CN112657339A - Electrodialysis device, electrodialysis system, and method for purifying glycolic acid raw material - Google Patents
Electrodialysis device, electrodialysis system, and method for purifying glycolic acid raw material Download PDFInfo
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- CN112657339A CN112657339A CN201910980076.8A CN201910980076A CN112657339A CN 112657339 A CN112657339 A CN 112657339A CN 201910980076 A CN201910980076 A CN 201910980076A CN 112657339 A CN112657339 A CN 112657339A
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Abstract
The present invention relates to the field of purification of glycolic acid products, and more particularly to an electrodialysis device, an electrodialysis system, and a method for purifying a glycolic acid raw material. The electrodialysis device comprises at least one electrodialysis unit, wherein the electrodialysis unit comprises a cathode, a cathode chamber, a membrane stack, an anode chamber and an anode which are sequentially arranged, the membrane stack comprises at least two groups of membrane groups which are sequentially arranged, each group of membrane group comprises a cation exchange membrane and an anion exchange membrane, a raw material chamber is formed between the cation exchange membrane and the anion exchange membrane of the same membrane group, a concentration chamber is formed between the two adjacent groups of membrane groups, the raw material chamber is filled with ion exchange resin, and the cation exchange membrane and/or the anion exchange membrane is/are selected from at least one of a polychlorotrifluoroethylene homogeneous ion exchange membrane, a polyvinylidene fluoride homogeneous ion exchange membrane and an alloy membrane. The refining method provided by the invention can obviously reduce the impurity content in the ethanol product, improve the purity of the glycolic acid product and reduce the loss rate of glycolic acid in the refining process.
Description
Technical Field
The present invention relates to the field of purification of glycolic acid products, and more particularly to an electrodialysis device, an electrodialysis system, and a method for purifying a glycolic acid raw material.
Background
High-quality glycolic acid is widely applied to the fields of organic synthesis, chemical cleaning, electroplating, spinning, leather, sterilization and the like. The prior synthesis process of glycolic acid mainly comprises a chloroacetic acid hydrolysis method and a methyl glycolate hydrolysis method. Among them, the hydrolysis method of methyl glycolate is affected by the selectivity and conversion rate of the upstream catalyst, and glycolic acid obtained by hydrolysis contains a small amount of impurities such as oxalic acid and acetic acid, and also contains some impurities such as metal ions due to the corrosivity of glycolic acid itself.
Because the chemical properties of the organic acid impurities are similar to those of glycolic acid, the refining and purification are difficult, and the prior art generally adopts the traditional refining methods such as crystallization, rectification and the like, and the processes have the problems of high energy consumption, low impurity removal rate, high glycolic acid loss rate and the like. Therefore, a more efficient method for purifying glycolic acid is desired.
Disclosure of Invention
The invention aims to provide an electrodialysis device, an electrodialysis system and a method for refining glycolic acid raw material, which aim to overcome the problems of high energy consumption, low impurity removal rate, high glycolic acid loss rate and the like in the prior art.
In order to achieve the above object, a first aspect of the present invention provides an electrodialysis apparatus, including at least one electrodialysis unit, the electrodialysis unit including a cathode, a cathode chamber, a membrane stack, an anode chamber, and an anode, the membrane stack including at least two sets of membrane groups, each set of membrane group being composed of a cation exchange membrane and an anion exchange membrane, a raw material chamber being formed between the cation exchange membrane and the anion exchange membrane of the same membrane group, and a concentration chamber being formed between the two adjacent sets of membrane groups, wherein the raw material chamber is filled with an ion exchange resin, and the cation exchange membrane and/or the anion exchange membrane is selected from at least one of a polychlorotrifluoroethylene homogeneous ion exchange membrane, a polyvinylidene fluoride homogeneous ion exchange membrane, and an alloy membrane.
In a second aspect, the present invention provides a method for purifying a glycolic acid raw material, comprising:
(i) introducing a glycolic acid feedstock into a feedstock compartment in an electrodialysis unit, introducing electrode compartment solutions into an anode compartment and a cathode compartment in the electrodialysis unit, and introducing deionized water into a concentration compartment in the electrodialysis unit, the electrodialysis unit being an electrodialysis unit according to the first aspect of the invention;
(ii) performing electrodialysis, circulating glycolic acid raw material in a raw material chamber, circulating electrode chamber solution in an anode chamber and a cathode chamber respectively, and circulating deionized water in a concentration chamber;
(iii) the purity of the first fluid exiting the outlet of the feed chamber is monitored, and when the first fluid exiting the outlet of the feed chamber has a predetermined purity, the circulation of glycolic acid feed material in the feed chamber is stopped and the first fluid is collected.
In a third aspect the invention provides an electrodialysis system comprising:
at least one electrodialysis unit, the electrodialysis unit being an electrodialysis unit according to the first aspect of the invention;
at least one neutralization unit for adjusting the first wastewater discharged from the concentration chamber to be neutral to obtain second wastewater, and the outlet of the concentration chamber is communicated with the concentration chamber;
at least one reverse osmosis unit for purifying the second wastewater, in communication with the neutralization unit; and
at least one nanofiltration unit for purifying a first fluid, communicating with the electrodialysis device through a feed compartment outlet;
preferably, the electrodialysis system further comprises at least one first fluid storage device located between the electrodialysis device and the nanofiltration unit.
