CN114249633A - 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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- CN114249633A CN114249633A CN202210005636.XA CN202210005636A CN114249633A CN 114249633 A CN114249633 A CN 114249633A CN 202210005636 A CN202210005636 A CN 202210005636A CN 114249633 A CN114249633 A CN 114249633A
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- membrane separation
- propylene glycol
- propanediol
- reverse osmosis
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- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000012528 membrane Substances 0.000 claims abstract description 174
- 238000000926 separation method Methods 0.000 claims abstract description 119
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical group C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims abstract description 74
- 229940035437 1,3-propanediol Drugs 0.000 claims abstract description 74
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims abstract description 74
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims description 71
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 34
- 238000001704 evaporation Methods 0.000 claims description 25
- 238000001471 micro-filtration Methods 0.000 claims description 25
- 230000008020 evaporation Effects 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000010992 reflux Methods 0.000 claims description 18
- 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 15
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 claims description 15
- 230000036571 hydration Effects 0.000 claims description 15
- 238000006703 hydration reaction Methods 0.000 claims description 15
- 238000010790 dilution Methods 0.000 claims description 14
- 239000012895 dilution Substances 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 13
- VFTQJKSRDCKVQA-UHFFFAOYSA-N oxan-3-ylmethanol Chemical compound OCC1CCCOC1 VFTQJKSRDCKVQA-UHFFFAOYSA-N 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
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- 239000000047 product Substances 0.000 abstract description 58
- 239000006227 byproduct Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 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 14
- 238000000746 purification Methods 0.000 description 13
- 238000002835 absorbance Methods 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
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- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000000126 substance 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 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000000052 comparative effect Effects 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
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 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
- 238000007792 addition Methods 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 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
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000002360 preparation method 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
- 230000003595 spectral effect Effects 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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-propylene glycol, which comprises the following steps: sequentially carrying out precise filtration and reverse osmosis membrane separation on the 1, 3-propylene glycol reaction solution to obtain a membrane dilute solution; concentrating the obtained membrane diluted solution, and performing light component removal treatment on the obtained concentrated solution to obtain light component removal kettle materials; rectifying the light component removal kettle material to obtain a 1, 3-propylene glycol product. According to the composition of the 1, 3-propanediol reaction liquid, the method intercepts the by-products with relatively large molecular weight in the reaction liquid by utilizing the separation characteristic of reverse osmosis, reduces the separation difficulty of the 1, 3-propanediol product, and further purifies the by-products through concentration, lightness removal and rectification operations to obtain the high-purity 1, 3-propanediol product, wherein the purity of the high-purity 1, 3-propanediol product can reach more than 99.98 wt%, the total aldehyde content is below 10ppm, the product yield is high, and the waste liquid discharge is less; the method has the advantages of simple operation, mild process conditions, stable and reliable treatment effect and easy industrial implementation.
Description
Technical Field
The invention belongs to the technical field of chemical separation, and relates to a method for separating and purifying 1, 3-propylene glycol.
Background
1, 3-propanediol is used as an important organic chemical raw material, can be applied to the industries of printing ink, coating, cosmetics, pharmacy, antifreeze and the like, and is especially used as a main raw material for producing 1, 3-propanediol terephthalate (PTT); and when the PTT is used as a fiber material, the PTT not only has the characteristics of polyester fiber, but also has good rebound resilience and pollution resistance of nylon, is widely applied to the fields of carpets, engineering plastics, garment materials and the like, and is a hotspot for the development of the current synthetic fibers.
Since the quality of the 1, 3-propanediol product has a large influence on the characteristics of the PTT fiber, for example, the product purity affects its intrinsic viscosity, and the aldehyde content and color of the product affect the appearance of PTT; therefore, the research on synthesizing high-purity 1, 3-propylene glycol is one of the current hotspots, and mainly comprises two major types of chemical methods and biological methods, wherein an acrolein hydration hydrogenation process in the chemical method has the characteristics of low technical difficulty, mild process conditions, high atom utilization rate and the like, and is one of the current industrial routes, but in the method, acrolein and an intermediate product 3-hydroxypropionaldehyde are unstable and are easy to generate polycondensation reaction, so that aldehyde byproducts are generated, more byproducts are generated after hydrogenation, the reaction system components are complex, the difficulty of separating and purifying the 1, 3-propylene glycol 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 concentrated solution containing trace aldehyde group impurities, catalyzing aldehyde groups by the ionic liquid to carry out aldehyde removal reaction, and then carrying out reduced pressure rectification to obtain a product with low aldehyde content and high 1, 3-propylene glycol purity; 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 method for purifying 1, 3-propanediol, which comprises the following steps: adjusting the pH value of a raw material containing 1, 3-propylene glycol and reacting, wherein the raw material contains aldehyde organic matters to obtain a reaction product; carrying out first rectification and second reduced pressure rectification on the reaction product to obtain crude 1, 3-propylene glycol; and (3) subjecting the crude 1, 3-propanediol to resin adsorption and third rectification to obtain the 1, 3-propanediol. The method utilizes the characteristics of aldehyde substances, reactants are added to convert the aldehyde substances into macromolecular substances, but side reactions can also occur, the aldehyde content can be reduced, but the yield of the product is lower, resin adsorption operation is also needed, 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 need to be selected, 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 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 a 1, 3-propanediol reaction solution, a relatively high molecular weight byproduct in the reaction solution is intercepted by utilizing the separation characteristic of reverse osmosis, the separation difficulty of the 1, 3-propanediol product is reduced, and the 1, 3-propanediol product with high purity is obtained through light component removal and further purification by rectification operation, and the product yield is high; the method has the advantages of simple operation, mild conditions, low cost and easy industrial implementation.
