weight, the weight concentration of 1, 3-propanediol in the light ends was 98.5% by weight after the light ends were removed, 3-hydroxymethyltetrahydropyran and 1, 3-dioxane-2-ethanol were not detected, the mass concentration of the 1, 3-propanediol product at the top of the column was 99.98% by weight, the total aldehyde content was only 4.3ppm, the ultraviolet absorbance of the product at 270nm was 0.01, the chromaticity in the platinum-cobalt color number was 3, the index requirements for the polymer grade 1, 3-propanediol for fibers could be satisfied, and the separation yield of the single pass product was 92.7%.
Example 2:
the embodiment provides a method for separating and purifying 1, 3-propanediol, which comprises the following steps:
(1) Sequentially carrying out precise filtration and reverse osmosis membrane separation on a 1, 3-propylene glycol reaction solution, wherein the 1, 3-propylene glycol reaction solution is obtained by an acrolein hydration hydrogenation process, and the composition of the 1, 3-propylene glycol reaction solution comprises, by mass, 10.9wt% of 1, 3-propylene glycol, 50ppm of 3-hydroxy-propionaldehyde, 80ppm of 3-hydroxymethyl-tetrahydropyran, 70ppm of 1, 3-dioxane-2-ethanol, 20ppm of 4-hetero-oxo-heptanediol, 0.8wt% of 4-hetero-oxo-heptanediol and 88.3wt% of water, wherein the nickel metal content is 75ppm, the turbidity is 10NTU, and the total aldehyde content is 28ppm; the precise filtration is carried out in a precise filter, and the pore diameter of the precise filter is 100nm; the reverse osmosis membrane separation is carried out by adopting a disc type reverse osmosis membrane element, and the molecular weight cut-off is 100Da;
the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, wherein primary membrane separation is carried out to obtain primary membrane light liquor and primary membrane concentrated liquor, the operation pressure of the primary membrane separation is 7.5MPa, the operation temperature is 20 ℃, the primary membrane concentrated liquor is diluted and then subjected to secondary membrane separation, the dilution multiple is 1.0, the operation pressure of the secondary membrane separation is 7.5MPa, the operation temperature is 20 ℃, the secondary membrane light liquor is obtained, and the two membrane light liquors are combined and treated together;
(2) Evaporating and concentrating the membrane thin solution obtained in the step (1), wherein the evaporating and concentrating kettle temperature is 190 ℃, the absolute pressure is 50kPa, a concentrated solution is obtained, the water content of the concentrated solution is 0.04wt%, the evaporated and concentrated volatile matter is reused in the diluting and acrolein hydration hydrogenation process in the step (1), the concentrated solution is subjected to light removal treatment, the light removal treatment is carried out by a light removal tower, the theoretical plate number of the light removal tower is 30, the absolute pressure of the light removal treatment is 3.0kPa, the temperature is 121 ℃, the reflux ratio is 5, and the light removal kettle material is obtained, wherein the mass ratio of light components extracted from the top of the tower is 6.5wt%;
(3) Rectifying the light component removing kettle material obtained in the step (2), wherein the rectification is carried out by adopting a rectifying tower, the theoretical plate number of the rectifying tower is 20, the absolute pressure of the rectification is 3.0kPa, the temperature is 123 ℃, the reflux ratio is 5, and the 1, 3-propylene glycol product is extracted from the top of the rectifying tower and accounts for 95.2wt% of the light component removing kettle material.
The method was carried out in the same manner as in example 1, except that the relevant parameters of the individual strands of material were measured.
In this example, the mass concentration of the 1, 3-propanediol product is 99.99wt%, the total aldehyde content is only 5.3ppm, the ultraviolet absorbance of the product at 270nm is 0.01, the chromaticity in the platinum-cobalt color number is 3, the index requirement of the polymerization grade 1, 3-propanediol for fibers can be satisfied, and the separation yield of the single-pass product is 86.4%.