In a fourth aspect, the present invention provides a method for purifying a glycolic acid starting material using the system according to the third aspect of the present invention, comprising:
(a) feeding glycolic acid raw material, electrode chamber solution and deionized water to an electrodialysis unit in an electrodialysis device for electrodialysis, and circulating the glycolic acid raw material, the electrode chamber solution and the deionized water;
(b) detecting the purity of the first fluid flowing out of the outlet of the raw material chamber, stopping the circulation of the glycolic acid raw material when the first fluid flowing out of the outlet of the raw material chamber has a preset purity, and collecting the first fluid; detecting the concentration of first wastewater discharged from an outlet of a concentration chamber, stopping the circulation of deionized water when the concentration of organic acid of the first wastewater discharged from the outlet of the concentration chamber reaches a set concentration, and collecting the first wastewater;
(c1) introducing the collected first fluid into a nanofiltration unit, and carrying out nanofiltration membrane filtration treatment to obtain a glycolic acid product and a concentrated solution;
(c2) introducing the collected first wastewater into a neutralization unit and a reverse osmosis unit in sequence, adjusting the pH of the first wastewater to be neutral in the neutralization unit to obtain second wastewater, and performing reverse osmosis treatment on the second wastewater in the reverse osmosis unit to obtain fresh water and concentrated water;
(d) circulating the concentrated solution to a feed compartment of an electrodialysis unit and circulating the fresh water to a concentration compartment of the electrodialysis unit.
The glycolic acid raw material is refined by the electrodialysis method by using the electrodialysis device, the operation is simple, the operation energy consumption is low, the impurity removal rate is high, the organic acid content is less than or equal to 40ppm, the metal ion (metal complex such as Fe, Cu and the like) content is less than or equal to 10ppm, and the organic acid and metal ion impurity removal rate is more than 95%; the glycolic acid yield is 96% by weight or more. In a preferred embodiment, the glycolic acid product obtained has an organic acid content (based on the total amount of oxalic acid and acetic acid) of less than or equal to 5ppm and metal ions (based on Fe)2+、Cu2+Total amount) of less than or equal to 5ppm, a glycolic acid product purity of 99.99%, and a glycolic acid yield of 99.87%.
Drawings
Fig. 1 is an embodiment of an electrodialysis cell in an electrodialysis unit according to the invention.
Fig. 2 is a schematic view of the filling of the feed compartment with ion exchange resin in one embodiment of the electrodialysis unit of the invention.
FIG. 3 is a schematic diagram of one embodiment of a system according to the present invention.
Description of the reference numerals
1 feedstock supply unit 7 first fluid storage device
2 electrode chamber solution supply unit 8 neutralization unit
3 deionized water supply unit 9 product tank
4 electrodialysis unit 10 effluent water sump
5 reverse osmosis unit 11 centrifugal pump
6 nanofiltration unit
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides an electrodialysis device, which comprises at least one electrodialysis unit, wherein the electrodialysis unit comprises a cathode, a cathode chamber, a membrane stack, an anode chamber and an anode which are sequentially arranged, the membrane stack comprises at least two groups of membrane groups which are sequentially arranged, each group of membrane group consists of a cation exchange membrane and an anion exchange membrane, a raw material chamber is formed between the cation exchange membrane and the anion exchange membrane of the same membrane group, and a concentration chamber is formed between the two adjacent groups of membrane groups.
Herein, the cation exchange membrane (CM) selectively passes cations unidirectionally, and the anion exchange membrane (AM) selectively passes anions unidirectionally.
According to the electrodialysis apparatus of the present invention, preferably, the cation exchange membrane and the anion exchange membrane each have a membrane pore size of 0.03 to 0.08 μm and a membrane resistance of 1 to 10 Ω/m2The acid-base tolerance values are respectively 1-14; more preferably, the cation exchange membrane has a pore diameter of 0.04-0.06 μm and a membrane resistance of 2-4 Ω/m2The acid-base tolerance value is 1-14; the membrane aperture of the anion exchange membrane is 0.04-0.06 mu m, and the membrane resistance is 2-4 omega/m2The acid-base tolerance value is 1-14.
As used herein, the term "acid-base tolerance" refers to the pH range at which the ion exchange membrane maintains normal function.
According to the electrodialysis apparatus of the present invention, preferably, the ion exchange resin contains a cation exchange resin and an anion exchange resin. Preferably, the cation exchange resin is selected from at least one of Na type styrene macroporous cation exchange resin, H type styrene macroporous cation exchange resin, Na type styrene gel type cation exchange resin and H type styrene gel type cation exchange resin; preferably, the anion exchange resin is selected from at least one of a Cl type styrene macroporous anion exchange resin, an OH type styrene macroporous anion exchange resin, a Cl type styrene gel type anion exchange resin, and an OH type styrene gel type anion exchange resin. In order to further improve the electrodialysis efficiency and further reduce the glycolic acid loss rate, it is preferable that the ion exchange resin is filled in a mixed-packed and/or layered-packed manner, more preferably layered-packed manner, in the raw material compartment. Fig. 1 shows an embodiment of an electrodialysis cell in the electrodialysis unit. Preferably, the weight ratio of the packed cation exchange resin to the anion exchange resin is 1: 1-3, preferably 1: 1-2.
Preferably, the filling proportion (volume) of the ion exchange resin in the feed chamber is 50% to 95%, preferably 80% to 95%.