In order 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 carrying out precise filtration and reverse osmosis membrane separation on the 1, 3-propylene glycol reaction solution to obtain a membrane dilute solution;
(2) concentrating the membrane diluted solution obtained in the step (1), and performing light component removal treatment on the obtained concentrated solution to obtain a light component removal kettle material;
(3) and (3) rectifying the light component removal kettle material obtained in the step (2) to obtain a 1, 3-propylene glycol product.
According to the invention, for separation and purification after 1, 3-propanediol synthesis, according to the selection of reaction raw materials and a specific reaction process, various byproducts inevitably exist in the product, 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 former mainly separates solid particles, and the latter intercepts organic matters with relatively large molecular weight by utilizing the separation characteristic of reverse osmosis, so that the mode can realize effective separation of 1, 3-propanediol and related byproducts, simultaneously reduce the separation difficulty of reaction liquid, and realize full purification of 1, 3-propanediol through concentration, lightness removal and rectification operations, and has higher product yield and less waste liquid discharge; the method has the advantages of simple operation, mild process conditions, stable and reliable treatment effect and easy realization of industrial production.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferable technical scheme of the invention, the 1, 3-propylene glycol reaction liquid in the step (1) is obtained by acrolein through a hydration hydrogenation process.
Preferably, the 1, 3-propanediol reaction solution in the step (1) comprises 1, 3-propanediol, 3-hydroxypropionaldehyde, 3-hydroxymethyltetrahydropyran, 1, 3-dioxane-2-ethanol, 4-heterooxyheptanediol and water.
Preferably, the 1, 3-propanediol reaction solution of step (1) has a composition comprising, in terms of mass concentration, 1, 3-propanediol. ltoreq.20.0% by weight, such as 20.0%, 18.0%, 15.0%, 12.0%, 10.0%, 8.0%, or 5.0% by weight, 3-hydroxypropanal. ltoreq.0.1% by weight, such as 0.1%, 0.05%, 0.01%, or 0.005% by weight, etc., 3-hydroxymethyltetrahydropyran. ltoreq.0.1% by weight, such as 0.1%, 0.05%, 0.01%, or 0.005% by weight, etc., 1, 3-dioxane-2-ethanol. ltoreq.0.1% by weight, such as 0.1%, 0.05%, 0.01%, or 0.005% by weight, etc., 4-heteroxepinoxyl. ltoreq.0.1% by weight, such as 0.1%, 0.05%, 0.01%, or 0.005% by weight, 0.5% by weight, etc., 0.1% by weight, 0.005% by weight, 0.1% by weight, 0.005% by weight, 5% by weight, 0.005% by weight, etc., of heteroxepinoxyl, 0.1% by weight, 0.005% by weight, 5% by weight, etc., 1% by weight, 5% by weight, 0.005% by weight, 5% by weight, etc., of a diol, etc., or 5% by weight, etc., 1% by weight, etc., of the like, water ≥ 70.0 wt%, e.g. 70.0 wt%, 75.0 wt%, 80.0 wt%, 85.0 wt% or 90.0 wt%, etc.; but are not limited to the recited values and other values not recited within the respective numerical ranges are equally applicable.
Preferably, the 1, 3-propanediol reaction solution of step (1) has a metal content of 200ppm or less, such as 200ppm, 180ppm, 150ppm, 120ppm, 100ppm or 50ppm, etc., and a turbidity of 50NTU or less, such as 50NTU, 45NTU, 40NTU, 35NTU or 30NTU, etc., but is not limited to the recited values, and other unrecited values within the respective numerical ranges are equally applicable.
According to the invention, 3-hydroxypropionaldehyde is prepared by hydrating acrolein, the 3-hydroxypropionaldehyde is subjected to catalytic hydrogenation to obtain 1, 3-propylene glycol, meanwhile, a broken catalyst exists in a reaction liquid, and as the used catalyst usually contains transition metal, usually nickel, and causes the reaction liquid to have certain turbidity, in order to ensure the stable operation of a device and purify the 1, 3-propylene glycol, the metal content and the turbidity need to be correspondingly reduced.
Since the 1, 3-propanediol reaction liquid contains a plurality of aldehyde by-products, the aldehyde substances can obviously affect the product performance, and the total aldehyde content is usually determined to reflect the purity of the product, and the total aldehyde content is measured by taking formaldehyde as a reference.
As a preferred technical scheme of the invention, the microfiltration in the step (1) is carried out in a microfiltration machine.
Preferably, the pore size of the microfilter is no greater than 450nm, such as 450nm, 300nm, 200nm, 100nm, 50nm or 30nm, but is not limited to the recited values, and other values not recited within this range are equally applicable.
As a preferable technical scheme of the invention, the reverse osmosis membrane separation in the step (1) is carried out by adopting a disc type reverse osmosis membrane element.
In the invention, the disc type reverse osmosis membrane element is adopted during reverse osmosis membrane separation, and compared with a roll type reverse osmosis membrane element, the disc type reverse osmosis membrane element 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 reverse osmosis membrane separation has a molecular weight cut-off of not less than 100 Da.
As a preferable technical scheme of the invention, the reverse osmosis membrane separation in the step (1) comprises primary membrane separation and secondary membrane separation, wherein the primary membrane separation is carried out to obtain primary membrane weak solution and primary membrane thick solution, the primary membrane thick solution is diluted and then subjected to secondary membrane separation to obtain secondary membrane weak solution, and the two membrane weak solutions are combined and jointly treated.