Example 3:
the embodiment provides a method for separating and purifying 1, 3-propanediol, which comprises the following steps:
(1) Sequentially carrying out precise filtration and reverse osmosis membrane separation on a 1, 3-propylene glycol reaction solution, wherein the 1, 3-propylene glycol reaction solution is obtained by an acrolein hydration hydrogenation process, and the composition of the 1, 3-propylene glycol reaction solution comprises, by mass, 10.9wt% of 1, 3-propylene glycol, 50ppm of 3-hydroxy-propionaldehyde, 80ppm of 3-hydroxymethyl-tetrahydropyran, 70ppm of 1, 3-dioxane-2-ethanol, 20ppm of 4-hetero-oxo-heptanediol, 0.8wt% of 4-hetero-oxo-heptanediol and 88.3wt% of water, wherein the nickel metal content is 75ppm, the turbidity is 10NTU, and the total aldehyde content is 28ppm; the precise filtration is carried out in a precise filter, and the pore diameter of the precise filter is 60nm; the reverse osmosis membrane separation is carried out by adopting a disc type reverse osmosis membrane element, and the molecular weight cut-off is 100Da;
the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, wherein primary membrane separation is carried out to obtain primary membrane light liquor and primary membrane concentrated liquor, the operation pressure of the primary membrane separation is 6.0MPa, the operation temperature is 45 ℃, the primary membrane concentrated liquor is diluted and then subjected to secondary membrane separation, the dilution multiple is 1.0, the operation pressure of the secondary membrane separation is 6.0MPa, the operation temperature is 45 ℃, the secondary membrane light liquor is obtained, and the two membrane light liquors are combined and treated together;
(2) Evaporating and concentrating the membrane thin solution obtained in the step (1), wherein the evaporating and concentrating kettle temperature is 159 ℃, the absolute pressure is 15kPa, a concentrated solution is obtained, the water content of the concentrated solution is 0.05wt%, the evaporated and concentrated volatile matter is reused in the diluting and acrolein hydration hydrogenation process in the step (1), the concentrated solution is subjected to light removal treatment, the light removal treatment is carried out by a light removal tower, the theoretical plate number of the light removal tower is 35, the absolute pressure of the light removal treatment is 5.0kPa, the temperature is 133 ℃, the reflux ratio is 10, and the light removal kettle material is obtained, wherein the mass ratio of light components extracted from the tower top is 3.6wt%;
(3) Rectifying the light component removing kettle material obtained in the step (2), wherein the rectification is carried out by adopting a rectifying tower, the theoretical plate number of the rectifying tower is 25, the absolute pressure of the rectification is 5.0kPa, the temperature is 135 ℃, the reflux ratio is 4, and the 1, 3-propylene glycol product is extracted from the top of the rectifying tower and accounts for 96.7wt% of the light component removing kettle material.
The method was carried out in the same manner as in example 1, except that the relevant parameters of the individual strands of material were measured.
In this example, the mass concentration of the 1, 3-propanediol product is 99.99wt%, the total aldehyde content is only 3.3ppm, the ultraviolet absorbance of the product at 270nm is 0.01, the chromaticity in the platinum-cobalt color number is 1, the index requirement of the polymerization grade 1, 3-propanediol for fibers can be satisfied, and the separation yield of the single-pass product is 90.4%.