Fig. 2 shows a schematic diagram of the filling of the ion exchange resin of the present invention in the raw material chamber, namely mixed filling and layered filling.
According to the electrodialysis device of the present invention, it is preferable that the electrodialysis device further includes a raw material supply unit that supplies raw material to the raw material chamber, an electrode chamber solution supply unit that supplies deionized water to the concentration chamber, and a deionized water supply unit that supplies electrode chamber solution to the anode chamber and the cathode chamber.
In a preferred embodiment, the cation exchange membrane is a polychlorotrifluoroethylene homogeneous ion exchange membrane, the pore diameter is 0.04-0.06 mu m, and the membrane resistance is 2-4 omega/m2The acid-base tolerance value is 1-14; the anion exchange membrane is a polychlorotrifluoroethylene homogeneous phase ion exchange membrane, the membrane aperture is 0.04-0.06 mu m, and the membrane resistance is 2-4 omega/m2The acid-base tolerance value is 1-14; the raw material chamber is filled with H-type styrene macroporous cation exchange resin and OH-type styrene macroporous anion exchange resin in a layered filling mode, and the filling proportion is 80-90%.
In a second aspect, the present invention provides a method for purifying a glycolic acid raw material, comprising:
(i) introducing a glycolic acid feedstock into a feedstock compartment in an electrodialysis unit, introducing electrode compartment solutions into an anode compartment and a cathode compartment in the electrodialysis unit, and introducing deionized water into a concentration compartment in the electrodialysis unit, the electrodialysis unit being an electrodialysis unit according to the first aspect of the invention;
(ii) performing electrodialysis, circulating glycolic acid raw material in a raw material chamber, circulating electrode chamber solution in an anode chamber and a cathode chamber respectively, and circulating deionized water in a concentration chamber;
(iii) the purity of the first fluid exiting the outlet of the feed chamber is monitored, and when the first fluid exiting the outlet of the feed chamber has a predetermined purity, the circulation of glycolic acid feed material in the feed chamber is stopped and the first fluid is collected.
According to the present invention, the glycolic acid starting material may be a glycolic acid material produced by any process, the glycolic acid material containing organic acid impurities such as oxalic acid, formic acid, acetic acid and the like, Fe2+、Cu2+And the like.
In this context, the determination of the content of organic acids (including oxalic acid, acetic acid) is carried out by High Performance Ion Chromatography (HPIC) by diluting the sample in equal proportions into ion chromatography, separating the dissociable ions on the ion exchange resin from the solute ions of the same charge in the mobile phase by reversible exchange and the difference in the affinity of the analyte solute for the exchanger. Comparing and calibrating the chromatogram corresponding to the analysis sample with the chromatogram of the known standard sample, and determining the type and the content of the organic acid, wherein the content is the percentage content of the organic acid in the total weight of the glycolic acid raw material.
In this context, metal ions (including Fe)2+、Cu2+) The content is measured by atomic emission spectrometer (ICP), and Fe is obtained2+、Cu2+The ICP standard of (1) was used as a standard (external standard method). Establishing an analysis method corresponding to the ions, selecting the strongest part of the signal as a detection point, Fe2+249.7nm and 208.9nm of Cu are selected2+Selecting 309.3nm and 292.4nm, drawing a standard curve, then formally measuring the sample, exposing and scanning each point for 3 times, and taking an average value. And (4) comparing with a standard curve to obtain the type and content of the metal ions, wherein the content refers to the percentage content of the metal ions in the total weight of the glycolic acid raw material.
According to the purification method of the present invention, in order to further remove impurities in a glycolic acid raw material while maintaining a low loss rate of glycolic acid, it is preferable that in the electrodialysis apparatus used, the cation exchange membrane is a polychlorotrifluoroethylene homogeneous ion exchange membrane having a pore diameter of 0.04 to 0.06. mu.m and a membrane resistance of 2 to 4. omega./m2The acid-base tolerance value is 1-14; the anion exchange membrane is a polychlorotrifluoroethylene homogeneous phase ion exchange membrane, the membrane aperture is 0.04-0.06 mu m, and the membrane resistance is 2-4 omega/m2The acid-base tolerance value is 1-14; the raw material chamber is formed by H-type styrene macroporous cation exchange resin and OH-type styrene macroporous anion exchangeThe resin is filled in a layered filling mode, and the filling proportion is 80-90%.
According to the refining method of the invention, preferably, the electrode chamber solution is an aqueous solution of sodium salt selected from but not limited to NaCl, NaHSO4、Na2SO4And NaNO3At least one of (1). In a preferred embodiment, the electrode compartment solution is NaCl or NaHSO in a concentration of 0.5 to 5 wt. -%4And (3) solution.
According to the purification method of the present invention, preferably, in step (ii), the conditions of the electrodialysis include: the voltage of the electrodialysis device is controlled to be 10-40V, and the current density is controlled to be 100-2The respective circulation amounts of the raw material chamber, the anode chamber, the cathode chamber and the concentration chamber are controlled to be 300-1500L/h.
In the present invention, in step (iii), the purity of the first fluid flowing out of the outlet of the raw material chamber can be detected by means of a common technical means in the field, such as sampling or online real-time monitoring.
According to the refining method of the present invention, preferably, in step (iii), the predetermined purity includes an organic acid impurity content of not more than 40 ppm.
According to the purification method of the present invention, when the first fluid flowing out of the outlet of the raw material chamber has a predetermined purity, the circulation of the glycolic acid raw material in the raw material chamber is stopped, and the first fluid is collected; in one embodiment, the first fluid is collected in a first fluid storage device.