Preferably, the operating pressure of the primary membrane separation is 6.0 to 9.0MPa, such as 6.0MPa, 6.5MPa, 7.0MPa, 7.5MPa, 8.0MPa, 8.5MPa or 9.0MPa, but not limited to the recited values, and other values not recited in the range of values are also applicable; the operation temperature is 5 to 45 ℃, for example, 5 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃ or 45 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the dilution ratio of the primary membrane 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, but is not limited to the enumerated values, and other values not enumerated within the numerical range are also applicable.
Preferably, the operating pressure of the secondary membrane separation is 6.0 to 9.0MPa, such as 6.0MPa, 6.5MPa, 7.0MPa, 7.5MPa, 8.0MPa, 8.5MPa or 9.0MPa, but not limited to the recited values, and other values not recited in the range of values are also applicable; the operation temperature is 5 to 45 ℃, for example, 5 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃ or 45 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
As a preferred technical scheme of the invention, the concentration in the step (2) comprises evaporation concentration.
Preferably, the evaporation concentration is carried out at a temperature of 133 to 190 ℃, for example, 133 ℃, 140 ℃, 155 ℃, 163 ℃, 170 ℃, 180 ℃ or 190 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the absolute pressure of the evaporation concentration is 5 to 50kPa, for example, 5kPa, 10kPa, 15kPa, 25kPa, 35kPa, 45kPa, or 50kPa, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the concentrate of step (2) has a water content of not more than 0.05 wt.%, such as 0.05 wt.%, 0.04 wt.%, 0.03 wt.%, 0.02 wt.%, or 0.01 wt.%, and the like, but is not limited to the recited values, and other values not recited within this range are equally applicable.
As a preferable technical scheme of the invention, the light component removal treatment in the step (2) is carried out by adopting a light component removal tower.
Preferably, the number of theoretical plates in the light ends removal column is not greater than 40, e.g., 40, 35, 30, 25, or 20, etc., but is not limited to the recited values, and other values not recited within the range are equally applicable.
Preferably, the absolute pressure of the light removal treatment in 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, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the overhead temperature of the lightness-removing treatment in the step (2) is 65 to 133 ℃, for example, 65 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃ or 133 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reflux ratio of the lightness-removing treatment in step (2) is not more than 10, such as 10, 9, 8, 7, 6 or 5, etc., but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
As a preferable technical scheme of the invention, the rectification in the step (3) is carried out by adopting a rectification tower.
Preferably, the number of theoretical plates of the rectification column is not more than 30, for example 30, 25, 20, 15 or 10, etc., but is not limited to the values listed, and other values not listed in this range are equally applicable.
Preferably, the absolute pressure of the distillation in step (3) is 0.1 to 5.0kPa, such as 0.1kPa, 0.5kPa, 1.0kPa, 2.0kPa, 3.0kPa, 4.0kPa, or 5.0kPa, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the rectification in step (3) has a top temperature of 67 to 135 ℃, for example 67 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃ or 135 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the reflux ratio of the distillation of step (3) is not more than 5, such as 5, 4, 3, 2 or 1, etc., but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
In a preferred embodiment of the present invention, the weight ratio of the light components at the top of the light component removal column in the step (2) is 1.0 to 10.0 wt%, for example, 1.0 wt%, 2.0 wt%, 3.0 wt%, 4.0 wt%, 5.0 wt%, 6.0 wt%, 7.0 wt%, 8.0 wt%, 9.0 wt%, or 10.0 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable.
Preferably, the rectification in step (3) produces 1, 3-propanediol product at the top of the column, and the mass proportion of the 1, 3-propanediol product in the light ends removal residue is 95.0-99.0 wt%, such as 95.0 wt%, 95.5 wt%, 96.0 wt%, 97.0 wt%, 98.0 wt% or 99.0 wt%, but not limited to the recited values, and other values in the range of the recited values are also applicable.
As a preferred technical scheme of the invention, the method comprises the following steps:
(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 acrolein through a hydration hydrogenation process, and the 1, 3-propylene glycol reaction liquid comprises the following components, by mass, not more than 20.0 wt% of 1, 3-propylene glycol, not more than 0.1 wt% of 3-hydroxypropionaldehyde, not more than 0.1 wt% of 3-hydroxymethyl tetrahydropyran, not more than 0.1 wt% of 1, 3-dioxane-2-ethanol, not more than 0.1 wt% of 4-heteroxy heptanediol, not more than 10.0 wt% of 4-heteroxy heptanediol, not less than 70.0 wt% of water, wherein the metal content is not more than 200ppm, and the turbidity is not more than 50 NTU; the microfiltration is carried out in a microfiltration filter, and the pore size of the microfiltration filter is not more than 450 nm; 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 100 Da;
the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, wherein primary membrane separation is carried out to obtain primary membrane dilute liquid and primary membrane concentrated liquid, the operating pressure of the primary membrane separation is 6.0-9.0 MPa, the operating temperature is 5-45 ℃, the primary membrane concentrated liquid is diluted and then subjected to secondary membrane separation, the dilution multiple is 1.0-3.0 times, the operating pressure of the secondary membrane separation is 6.0-9.0 MPa, the operating temperature is 5-45 ℃, secondary membrane dilute liquid is obtained, and the two membrane dilute liquids are combined for common treatment;
(2) carrying out evaporation concentration on the membrane diluted solution obtained in the step (1), wherein the temperature of an evaporation concentration kettle is 133-190 ℃ and the absolute pressure is 5-50 kPa to obtain a concentrated solution, the water content of the concentrated solution is not more than 0.05 wt%, the concentrated solution is subjected to lightness removing treatment, the lightness removing treatment is carried out by adopting a lightness removing tower, the theoretical number of tower plates of the lightness removing tower is not more than 40, the absolute pressure of the lightness removing treatment is 0.1-5.0 kPa, the temperature of the top of the tower is 65-133 ℃, the reflux ratio is not more than 10 to obtain a lightness removing kettle material, and the mass ratio of light components extracted from the top of the tower is 1.0-10.0 wt%;
(3) and (3) rectifying the light 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 95.0-99.0 wt% of the light 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 intercepts the by-products with relatively large molecular weight in the reaction liquid by utilizing the separation characteristic of reverse osmosis, reduces the separation difficulty of the 1, 3-propanediol product, and further purifies the by-products through concentration, lightness removal and rectification operations to obtain the high-purity 1, 3-propanediol product, wherein the purity of the high-purity 1, 3-propanediol product can reach more than 99.98 wt%, the total aldehyde content is below 10ppm, the product yield is high, and the waste liquid discharge is less;
(2) the method has the advantages of simple operation, mild process conditions, stable and reliable treatment effect and easy industrial implementation.