Example 4:
the embodiment provides a method for separating and purifying 1, 3-propanediol, which comprises the following steps:
(1) Sequentially carrying out precise filtration and reverse osmosis membrane separation on a 1, 3-propylene glycol reaction solution, wherein the 1, 3-propylene glycol reaction solution is obtained by an acrolein hydration hydrogenation process, and the composition of the 1, 3-propylene glycol reaction solution comprises, by mass, 15.0% of 1, 3-propylene glycol, 100ppm of 3-hydroxypropionaldehyde, 60ppm of 3-hydroxymethyl tetrahydropyran, 80ppm of 1, 3-dioxane-2-ethanol, 50ppm of 4-hetero-oxo-heptanediol, 1.0% of 4-hetero-oxo-heptanediol and 84.0% of water, wherein the nickel metal content is 100ppm, the turbidity is 30NTU, and the total aldehyde content is 47ppm; the precise filtration is carried out in a precise filter, and the pore diameter of the precise filter is 150nm; the reverse osmosis membrane separation is carried out by adopting a disc type reverse osmosis membrane element, and the molecular weight cut-off is 100Da;
the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, wherein primary membrane separation is carried out to obtain primary membrane light liquor and primary membrane concentrated liquor, the operation pressure of the primary membrane separation is 9.0MPa, the operation temperature is 40 ℃, the primary membrane concentrated liquor is diluted and then subjected to secondary membrane separation, the dilution multiple is 2.0 times, the operation pressure of the secondary membrane separation is 9.0MPa, the operation temperature is 40 ℃, secondary membrane light liquor is obtained, and the two membrane light liquors are combined and treated together;
(2) Evaporating and concentrating the membrane thin solution obtained in the step (1), wherein the kettle temperature of the evaporating and concentrating is 185 ℃, the absolute pressure is 40kPa, a concentrated solution is obtained, the water content of the concentrated solution is 0.05wt%, the volatile matters of the evaporating and concentrating are reused in the diluting and acrolein hydration hydrogenation process in the step (1), the concentrated solution is subjected to light removal treatment, the light removal treatment is carried out by a light removal tower, the theoretical plate number of the light removal tower is 40, the absolute pressure of the light removal treatment is 0.5kPa, the temperature is 90 ℃, the reflux ratio is 6, and the light removal kettle material is obtained, wherein the mass ratio of light components extracted from the top of the tower is 3.1wt%;
(3) Rectifying the light component removing kettle material obtained in the step (2), wherein the rectification is carried out by adopting a rectifying tower, the theoretical plate number of the rectifying tower is 30, the absolute pressure of the rectification is 0.5kPa, the temperature is 91 ℃, the reflux ratio is 2, and the 1, 3-propylene glycol product is extracted from the top of the rectifying tower and accounts for 96.9wt% of the light component removing kettle material.
The method was carried out in the same manner as in example 1, except that the relevant parameters of the individual strands of material were measured.
In this example, the mass concentration of the 1, 3-propanediol product is 99.98wt%, the total aldehyde content is only 4.4ppm, the ultraviolet absorbance of the product at 270nm is 0.01, the chromaticity in the platinum-cobalt color number is 2, the index requirement of the polymerization grade 1, 3-propanediol for fibers can be satisfied, and the separation yield of the single-pass product is 93.0%.
Example 5:
the embodiment provides a method for separating and purifying 1, 3-propanediol, which comprises the following steps:
(1) Sequentially carrying out precise filtration and reverse osmosis membrane separation on a 1, 3-propylene glycol reaction solution, wherein the 1, 3-propylene glycol reaction solution is obtained by an acrolein hydration hydrogenation process, and the composition of the 1, 3-propylene glycol reaction solution comprises, by mass, 6.0wt% of 1, 3-propylene glycol, 80ppm of 3-hydroxypropionaldehyde, 100ppm of 3-hydroxymethyl tetrahydropyran, 120ppm of 1, 3-dioxane-2-ethanol, 70ppm of 4-hetero-oxo-heptanediol, 0.6wt% of 4-hetero-oxo-heptanediol, 93.4wt% of water, wherein the nickel metal content is 100ppm, the turbidity is 30NTU, and the total aldehyde content is 62ppm; the precise filtration is carried out in a precise filter, and the pore diameter of the precise filter is 300nm; the reverse osmosis membrane separation is carried out by adopting a disc type reverse osmosis membrane element, and the molecular weight cut-off is 100Da;
the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, wherein primary membrane separation is carried out to obtain primary membrane light liquor and primary membrane concentrated liquor, the operation pressure of the primary membrane separation is 8.0MPa, the operation temperature is 25 ℃, the primary membrane concentrated liquor is diluted and then subjected to secondary membrane separation, the dilution multiple is 3.0 times, the operation pressure of the secondary membrane separation is 8.0MPa, the operation temperature is 25 ℃, the secondary membrane light liquor is obtained, and the two membrane light liquors are combined and treated together;
(2) Evaporating and concentrating the membrane thin solution obtained in the step (1), wherein the kettle temperature of the evaporating and concentrating is 175 ℃, the absolute pressure is 25kPa, a concentrated solution is obtained, the water content of the concentrated solution is 0.045wt%, the volatile matters of the evaporating and concentrating are reused in the diluting and acrolein hydration hydrogenation process in the step (1), the concentrated solution is subjected to light removal treatment, the light removal treatment is carried out by a light removal tower, the theoretical plate number of the light removal tower is 38, the absolute pressure of the light removal treatment is 2.0kPa, the temperature is 114 ℃, the reflux ratio is 8, and the light removal kettle material is obtained, wherein the mass ratio of light components extracted from the top of the tower is 5.7wt%;
(3) Rectifying the light component removing kettle material obtained in the step (2), wherein the rectification is carried out by adopting a rectifying tower, the theoretical plate number of the rectifying tower is 27, the absolute pressure of the rectification is 2.5kPa, the temperature is 119 ℃, the reflux ratio is 5, and the 1, 3-propylene glycol product is extracted from the top of the rectifying tower and accounts for 97.7wt% of the light component removing kettle material.