According to the refining method of the invention, the method preferably further comprises filtering the collected first fluid by using a nanofiltration membrane, wherein the nanofiltration membrane preferably has a molecular weight cut-off of 200-500 to obtain the glycolic acid product. The nanofiltration membrane is used for removing organic small molecules in the first fluid by interception, such as decoloration.
In one embodiment, the nanofiltration membrane filtration is performed in a nanofiltration unit.
Preferably, the selective permeability of the nanofiltration membrane is greater than 97%. In this context, membrane permselectivity is understood to be the ratio of the glycolic acid content of the filtrate to the glycolic acid content of the feed solution.
In order to further improve the purity of the obtained glycolic acid product, preferably, the nanofiltration membrane is a polychlorotrifluoroethylene homogeneous ion exchange membrane.
Preferably, the operating pressure of the nanofiltration membrane filtration is 1-5 MPa.
In the process of nanofiltration membrane filtration treatment, the filtered solution is glycolic acid product, and the trapped solution is concentrated solution. In a preferred embodiment, the concentrated solution is recycled to the electrodialysis device feed compartment.
According to the refining method of the present invention, preferably, the method further comprises, during the electrodialysis in step (ii), collecting the first wastewater discharged from the outlet of the concentration chamber and adjusting the pH of the first wastewater to be neutral to obtain the second wastewater.
In a preferred embodiment, when the organic acid concentration of the first wastewater discharged from the outlet of the concentrating compartment reaches a set concentration, which may be 5 wt% to 15 wt%, for example 10 wt%, the first wastewater is collected to a neutralization unit, and the pH of the first wastewater is adjusted to neutral in the neutralization unit to obtain the second wastewater.
Preferably, the method further comprises subjecting the second wastewater to reverse osmosis treatment, preferably, the reverse osmosis operation pressure is 1-5MPa, to obtain fresh water. In one embodiment, the reverse osmosis treatment is performed in a reverse osmosis unit.
The reverse osmosis membrane used for the reverse osmosis treatment is not particularly limited as long as the reverse osmosis can be achieved. The reverse osmosis treatment process obtains fresh water and concentrated water, and the concentrated water is preferably introduced into a sewage tank for biochemical treatment or incineration treatment.
Preferably, the fresh water is recycled to a concentration compartment and/or a deionized water supply unit in the electrodialysis device.
According to the purification method of the present invention, preferably, in the glycolic acid raw material, the concentration of glycolic acid is 10 to 70% by weight, the mass fraction of oxalic acid is 0.5 to 2%, and the mass fraction of acetic acid is 0.1 to 0.5%; the mass fraction of the metal ions is 100-500 ppm; more preferably, the glycolic acid raw material has a glycolic acid concentration of 10 to 30% by weight.
In a third aspect the invention provides an electrodialysis system comprising:
at least one electrodialysis unit, the electrodialysis unit being an electrodialysis unit according to the first aspect of the invention;
at least one neutralization unit for adjusting the first wastewater discharged from the concentration chamber to be neutral to obtain second wastewater, and the outlet of the concentration chamber is communicated with the concentration chamber;
at least one reverse osmosis unit for purifying the second wastewater, in communication with the neutralization unit; and
at least one nanofiltration unit for purifying a first fluid, communicating with the electrodialysis device through a feed compartment outlet;
preferably, the electrodialysis system further comprises at least one first fluid storage device located between the electrodialysis device and the nanofiltration unit.
In the nanofiltration unit, a nanofiltration membrane is provided, preferably with a molecular weight cut-off of 200-. More preferably, the nanofiltration membrane has a permselectivity of greater than 97%.
In order to further improve the purity of the obtained glycolic acid product, preferably, the nanofiltration membrane is a polychlorotrifluoroethylene homogeneous ion exchange membrane.
Preferably, the system further comprises at least one centrifugal pump for accelerating the material transport.
Preferably, the system further includes a raw material supply unit supplying a raw material to the raw material chamber, an electrode chamber solution supply unit supplying deionized water to the concentration chamber, and a deionized water supply unit supplying an electrode chamber solution to the anode chamber and the cathode chamber.
In a fourth aspect, the present invention provides a method for purifying a glycolic acid starting material using the system according to the third aspect of the present invention, comprising:
(a) feeding glycolic acid raw material, electrode chamber solution and deionized water to an electrodialysis unit in an electrodialysis device for electrodialysis, and circulating the glycolic acid raw material, the electrode chamber solution and the deionized water;
(b) detecting the purity of the first fluid flowing out of the outlet of the raw material chamber, stopping the circulation of the glycolic acid raw material when the first fluid flowing out of the outlet of the raw material chamber has a preset purity, and collecting the first fluid; detecting the concentration of the first wastewater discharged from the outlet of the concentration chamber, stopping the circulation of deionized water when the concentration of the organic acid of the first wastewater discharged from the outlet of the concentration chamber reaches a set concentration, preferably 10 wt%, and collecting the first wastewater;
(c1) introducing the collected first fluid into a nanofiltration unit, and carrying out nanofiltration membrane filtration treatment to obtain a glycolic acid product and a concentrated solution;
(c2) introducing the collected first wastewater into a neutralization unit and a reverse osmosis unit in sequence, adjusting the pH of the first wastewater to be neutral in the neutralization unit to obtain second wastewater, and performing reverse osmosis treatment on the second wastewater in the reverse osmosis unit to obtain fresh water and concentrated water;
(d) the concentrated solution is circulated to the electrodialysis unit feed compartment and/or the feed supply unit, and the fresh water is circulated to the concentration compartment of the electrodialysis unit.