Drawings
FIG. 1 is a process flow diagram of a method for separating and purifying a 1, 3-propanediol reaction solution according to example 1 of the present invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The invention provides, in part, a method for the separation and purification of 1, 3-propanediol comprising the steps of:
(1) sequentially carrying out precise filtration and reverse osmosis membrane separation on the 1, 3-propylene glycol reaction solution to obtain a membrane dilute solution;
(2) concentrating the membrane diluted solution obtained in the step (1), and performing light component removal treatment on the obtained concentrated solution to obtain a light component removal kettle material;
(3) and (3) rectifying the light component removal kettle material obtained in the step (2) to obtain a 1, 3-propylene glycol product.
The following are typical but non-limiting examples of the invention:
example 1:
the present embodiment provides a method for separating and purifying 1, 3-propanediol, the process flow diagram 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 1, 3-propylene glycol reaction liquid, wherein the 1, 3-propylene glycol reaction liquid is obtained by acrolein through a hydration hydrogenation process, and the 1, 3-propylene glycol reaction liquid comprises 10.9 wt% of 1, 3-propylene glycol, 50ppm of 3-hydroxypropionaldehyde, 80ppm of 3-hydroxymethyl tetrahydropyran, 70ppm of 1, 3-dioxane-2-ethanol, 20ppm of 4-heteroxy heptanediol, 0.8 wt% of 4-heteroxy heptanediol and 88.3 wt% of water according to mass concentration, wherein the nickel content is 75ppm, the turbidity is 10NTU, and the total aldehyde content is 28 ppm; the microfiltration is carried out in a microfiltration machine, and the pore diameter of the microfiltration machine is 450 nm; the reverse osmosis membrane separation is carried out by adopting a disc type reverse osmosis membrane element, and the molecular weight cutoff is 100 Da;
the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, wherein primary membrane separation is carried out to obtain primary membrane dilute liquid and primary membrane concentrated liquid, the operating pressure of the primary membrane separation is 9.0MPa, the operating temperature is 30 ℃, the primary membrane concentrated liquid is diluted and then subjected to secondary membrane separation, the dilution multiple is 1.0 time, the operating pressure of the secondary membrane separation is 9.0MPa, the operating temperature is 30 ℃, secondary membrane dilute liquid is obtained, and the two membrane dilute liquids are combined for common treatment;
(2) evaporating and concentrating the membrane weak solution obtained in the step (1), wherein the temperature of an evaporation and concentration kettle is 133 ℃, and the absolute pressure is 5kPa, so as to obtain a concentrated solution, the water content of the concentrated solution is 0.05 wt%, volatile components of evaporation and concentration are recycled for the dilution and acrolein hydration hydrogenation process in the step (1), the concentrated solution is subjected to light component removal treatment, the light component removal treatment is carried out by adopting a light component removal tower, the theoretical number of tower plates of the light component removal tower is 40, the absolute pressure of the light component removal treatment is 1.0kPa, the temperature is 102 ℃, and the reflux ratio is 3, so as to obtain a light component removal kettle material, wherein the mass ratio of light components extracted from the top of the tower is 3.7 wt%;
(3) and (3) rectifying the light kettle material obtained in the step (2) by using a rectifying tower, wherein 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 a 1, 3-propylene glycol product is extracted from the top of the rectifying tower, and accounts for 97.6 wt% of the light kettle material.
Measuring the mass concentrations of 3-hydroxypropionaldehyde, 1, 3-propanediol, 3-hydroxymethyl tetrahydropyran, 1, 3-dioxane-2-ethanol, 4-heteroxoheptanediol and 4-heteroxoheptanediol in each strand of material by adopting a gas chromatography; detecting the COD value by adopting an oxidation-reduction potentiometric titration method; detecting the nickel content by adopting an inductively coupled plasma spectral generator; ultraviolet absorbance and total aldehyde content are measured by adopting an ultraviolet spectrophotometry, and chromaticity is measured by adopting a platinum-cobalt colorimetric method.