The method was carried out in the same manner as in example 1, except that the relevant parameters of the individual strands of material were measured.
In this example, the mass concentration of the 1, 3-propanediol product is 99.98wt%, the total aldehyde content is only 6.8ppm, the ultraviolet absorbance of the product at 270nm is 0.01, the chromaticity in the platinum-cobalt color number is 4, the index requirement of the polymerization grade 1, 3-propanediol for fibers can be satisfied, and the separation yield of the single-pass product is 90.2%.
Example 6:
this example provides a method for separating and purifying 1, 3-propanediol, which is different from the method of example 1 only in that: the reverse osmosis membrane separation in the step (1) is performed only once.
In this embodiment, since reverse osmosis membrane separation is an important operation for removing the organic byproducts with large molecular weight, only one membrane separation is performed, the membrane concentrate reaches a certain concentration, which makes it difficult to proceed, so that the 1, 3-propanediol component to be recovered cannot fully enter the membrane light solution, resulting in a reduction of the separation yield of the once-through 1, 3-propanediol to 86.2%.
Example 7:
this example provides a method for separating and purifying 1, 3-propanediol, which is different from the method of example 1 only in that: the reverse osmosis membrane separation in the step (1) is performed by adopting a coiled reverse osmosis membrane element.
In this example, due to the use of the roll reverse osmosis membrane element, the rejection rate of impurities in the reaction liquid is lowered compared with the disc reverse osmosis membrane element to the 1, 3-propanediol reaction liquid, thereby affecting the quality and yield of the 1, 3-propanediol product, at this time, the mass concentration of 1, 3-propanediol is 99.97wt%, the total aldehyde mass concentration is 9.5ppm, the corresponding ultraviolet absorbance is 0.04, the chromaticity is 5, and the single pass product separation yield is only 88.3%.
Comparative example 1:
this comparative example provides a method for separating and purifying 1, 3-propanediol, which is different from the method of example 1 only in that: the reverse osmosis membrane separation in the step (1) is not included.
In the comparative example, as the separation and purification of the 1, 3-propanediol reaction liquid are not performed with reverse osmosis, various impurities are required to be removed in the light removal and rectification stages, but the separation difficulty is relatively large due to the fact that the difference between the impurities and the boiling point of the product is small, the aldehyde impurities are not completely removed, meanwhile, a large amount of 1, 3-propanediol is lost, the mass concentration of the obtained 1, 3-propanediol is 99.93wt%, the mass concentration of the total aldehyde reaches 83.1ppm, the corresponding ultraviolet absorbance is 0.08, the chromaticity is 9, and the single-pass product separation yield is only 69.5%.