According to the present invention, the glycolic acid starting material may be a glycolic acid material produced by any process, the glycolic acid material containing organic acid impurities such as oxalic acid, formic acid, acetic acid and the like, Fe2+、Cu2+And the like.
Preferably, in the electrodialysis device used, the cation exchange membrane is a polychlorotrifluoroethylene homogeneous ion exchange membrane with a pore diameter of 0.04-0.06 μm and a membrane resistance of 2-4 Ω/m2The acid-base tolerance value is 1-14; the anion exchange membrane is a polychlorotrifluoroethylene homogeneous phase ion exchange membrane, the membrane aperture is 0.04-0.06 mu m, and the membrane resistance is 2-4 omega/m2The acid-base tolerance value is 1-14; the raw material chamber is filled with H-type styrene macroporous cation exchange resin and OH-type styrene macroporous anion exchange resin in a layered filling mode, and the filling proportion is 80-90%. Preferably, the electrode compartment solution is an aqueous solution of a sodium salt selected from, but not limited to, NaCl, NaHSO4、Na2SO4And NaNO3At least one of (1). In aIn a preferred embodiment, the electrode compartment solution is NaCl or NaHSO with a concentration of 0.5-5%4And (3) solution.
According to the present invention, in step (a), a glycolic acid raw material and deionized water are supplied to a raw material chamber and a concentration chamber of an electrodialysis unit in an electrodialysis device, respectively, an electrode chamber solution is supplied to an anode chamber and a cathode chamber of the electrodialysis unit in the electrodialysis device, respectively, electrodialysis is performed, and the glycolic acid raw material is circulated in the raw material chamber, the deionized water is circulated in the concentration chamber, and the electrode chamber solution is circulated in the anode chamber and the cathode chamber, respectively.
Preferably, in step (a), the conditions of the electrodialysis comprise: the voltage of the electrodialysis device is controlled to be 10-40V, and the current density is controlled to be 100-2The circulation amount of the raw material chamber, the anode chamber, the cathode chamber and the concentration chamber is controlled to be 300-1500L/h.
Preferably, in step (b), the predetermined purity includes an organic acid impurity content of no more than 40ppm by mass.
In one embodiment, the first fluid is collected in a first fluid storage device.
In step (c1), the collected first fluid is filtered in a nanofiltration unit using nanofiltration membranes, preferably having a molecular weight cut-off of 200 and a selective permeability of more than 97%.
Preferably, the operating pressure of the nanofiltration membrane filtration is 1-5 MPa.
In the process of nanofiltration membrane filtration treatment, the filtered solution is glycolic acid product, and the trapped solution is concentrated solution. Glycolic acid product is collected into a product tank and the concentrated solution is recycled to a feed compartment and/or feed unit in the electrodialysis device.
In a preferred embodiment, the first wastewater is collected into a neutralization unit, in which the pH of the first wastewater is adjusted to neutral, resulting in a second wastewater.
In the reverse osmosis unit, the second wastewater is subjected to reverse osmosis treatment, preferably at a reverse osmosis operating pressure of 1-5MPa, to obtain fresh water and concentrated water. The fresh water is recycled to a concentration compartment and/or a deionized water supply unit in the electrodialysis device. The concentrated water is preferably introduced into a sewage tank for biochemical treatment or incineration treatment.
According to the purification method of the present invention, preferably, in the glycolic acid raw material, the concentration of glycolic acid is 10 to 70% by weight, the mass fraction of oxalic acid is 0.5 to 2%, and the mass fraction of acetic acid is 0.1 to 0.5%; the mass fraction of the metal ions was 100-500 ppm. More preferably, the glycolic acid raw material has a glycolic acid concentration of 10 to 30% by weight.
Fig. 3 shows a schematic diagram of an embodiment of the system according to the invention, which comprises: a raw material supply unit 1, an electrode compartment solution supply unit 2, a deionized water supply unit 3, an electrodialysis unit 4, a reverse osmosis unit 5, a nanofiltration unit 6, a first fluid storage device 7, a neutralization unit 8, a product storage unit 9, a wastewater tank 10, and a centrifugal pump 11. A method for purifying a glycolic acid raw material using the system, comprising:
(a) glycolic acid raw material stored in the raw material supply unit 1 is pumped into a raw material chamber of an electrodialysis device by a centrifugal pump 11, electrode chamber solution stored in the electrode chamber solution supply unit 2 is pumped into an electrode chamber of the electrodialysis device by the centrifugal pump 11, and deionized water stored in the deionized water supply unit 3 is pumped into a concentration chamber of the electrodialysis device by the centrifugal pump to perform electrodialysis. The circulation amounts of the raw material chamber, the anode chamber, the cathode chamber and the concentration chamber are controlled to be set values.