In this example, the membrane separation yield of 1, 3-propanediol after the treatment in step (1) was 97.0%, the evaporation fraction did not contain 1, 3-propanediol after the concentration in step (2), the COD value was 58ppm, the mass concentration of 1, 3-propanediol in the concentrated solution was 98.5 wt%, the mass concentration of 1, 3-propanediol in the lightness-removing residue was 98.5 wt% after the lightness-removing treatment, 3-hydroxymethyltetrahydropyran and 1, 3-dioxane-2-ethanol were not detected, the mass concentration of 1, 3-propanediol product at the top of the column was 99.98 wt% after the rectification in step (3), the total aldehyde content was only 4.3ppm, the ultraviolet absorbance of the product at 270nm was 0.01, the chroma in platinum-cobalt color number was 3, and the index requirement for polymer grade 1, 3-propanediol for fibers could be satisfied, and the separation yield for a single pass product was 92.7%.
Example 2:
this example provides a method for the isolation and purification of 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 acrolein through a hydration hydrogenation process, and the 1, 3-propylene glycol reaction liquid comprises 10.9 wt% of 1, 3-propylene glycol, 50ppm of 3-hydroxypropionaldehyde, 80ppm of 3-hydroxymethyl tetrahydropyran, 70ppm of 1, 3-dioxane-2-ethanol, 20ppm of 4-heteroxy heptanediol, 0.8 wt% of 4-heteroxy heptanediol and 88.3 wt% of water according to mass concentration, wherein the nickel content is 75ppm, the turbidity is 10NTU, and the total aldehyde content is 28 ppm; the microfiltration is carried out in a microfiltration machine, and the pore diameter of the microfiltration machine is 100 nm; the reverse osmosis membrane separation is carried out by adopting a disc type reverse osmosis membrane element, and the molecular weight cutoff is 100 Da;
the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, wherein the primary membrane separation is used for obtaining primary membrane dilute liquid and primary membrane concentrated liquid, the operating pressure of the primary membrane separation is 7.5MPa, the operating temperature is 20 ℃, the primary membrane concentrated liquid is diluted and then subjected to secondary membrane separation, the dilution multiple is 1.0 time, the operating pressure of the secondary membrane separation is 7.5MPa, the operating temperature is 20 ℃, secondary membrane dilute liquid is obtained, and the two membrane dilute liquids are combined for common treatment;
(2) evaporating and concentrating the membrane diluted solution obtained in the step (1), wherein the temperature of an evaporation and concentration kettle is 190 ℃ and the absolute pressure is 50kPa to obtain a concentrated solution, the water content of the concentrated solution is 0.04 wt%, the volatile components of evaporation and concentration are recycled for the dilution and acrolein hydration hydrogenation process in the step (1), the concentrated solution is subjected to light component removal treatment, the light component removal treatment is carried out by adopting a light component removal tower, the theoretical plate number of the light component removal tower is 30, the absolute pressure of the light component removal treatment is 3.0kPa, the temperature is 121 ℃, and the reflux ratio is 5 to obtain a light component removal kettle material, wherein the mass ratio of light components extracted from the top of the tower is 6.5 wt%;
(3) and (3) rectifying the light kettle material obtained in the step (2) by using a rectifying tower, wherein 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 1, 3-propylene glycol products are extracted from the top of the rectifying tower and account for 95.2 wt% of the light kettle material.
The parameters associated with each strand of the process were determined in the same manner as in example 1.
In this example, the mass concentration of the 1, 3-propanediol product is 99.99 wt%, the total aldehyde content is only 5.3ppm, the ultraviolet absorbance of the product at 270nm is 0.01, the chroma in the platinum-cobalt color number is 3, the index requirement of the fiber polymer grade 1, 3-propanediol can be met, and the separation yield of a single-pass product is 86.4%.
Example 3:
this example provides a method for the isolation and purification of 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 acrolein through a hydration hydrogenation process, and the 1, 3-propylene glycol reaction liquid comprises 10.9 wt% of 1, 3-propylene glycol, 50ppm of 3-hydroxypropionaldehyde, 80ppm of 3-hydroxymethyl tetrahydropyran, 70ppm of 1, 3-dioxane-2-ethanol, 20ppm of 4-heteroxy heptanediol, 0.8 wt% of 4-heteroxy heptanediol and 88.3 wt% of water according to mass concentration, wherein the nickel content is 75ppm, the turbidity is 10NTU, and the total aldehyde content is 28 ppm; the microfiltration is carried out in a microfiltration machine, and the pore diameter of the microfiltration machine is 60 nm; the reverse osmosis membrane separation is carried out by adopting a disc type reverse osmosis membrane element, and the molecular weight cutoff is 100 Da;
the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, wherein the primary membrane separation is used for obtaining primary membrane dilute liquid and primary membrane concentrated liquid, the operating pressure of the primary membrane separation is 6.0MPa, the operating temperature is 45 ℃, the primary membrane concentrated liquid is diluted and then subjected to secondary membrane separation, the dilution multiple is 1.0 time, the operating pressure of the secondary membrane separation is 6.0MPa, the operating temperature is 45 ℃, secondary membrane dilute liquid is obtained, and the two membrane dilute liquids are combined for common treatment;
(2) evaporating and concentrating the membrane diluted solution obtained in the step (1), wherein the temperature of an evaporation and concentration kettle is 159 ℃, the absolute pressure is 15kPa, so as to obtain a concentrated solution, the water content of the concentrated solution is 0.05 wt%, the volatile components of evaporation and concentration are reused in the dilution and acrolein hydration hydrogenation process in the step (1), the concentrated solution is subjected to lightness removing treatment, the lightness removing treatment is performed by adopting a lightness removing tower, the theoretical number of tower plates of the lightness removing tower is 35, the absolute pressure of the lightness removing treatment is 5.0kPa, the temperature is 133 ℃, the reflux ratio is 10, so as to obtain a lightness removing kettle material, and the mass ratio of light components extracted from the top of the tower is 3.6 wt%;
(3) and (3) rectifying the light kettle material obtained in the step (2) by adopting a rectifying tower, wherein 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 1, 3-propylene glycol products are extracted from the top of the rectifying tower and account for 96.7 wt% of the light kettle material.