It can be seen from the above examples and comparative examples that the method of the present invention uses the separation characteristic of reverse osmosis to intercept the byproduct with relatively large molecular weight in the reaction solution according to the composition of the reaction solution of 1, 3-propanediol, reduces the separation difficulty of the 1, 3-propanediol product, and further purifies the product by concentrating, light removal and rectification operations to obtain the high-purity 1, 3-propanediol product, wherein the purity can reach more than 99.98wt%, the total aldehyde content is below 10ppm, the product yield is high, and the waste liquid emission is low; the method is simple to operate, mild in process condition, stable and reliable in treatment effect and easy to implement industrially.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions for the method of the present invention, addition of auxiliary steps, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
Claims (20)
1. A method for separating and purifying 1, 3-propanediol, comprising the steps of:
(1) Sequentially carrying out precise filtration and reverse osmosis membrane separation on 1, 3-propylene glycol reaction liquid, wherein the 1, 3-propylene glycol reaction liquid is obtained by an acrolein hydration hydrogenation process, and the composition of the 1, 3-propylene glycol reaction liquid comprises less than or equal to 20.0wt% of 1, 3-hydroxy propanal less than or equal to 0.1wt% of 3-hydroxymethyl tetrahydropyran less than or equal to 0.1wt% of 1, 3-dioxane-2-ethanol less than or equal to 0.1wt% of 4-hetero-oxo-heptanediol and water more than or equal to 70.0wt% of water according to mass concentration; the metal content of the 1, 3-propanediol reaction liquid is less than or equal to 200ppm, and the turbidity is less than or equal to 50NTU;
the reverse osmosis membrane separation is carried out by adopting a disc type reverse osmosis membrane element, the molecular weight cut-off of the reverse osmosis membrane separation is not less than 100Da, the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, primary membrane separation is carried out to obtain primary membrane light liquor and primary membrane thick liquor, the primary membrane thick liquor is diluted and then is subjected to secondary membrane separation to obtain secondary membrane light liquor, and the secondary membrane light liquor is combined and treated together;
(2) Evaporating and concentrating the membrane light liquid obtained in the step (1), and carrying out light removal treatment on the obtained concentrated liquid, wherein the water content of the concentrated liquid is not more than 0.05wt% to obtain a light removal kettle material, and the mass ratio of light components at the top of the light removal treatment is 1.0-10.0 wt%;
(3) Rectifying the light component removing kettle material obtained in the step (2) to obtain a 1, 3-propylene glycol product.
2. The method of claim 1, wherein the microfiltration of step (1) is performed in a microfilter.
3. The method of claim 2, wherein the pore size of the precision filter is no greater than 450nm.
4. The method according to claim 1, wherein the primary membrane separation in step (1) is operated at a pressure of 6.0 to 9.0MPa and at a temperature of 5 to 45 ℃.
5. The method of claim 1, wherein the primary membrane dope has a dilution factor of 1.0 to 3.0.
6. The method according to claim 1, wherein the secondary membrane separation is operated at a pressure of 6.0 to 9.0MPa and at a temperature of 5 to 45 ℃.
7. The method according to claim 1, wherein the evaporator concentration is carried out at a kettle temperature of 133-190 ℃.
8. The method according to claim 1, wherein the absolute pressure of the evaporative concentration is 5 to 50kPa.
9. The method of claim 1, wherein the light ends treatment of step (2) is performed using a light ends column.
10. The method of claim 9, wherein the theoretical plate number of the light ends column is no greater than 40.
11. The method of claim 1, wherein the absolute pressure of the light ends treatment of step (2) is from 0.1 to 5.0kPa.
12. The process of claim 1 wherein the overhead temperature of the light ends treatment of step (2) is from 65 to 133 ℃.
13. The method of claim 1, wherein the light ends treatment of step (2) has a reflux ratio of no greater than 10.
14. The method of claim 1, wherein the rectifying of step (3) is performed using a rectifying column.
15. The method of claim 14, wherein the theoretical plate number of the rectifying column is no greater than 30.
16. The method according to claim 1, wherein the absolute pressure of the rectification in step (3) is 0.1 to 5.0kPa.
17. The process of claim 1, wherein the overhead temperature of the rectification of step (3) is 67 to 135 ℃.
18. The process of claim 1, wherein the reflux ratio of the rectification of step (3) is no greater than 5.
19. The method according to claim 1, wherein the 1, 3-propylene glycol product is taken out from the top of the tower during the rectification in the step (3), and the mass proportion of the 1, 3-propylene glycol product in the light component removing kettle material is 95.0-99.0 wt%.