(b) Detecting the purity of the first fluid flowing out of the outlet of the raw material chamber, and collecting the first fluid to a first fluid storage device 7 when the total content of organic acid and metal ions in the first fluid is not more than 40 ppm; detecting the concentration of the first wastewater discharged from the outlet of the concentration chamber, stopping the circulation of deionized water when the concentration of organic acid of the first wastewater discharged from the outlet of the concentration chamber reaches a set concentration, preferably 10 wt%, and collecting the first wastewater to a neutralization unit;
(c1) the first fluid collected by the first fluid storage means 7 is introduced into the nanofiltration unit 6 where it is filtered through a nanofiltration membrane. The filtered solution of the nanofiltration membrane is glycolic acid product, which is introduced into a product tank, the trapped solution is concentrated solution, and the concentrated solution is circulated back to the raw material chamber of the electrodialysis device.
(c2) In a neutralization unit, adding NaOH into the collected first wastewater for neutralization treatment until the pH value reaches 7 to obtain second wastewater; and introducing the second wastewater into a reverse osmosis unit for reverse osmosis treatment to obtain fresh water and concentrated water, circulating the fresh water into a concentration chamber of the electrodialysis device, and introducing the concentrated water into a sewage tank for biochemical or incineration treatment.
The beneficial effects of refining the glycolic acid raw material by using the method of the invention comprise:
(1) compared with the prior art, the electrodialysis device has small floor area and low operation energy consumption, and can quickly and effectively remove ionic impurities in the glycolic acid solution;
(2) the wastewater is effectively concentrated through reverse osmosis treatment, the external discharge capacity of the wastewater is greatly reduced, and the fresh water generated after treatment can be recycled to improve the process operation economy;
(3) nanofiltration membrane filtration belongs to a physical treatment process, the energy consumption is low, and the used permeable material can be cleaned and regenerated, so that the operation cost of the device is reduced, and the economy is good;
(4) the obtained glycolic acid product has high impurity removal rate, the content of organic acid is less than or equal to 40ppm, the content of metal ions (metal complexes such as Fe, Cu and the like) is less than or equal to 10ppm, and the impurity removal rate of organic acid and metal ions is more than 95 percent;
(5) the loss of glycolic acid is small and the yield of glycolic acid is 96 wt% or more.
The present invention will be described in detail below by way of examples.
Examples the test methods involved in the comparative examples are as follows:
1. the method for calculating the yield of glycolic acid is as follows:
the glycolic acid yield is (mass of glycolic acid product × mass fraction of glycolic acid in glycolic acid product)/(mass of raw material liquid × mass fraction of glycolic acid in raw material liquid) × 100%.
2. The calculation method of the purity of the glycolic acid product comprises the following steps:
glycolic acid product purity ═ (glycolic acid mass in glycolic acid product-organic acid mass in glycolic acid product-metal ion mass in glycolic acid product)/glycolic acid mass in glycolic acid product × 100%.
3. The method for measuring the chromaticity of the glycolic acid product comprises the following steps:
and (3) selecting a corresponding chromaticity standard by using a chromaticity instrument, taking the Gardner chromaticity standard as an example, and automatically comparing a glycolic acid product in a chromaticity instrument cuvette with a self-contained chromaticity standard liquid of a chromatograph to obtain a chromaticity value under the standard.
The glycolic acid starting material used in the examples and comparative examples was a glycolic acid solution having a concentration of 70% by weight, and had a pale yellow color, an organic acid content of 1% (based on the total amount of oxalic acid and acetic acid), and a metal ion content of 300ppm (based on Fe)2+、Cu2+Total amount).
The materials used in the examples and comparative examples are as follows:
the alloy film stack is purchased from Zhejiang Qianqiu environmental protection water treatment Co., Ltd;
the polytrifluorochloroethylene homogeneous ion exchange membrane is purchased from Zhejiang Qianqiu environmental protection water treatment Co., Ltd;
the polyacrylonitrile homogeneous membrane is purchased from Zhejiang Qianqiu environmental protection water treatment Co., Ltd;
the polyphenol sulfonic acid homogeneous membrane is purchased from Zhejiang Qianqiu environmental protection water treatment Co., Ltd;
the Na type styrene gel type cation exchange resin is purchased from Jiangsu Suqing water treatment engineering group, and has the brand number of 001x 7;
the Cl-type styrene gel anion exchange resin is purchased from Jiangsu Suqing water treatment engineering group, ltd, and has the brand number of 201x 4;
the H-type styrene macroporous cation exchange resin is purchased from Jiangsu Suqing water treatment engineering group, Inc., and has the brand number of 001x 7H;
the OH type styrene macroporous anion exchange resin is purchased from Jiangsu Suqing water treatment engineering group, Inc., and has the brand number of 201x4 OH;
the polychlorotrifluoroethylene homogeneous exchange membrane used as the nanofiltration membrane is purchased from Zhejiang Qianqiu environmental protection water treatment Co.
Example 1
The glycolic acid starting material was purified using the system shown in FIG. 3. Wherein the membrane stack used in the electrodialysis unit is an alloy membrane stack (the membrane aperture is 0.05 μm, and the membrane resistance is 3.5 omega/m2And the acid-base tolerance value is 1-14). The raw material chamber is filled with Na type styrene gel type cation exchange resin and Cl type styrene gel type anion exchange resin in a weight ratio of 1:1 (the filling ratio is 85 volume percent, and the filling mode is mixed filling); the nanofiltration membrane used in the nanofiltration unit is a polychlorotrifluoroethylene homogeneous exchange membrane (the molecular weight cut-off is 300, and the membrane selective permeability is 97%).