The parameters associated with each strand of the process were determined in the same manner as in example 1.
In this example, the mass concentration of the 1, 3-propanediol product is 99.99 wt%, the total aldehyde content is only 3.3ppm, the ultraviolet absorbance of the product at 270nm is 0.01, the chroma in the platinum-cobalt color number is 1, and the index requirement of the fiber polymer grade 1, 3-propanediol can be met, and the separation yield of the single-pass product is 90.4%.
Example 4:
this example provides a method for the isolation and purification of 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 acrolein through a hydration hydrogenation process, and the 1, 3-propylene glycol reaction liquid comprises 15.0 wt% of 1, 3-propylene glycol, 100ppm of 3-hydroxypropionaldehyde, 60ppm of 3-hydroxymethyl tetrahydropyran, 80ppm of 1, 3-dioxane-2-ethanol, 50ppm of 4-heteroxy heptanediol, 1.0 wt% of 4-heteroxy heptanediol and 84.0 wt% of water according to mass concentration, wherein the nickel content is 100ppm, the turbidity is 30NTU, and the total aldehyde content is 47 ppm; the microfiltration is carried out in a microfiltration machine, and the pore diameter of the microfiltration machine is 150 nm; the reverse osmosis membrane separation is carried out by adopting a disc type reverse osmosis membrane element, and the molecular weight cutoff is 100 Da;
the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, wherein primary membrane separation is carried out to obtain primary membrane dilute liquid and primary membrane concentrated liquid, the operating pressure of the primary membrane separation is 9.0MPa, the operating temperature is 40 ℃, the primary membrane concentrated liquid is diluted and then subjected to secondary membrane separation, the dilution multiple is 2.0 times, the operating pressure of the secondary membrane separation is 9.0MPa, the operating temperature is 40 ℃, secondary membrane dilute liquid is obtained, and the two membrane dilute liquids are combined for common treatment;
(2) evaporating and concentrating the membrane diluted solution obtained in the step (1), wherein the temperature of an evaporation and concentration kettle is 185 ℃, the absolute pressure is 40kPa, so as to obtain a concentrated solution, the water content of the concentrated solution is 0.05 wt%, the volatile components of evaporation and concentration are reused in the dilution and acrolein hydration hydrogenation process in the step (1), the concentrated solution is subjected to light component removal treatment, the light component removal treatment is carried out by adopting a light component removal tower, the theoretical number of tower plates of the light component removal tower is 40, the absolute pressure of the light component removal treatment is 0.5kPa, the temperature is 90 ℃, the reflux ratio is 6, so as to obtain a light component removal kettle material, and the mass ratio of light components extracted from the top of the tower is 3.1 wt%;
(3) and (3) rectifying the light 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 1, 3-propylene glycol products are extracted from the top of the rectifying tower, and account for 96.9 wt% of the light kettle material.
The parameters associated with each strand of the process were determined in the same manner as in example 1.
In this example, the mass concentration of the 1, 3-propanediol product is 99.98 wt%, the total aldehyde content is only 4.4ppm, the ultraviolet absorbance of the product at 270nm is 0.01, the chroma in the platinum-cobalt color number is 2, which can meet the index requirement of the fiber polymer grade 1, 3-propanediol, and the separation yield of the single-pass product is 93.0%.
Example 5:
this example provides a method for the isolation and purification of 1, 3-propanediol comprising the steps of:
(1) sequentially carrying out precise filtration and reverse osmosis membrane separation on 1, 3-propanediol reaction liquid, wherein the 1, 3-propanediol reaction liquid is obtained by acrolein through a hydration hydrogenation process, and the 1, 3-propanediol reaction liquid comprises 6.0 wt% of 1, 3-propanediol, 80ppm of 3-hydroxypropionaldehyde, 100ppm of 3-hydroxymethyl tetrahydropyran, 120ppm of 1, 3-dioxane-2-ethanol, 70ppm of 4-heteroxy heptanediol, 0.6 wt% of 4-heteroxy heptanediol and 93.4 wt% of water according to mass concentration, wherein the nickel content is 100ppm, the turbidity is 30NTU, and the total aldehyde content is 62 ppm; the microfiltration is carried out in a microfiltration machine, and the pore diameter of the microfiltration machine is 300 nm; the reverse osmosis membrane separation is carried out by adopting a disc type reverse osmosis membrane element, and the molecular weight cutoff is 100 Da;
the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, wherein the primary membrane separation is used for obtaining primary membrane dilute liquid and primary membrane concentrated liquid, the operating pressure of the primary membrane separation is 8.0MPa, the operating temperature is 25 ℃, the primary membrane concentrated liquid is diluted and then subjected to secondary membrane separation, the dilution multiple is 3.0 times, the operating pressure of the secondary membrane separation is 8.0MPa, the operating temperature is 25 ℃, secondary membrane dilute liquid is obtained, and the two membrane dilute liquids are combined for common treatment;
(2) evaporating and concentrating the membrane weak solution obtained in the step (1), wherein the temperature of an evaporation and concentration kettle is 175 ℃ and the absolute pressure is 25kPa to obtain a concentrated solution, the water content of the concentrated solution is 0.045 wt%, volatile components of evaporation and concentration are recycled for the dilution and acrolein hydration hydrogenation process in the step (1), the concentrated solution is subjected to lightness removing treatment, the lightness removing treatment is carried out by adopting a lightness removing tower, the theoretical number of tower plates of the lightness removing tower is 38, the absolute pressure of the lightness removing treatment is 2.0kPa, the temperature is 114 ℃, the reflux ratio is 8, and a lightness removing kettle material is obtained, wherein the mass proportion of light components extracted from the top of the tower is 5.7 wt%;
(3) and (3) rectifying the light kettle material obtained in the step (2) by adopting a rectifying tower, wherein 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 a 1, 3-propylene glycol product is extracted from the top of the rectifying tower, and accounts for 97.7 wt% of the light kettle material.