20. The method according to claim 1, characterized in that it comprises the steps of:
(1) Sequentially carrying out precise filtration and reverse osmosis membrane separation on 1, 3-propylene glycol reaction liquid, wherein the 1, 3-propylene glycol reaction liquid is obtained by an acrolein hydration hydrogenation process, and the composition of the 1, 3-propylene glycol reaction liquid comprises less than or equal to 20.0wt% of 1, 3-hydroxy propanal less than or equal to 0.1wt%, 3-hydroxymethyl tetrahydropyran less than or equal to 0.1wt% of 1, 3-dioxane-2-ethanol less than or equal to 0.1wt%, 4-hetero-oxo-heptanediol less than or equal to 10.0wt%, water more than or equal to 70.0wt%, wherein the metal content is less than or equal to 200ppm, and the turbidity is less than or equal to 50NTU; the precise filtration is carried out in a precise filter, and the pore diameter of the precise filter is not more than 450nm; the reverse osmosis membrane separation is carried out by adopting a disc type reverse osmosis membrane element, and the molecular weight cut-off is not less than 100Da;
the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, wherein primary membrane thin solution and primary membrane thick solution are obtained through the primary membrane separation, the operation pressure of the primary membrane separation is 6.0-9.0 MPa, the operation temperature is 5-45 ℃, the secondary membrane separation is carried out after the primary membrane thick solution is diluted, the dilution multiple is 1.0-3.0 times, the operation pressure of the secondary membrane separation is 6.0-9.0 MPa, the operation temperature is 5-45 ℃, secondary membrane thin solution is obtained, and the two membrane thin solutions are combined and treated together;
(2) Evaporating and concentrating the membrane thin solution obtained in the step (1), wherein the kettle temperature of the evaporating and concentrating is 133-190 ℃, the absolute pressure is 5-50 kPa, so as to obtain concentrated solution, the water content of the concentrated solution is not more than 0.05wt%, the concentrated solution is subjected to light removal treatment, the light removal treatment is performed by adopting a light removal tower, the theoretical plate number of the light removal tower is not more than 40, the absolute pressure of the light removal treatment is 0.1-5.0 kPa, the tower top temperature is 65-133 ℃, the reflux ratio is not more than 10, and the light removal kettle material is obtained, wherein the mass ratio of light components extracted from the tower top is 1.0-10.0 wt%;
(3) Rectifying the light component removing kettle material obtained in the step (2), wherein the rectification is carried out by adopting a rectifying tower, the theoretical plate number of the rectifying tower is not more than 30, the absolute pressure of the rectification is 0.1-5.0 kPa, the tower top temperature is 67-135 ℃, the reflux ratio is not more than 5, and the 1, 3-propylene glycol product is extracted from the tower top of the rectifying tower and accounts for 95.0-99.0wt% of the light component removing kettle material.
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| WO2004101479A2 (en) * | 2003-05-06 | 2004-11-25 | E.I. Dupont De Nemours And Company | Purification of biologically-produced 1,3-propanediol |
| CN110922300A (en) * | 2019-12-07 | 2020-03-27 | 江苏久吾高科技股份有限公司 | Alcohol recovery method and device |
| CN112920020A (en) * | 2021-01-29 | 2021-06-08 | 浙江恒澜科技有限公司 | Refining production line and method of 1, 3-propylene glycol |
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| WO2004101479A2 (en) * | 2003-05-06 | 2004-11-25 | E.I. Dupont De Nemours And Company | Purification of biologically-produced 1,3-propanediol |
| CN110922300A (en) * | 2019-12-07 | 2020-03-27 | 江苏久吾高科技股份有限公司 | Alcohol recovery method and device |
| CN112920020A (en) * | 2021-01-29 | 2021-06-08 | 浙江恒澜科技有限公司 | Refining production line and method of 1, 3-propylene glycol |
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