(a) The glycolic acid raw material stored in the raw material supply unit 1 was introduced into the raw material chamber of the electrodialysis device by the centrifugal pump 11, the 1 wt% NaCl solution stored in the electrode chamber solution supply unit 2 was introduced into the electrode chamber of the electrodialysis device by the centrifugal pump 11, and the deionized water stored in the deionized water supply unit 3 was introduced into the concentration chamber of the electrodialysis device by the centrifugal pump to conduct electrodialysis (the voltage of the electrodialysis device was controlled to 20V, and the current density was 200A/m)2). The respective circulation amounts of the raw material chamber, the anode chamber, the cathode chamber and the concentration chamber are controlled to be 300L/h.
(b) Detecting the purity of the first fluid flowing out of the outlet of the raw material chamber, and collecting the first fluid to a first fluid storage device 7 when the total content of organic acid and metal ions in the first fluid is not more than 40 ppm; detecting the concentration of first wastewater discharged from an outlet of the concentration chamber, stopping the circulation of deionized water when the concentration of organic acid in the first wastewater discharged from the outlet of the concentration chamber reaches 10 wt%, and collecting the first wastewater to a neutralization unit;
(c1) and introducing the first fluid collected by the first fluid storage device 7 into a nanofiltration unit 6, and filtering the first fluid by using a nanofiltration membrane in the nanofiltration unit, wherein the operating pressure of the nanofiltration membrane is controlled to be 2 MPa. The filtered solution of the nanofiltration membrane is glycolic acid product, which is introduced into a product tank, the trapped solution is concentrated solution, and the concentrated solution is circulated back to the raw material chamber of the electrodialysis device.
(c2) In a neutralization unit, adding NaOH into the collected first wastewater for neutralization treatment until the pH value reaches 7 to obtain second wastewater; and introducing the second wastewater into a reverse osmosis unit for reverse osmosis treatment, controlling the reverse osmosis operation pressure to be 2MPa, performing reverse osmosis treatment to obtain fresh water and concentrated water, circulating the fresh water into a concentration chamber of an electrodialysis device, and introducing the concentrated water into a sewage tank for biochemical treatment or incineration treatment.
The glycolic acid product obtained contained 25ppm of organic acid (based on the total amount of oxalic acid and acetic acid) and 25ppm of metal ions (based on Fe)2+、Cu2+Total amount) of 8ppm, a liquid color of 15, and a glycolic acid product purity of 99.86%. Finally, the yield of glycolic acid was 97.14%.
Example 2
Glycolic acid starting material was purified by the method described in example 1, except that the Na-type styrene gel type cation exchange resin and the Cl-type styrene gel type anion exchange resin were filled in layers in the starting material chamber, and the same was applied to example 1.
The glycolic acid product finally obtained had an organic acid content (based on the total amount of oxalic acid and acetic acid) of 21ppm and metal ions (based on Fe)2+、Cu2+Total amount) of 6ppm, a liquid color of 15, and a glycolic acid product purity of 99.92%. Finally, the yield of glycolic acid was 98.08%.
Example 3
Glycolic acid starting material was purified by the method described in example 1, except that an H-type styrene macroporous cation exchange resin and an OH-type styrene macroporous anion exchange resin were used in a weight ratio of 1:2 in place of the Na-type styrene gel cation exchange resin and the Cl-type styrene gel anion exchange resin, and a layered packing method was used, and the same as in example 1 was repeated.
The glycolic acid product finally obtained had an organic acid content (based on the total amount of oxalic acid and acetic acid) of 16ppm and metal ions (based on Fe)2+、Cu2+Total amount) of 5ppm, a liquid color of 15, and a glycolic acid product purity of 99.94%. Finally, the yield of glycolic acid was 98.63%.
Example 4
Glycolic acid feedstock was purified as described in example 3, except that the electrodialysis cell used a polychlorotrifluoroethylene homogeneous ion exchange membrane stack (membrane pore size 0.04 μm, membrane resistance 2 Ω/m)2Acid baseTolerance value of 1 to 14), the rest is the same as in example 3.
The glycolic acid product finally obtained had an organic acid content (in terms of oxalic acid and acetic acid) of 8ppm and metal ions (in terms of Fe)2 +、Cu2+Total amount) of 2ppm, a liquid color of 15, and a glycolic acid product purity of 99.98%. Finally, the yield of glycolic acid was 99.28%.
Example 5
The glycolic acid raw material was purified by the method described in example 4, except that the concentration of the glycolic acid solution in the raw material supply unit was adjusted to 10 to 30%, and the procedure was the same as in example 4.
The glycolic acid product finally obtained had an organic acid content (in terms of oxalic acid and acetic acid) of 2ppm and metal ions (in terms of Fe)2 +、Cu2+Total amount) of 1ppm, a liquid color of 15, and a glycolic acid product purity of 99.99%. Finally, the yield of glycolic acid was 99.87%.
Example 6
The glycolic acid raw material was purified by the method described in example 1, except that the weight ratio of the Na type styrene gel type cation exchange resin and the Cl type styrene gel type anion exchange resin filled in the raw material chamber was 1:4, and the rest was the same as example 1.
The glycolic acid product finally obtained had an organic acid content (in terms of oxalic acid and acetic acid) of 2ppm and metal ions (in terms of Fe)2 +、Cu2+Total amount) of 1ppm, a liquid color of 15, and a glycolic acid product purity of 99%. Finally, the yield of glycolic acid was 96.5%.