The parameters associated with each strand of the process were determined in the same manner as in example 1.
In this example, the mass concentration of the 1, 3-propanediol product is 99.98 wt%, 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 fiber polymer grade 1, 3-propanediol can be met, and the separation yield of the single-pass product is 90.2%.
Example 6:
this example provides a process for the isolation and purification of 1, 3-propanediol by reference to the process of example 1, except that: the reverse osmosis membrane separation in step (1) is performed only once.
In this embodiment, since reverse osmosis membrane separation is an important operation for removing organic byproducts with large molecular weight, membrane separation is performed only once, and the membrane concentrate reaches a certain concentration, which may cause difficulty in further performing, so that the 1, 3-propanediol component to be recovered may not sufficiently enter the membrane dilute solution, and the separation yield of 1, 3-propanediol per pass is reduced to 86.2%.
Example 7:
this example provides a process for the isolation and purification of 1, 3-propanediol by reference to the process of example 1, except that: and (2) the reverse osmosis membrane separation in the step (1) is carried out by adopting a roll type reverse osmosis membrane element.
In this embodiment, due to the use of the roll-type reverse osmosis membrane element, compared with the disc-type reverse osmosis membrane element, the tolerance of the roll-type reverse osmosis membrane element to the 1, 3-propanediol reaction liquid is poor, and the rejection rate of impurities in the reaction liquid is reduced, so that the quality and yield of the 1, 3-propanediol product are affected, at this time, the mass concentration of the 1, 3-propanediol is 99.97 wt%, the mass concentration of total aldehyde is 9.5ppm, the corresponding ultraviolet absorbance is 0.04, the chromaticity is 5, and the separation yield of a single-pass product is only 88.3%.
Comparative example 1:
this comparative example provides a process for the isolation and purification of 1, 3-propanediol by reference to the process of example 1, except that: the reverse osmosis membrane separation in the step (1) is not included.
In the comparative example, because the separation and purification of the 1, 3-propylene glycol reaction liquid are not carried out by reverse osmosis, various impurities need to be removed in the light removal and rectification stages, but because the boiling point difference between the 1, 3-propylene glycol reaction liquid and the product is not large, the separation difficulty is relatively large, the aldehyde impurities are not completely removed, and simultaneously, a large amount of 1, 3-propylene glycol is lost, the mass concentration of the obtained 1, 3-propylene glycol is 99.93 wt%, the mass concentration of total aldehyde reaches 83.1ppm, the corresponding ultraviolet absorbance is 0.08, the chroma is 9, and the separation yield of the product per pass is only 69.5%.
It can be seen from the above examples and comparative examples that, according to the composition of the 1, 3-propanediol reaction solution, the method of the present invention utilizes the separation characteristic of reverse osmosis to intercept the by-products with relatively large molecular weight in the reaction solution, reduce the separation difficulty of the 1, 3-propanediol product, and further purify the product through the operations of concentration, lightness removal and rectification to obtain the high purity 1, 3-propanediol product, the purity of which can reach more than 99.98 wt%, the total aldehyde content of which is less than 10ppm, the product yield is high, and the waste liquid discharge is low; the method has the advantages of simple operation, mild process conditions, stable and reliable treatment effect and easy industrial implementation.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It will be apparent to those skilled in the art that any modifications to the present invention, equivalents of the method of the present invention and additions of ancillary steps, selection of specific means, etc., are within the scope and disclosure of the present invention.
Claims (10)
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 the 1, 3-propylene glycol reaction solution to obtain a membrane dilute solution;
(2) concentrating the membrane diluted solution obtained in the step (1), and performing light component removal treatment on the obtained concentrated solution to obtain a light component removal kettle material;
(3) and (3) rectifying the light component removal kettle material obtained in the step (2) to obtain a 1, 3-propylene glycol product.
2. The method according to claim 1, wherein the 1, 3-propanediol reaction liquid in step (1) is obtained by hydration hydrogenation of acrolein;
preferably, the 1, 3-propanediol reaction solution in the step (1) comprises 1, 3-propanediol, 3-hydroxypropionaldehyde, 3-hydroxymethyl tetrahydropyran, 1, 3-dioxane-2-ethanol, 4-heterooxyheptanediol and water;
preferably, the 1, 3-propanediol reaction solution in the step (1) comprises, by mass concentration, 1, 3-propanediol no more than 20.0 wt%, 3-hydroxypropionaldehyde no more than 0.1 wt%, 3-hydroxymethyltetrahydropyran no more than 0.1 wt%, 1, 3-dioxane-2-ethanol no more than 0.1 wt%, 4-heteroxy heptanediol no more than 10.0 wt%, and water no less than 70.0 wt%;
preferably, the 1, 3-propanediol reaction solution in the step (1) has the metal content of less than or equal to 200ppm and the turbidity of less than or equal to 50 NTU.
3. The method of claim 1 or 2, wherein the microfiltration of step (1) is performed in a microfiltration machine;
preferably, the pore size of the precision filter is not greater than 450 nm.
4. The method according to any one of claims 1 to 3, wherein the reverse osmosis membrane separation of step (1) is performed using a disk type reverse osmosis membrane element;
preferably, the reverse osmosis membrane separation has a molecular weight cut-off of not less than 100 Da.
5. The method according to any one of claims 1 to 4, wherein the reverse osmosis membrane separation in the step (1) comprises a primary membrane separation and a secondary membrane separation, wherein the primary membrane separation is performed to obtain a primary membrane dilute solution and a primary membrane concentrated solution, the primary membrane concentrated solution is diluted and then subjected to the secondary membrane separation to obtain a secondary membrane dilute solution, and the two membrane dilute solutions are combined and treated together;
preferably, the operation pressure of the primary membrane separation is 6.0-9.0 MPa, and the operation temperature is 5-45 ℃;
preferably, the dilution multiple of the primary membrane concentrated solution is 1.0-3.0 times;
preferably, the operating pressure of the secondary membrane separation is 6.0-9.0 MPa, and the operating temperature is 5-45 ℃.
6. The method according to any one of claims 1 to 5, wherein the concentration of step (2) comprises evaporative concentration;
preferably, the temperature of the evaporation concentration kettle is 133-190 ℃;
preferably, the absolute pressure of the evaporation concentration is 5-50 kPa;
preferably, the water content of the concentrate of step (2) is not more than 0.05 wt%.
7. The method according to any one of claims 1 to 6, wherein the light component removal treatment in step (2) is performed by using a light component removal column;
preferably, the theoretical plate number of the lightness-removing column is not more than 40;
preferably, the absolute pressure of the light component removal treatment in the step (2) is 0.1-5.0 kPa;
preferably, the tower top temperature of the light component removal treatment in the step (2) is 65-133 ℃;
preferably, the reflux ratio of the light component removal treatment in the step (2) is not more than 10.
8. The method according to any one of claims 1 to 7, wherein the distillation in the step (3) is performed by using a distillation column;
preferably, the theoretical plate number of the rectifying tower is not more than 30;
preferably, the absolute pressure of the rectification in the step (3) is 0.1-5.0 kPa;
preferably, the tower top temperature of the rectification in the step (3) is 67-135 ℃;
preferably, the reflux ratio of the distillation in the step (3) is not more than 5.
9. The method according to any one of claims 1 to 8, wherein the weight proportion of the light components at the top of the light component removal tower in the step (2) is 1.0-10.0 wt%;
preferably, a 1, 3-propylene glycol product is extracted from the top of the tower during rectification in the step (3), and the mass proportion of the 1, 3-propylene glycol product in the light component removal kettle material is 95.0-99.0 wt%.
10. Method according to any of claims 1-9, characterized in that 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 acrolein through a hydration hydrogenation process, and the 1, 3-propylene glycol reaction liquid comprises the following components, by mass, not more than 20.0 wt% of 1, 3-propylene glycol, not more than 0.1 wt% of 3-hydroxypropionaldehyde, not more than 0.1 wt% of 3-hydroxymethyl tetrahydropyran, not more than 0.1 wt% of 1, 3-dioxane-2-ethanol, not more than 0.1 wt% of 4-heteroxy heptanediol, not more than 10.0 wt% of 4-heteroxy heptanediol, not less than 70.0 wt% of water, wherein the metal content is not more than 200ppm, and the turbidity is not more than 50 NTU; the microfiltration is carried out in a microfiltration filter, and the pore size of the microfiltration filter is not more than 450 nm; 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 100 Da;
the reverse osmosis membrane separation comprises primary membrane separation and secondary membrane separation, wherein primary membrane separation is carried out to obtain primary membrane dilute liquid and primary membrane concentrated liquid, the operating pressure of the primary membrane separation is 6.0-9.0 MPa, the operating temperature is 5-45 ℃, the primary membrane concentrated liquid is diluted and then subjected to secondary membrane separation, the dilution multiple is 1.0-3.0 times, the operating pressure of the secondary membrane separation is 6.0-9.0 MPa, the operating temperature is 5-45 ℃, secondary membrane dilute liquid is obtained, and the two membrane dilute liquids are combined for common treatment;
(2) carrying out evaporation concentration on the membrane diluted solution obtained in the step (1), wherein the temperature of an evaporation concentration kettle is 133-190 ℃ and the absolute pressure is 5-50 kPa to obtain a concentrated solution, the water content of the concentrated solution is not more than 0.05 wt%, the concentrated solution is subjected to lightness removing treatment, the lightness removing treatment is carried out by adopting a lightness removing tower, the theoretical number of tower plates of the lightness removing tower is not more than 40, the absolute pressure of the lightness removing treatment is 0.1-5.0 kPa, the temperature of the top of the tower is 65-133 ℃, the reflux ratio is not more than 10 to obtain a lightness removing kettle material, and the mass ratio of light components extracted from the top of the tower is 1.0-10.0 wt%;
(3) and (3) rectifying the light 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 at the top of the tower is 67-135 ℃, the reflux ratio is not more than 5, and a 1, 3-propylene glycol product is extracted from the top of the rectifying tower and accounts for 95.0-99.0 wt% of the light 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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| CN115521197A (en) * | 2022-10-28 | 2022-12-27 | 江苏扬农化工集团有限公司 | Method for concentrating 3-hydroxypropionaldehyde aqueous solution |
| CN115521197B (en) * | 2022-10-28 | 2023-10-13 | 江苏扬农化工集团有限公司 | Concentration method of 3-hydroxy propanal aqueous solution |
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