Comparative example 1
Glycolic acid starting material was purified by the method described in reference example 1, except that the feed chamber was not filled with an ion exchange resin, and the method was the same as in example 1.
The glycolic acid product obtained finally had an organic acid content (measured as oxalic acid and acetic acid) of 28ppm and metal ions (measured as Fe)2+、Cu2+Total amount) of 8ppm, a liquid color of 15, and a glycolic acid product purity of 99.73%. Finally, the yield of glycolic acid was 93.27%.
Comparative example 2
Glycolic acid feedstock was purified as described in example 1, except that the membrane stack used was a polyacrylonitrile homogeneous membrane stack, which was otherwise the same as in example 1.
The glycolic acid product finally obtained had an organic acid content (calculated as oxalic acid and acetic acid) of 34ppm and metal ions (calculated as Fe)2+、Cu2+Total amount) of 13ppm, a liquid color of 15, and a glycolic acid product purity of 99.61%. Finally, the yield of glycolic acid was 89.63%.
Comparative example 3
Glycolic acid feedstock was purified according to the procedure described in example 1, except that the membrane stack used was a polyphenol sulfonic acid homogeneous membrane stack and the feed compartment was not filled with ion exchange resin.
The glycolic acid product finally obtained had an organic acid content (in terms of oxalic acid and acetic acid) of 37ppm and metal ions (in terms of Fe)2+、Cu2+Total amount) of 16ppm, a liquid color of 15, and a glycolic acid product purity of 99.56%. Finally, the yield of glycolic acid was 89.38%.
The refining method of the glycolic acid is simple to operate and low in operation energy consumption; the electrodialysis stack used in the present invention has a synergistic effect with the ion exchange resin packed in the feed compartment with respect to increasing the purity of the glycolic acid product. For example, in the glycolic acid products obtained in examples 1 to 6 of the present invention, the organic acid (in terms of the total amount of oxalic acid and acetic acid) and the metal ion (in terms of Fe) were contained in comparison with those in comparative examples 1 to 32+、Cu2+Total amount) is significantly lower; moreover, the purity of the glycolic acid product is more than 99 percent, the yield of the glycolic acid is more than 96 percent, and the glycolic acid has obviously better refining and purifying effects.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. The electrodialysis device comprises at least one electrodialysis unit, wherein the electrodialysis unit comprises a cathode, a cathode chamber, a membrane stack, an anode chamber and an anode which are sequentially arranged, the membrane stack comprises at least two groups of membrane groups which are sequentially arranged, each group of membrane group comprises a cation exchange membrane and an anion exchange membrane, a raw material chamber is formed between the cation exchange membrane and the anion exchange membrane of the same membrane group, and a concentration chamber is formed between the two adjacent groups of membrane groups.
2. An electrodialysis unit according to claim 1, wherein the cation exchange membrane and the anion exchange membrane each have a membrane pore size of 0.03 to 0.08 μm and a membrane resistance of 1 to 10 Ω/m2The acid-base tolerance values are each from 1 to 14.
3. An electrodialysis unit according to claim 1 or 2, wherein the ion exchange resin comprises a cation exchange resin and an anion exchange resin,
preferably, the cation exchange resin is selected from at least one of Na type styrene macroporous cation exchange resin, H type styrene macroporous cation exchange resin, Na type styrene gel type cation exchange resin and H type styrene gel type cation exchange resin;
preferably, the anion exchange resin is selected from at least one of a Cl type styrene macroporous anion exchange resin, an OH type styrene macroporous anion exchange resin, a Cl type styrene gel type anion exchange resin, and an OH type styrene gel type anion exchange resin.
Preferably, in the raw material chamber, the ion exchange resin is filled in a mixed filling and/or layered filling manner;
preferably, in the raw material chamber, the filling proportion of the ion exchange resin is 50% -95%,
preferably, the weight ratio of the packed cation exchange resin to the anion exchange resin is 1: 1-3.
4. An electrodialysis unit according to any one of claims 1 to 3, further comprising a raw material supply unit that supplies raw material to the raw material compartment, an electrode compartment solution supply unit that supplies deionized water to the concentration compartment, and a deionized water supply unit that supplies electrode compartment solutions to the anode compartment and the cathode compartment.
5. A method for refining a glycolic acid starting material, the method comprising:
(i) introducing a glycolic acid feedstock into a feedstock compartment in an electrodialysis unit, introducing an electrode compartment solution into an anode compartment and a cathode compartment in the electrodialysis unit, and introducing deionized water into a concentration compartment in the electrodialysis unit, the electrodialysis unit being as claimed in any one of claims 1 to 4;
(ii) performing electrodialysis, circulating glycolic acid raw material in a raw material chamber, circulating electrode chamber solution in an anode chamber and a cathode chamber respectively, and circulating deionized water in a concentration chamber;
(iii) the purity of the first fluid exiting the outlet of the feed chamber is monitored, and when the first fluid exiting the outlet of the feed chamber has a predetermined purity, the circulation of glycolic acid feed material in the feed chamber is stopped and the first fluid is collected.
6. The refining method of claim 5, wherein, in step (b), the conditions of electrodialysis comprise: the voltage of the electrodialysis device is controlled to be 10-40V, and the current density is controlled to be 100-2The respective circulation amounts of the raw material chamber, the anode chamber, the cathode chamber and the concentration chamber are controlled to be 300-1500L/h.
7. The refining method of claim 5 or 6, wherein, in step (c), the predetermined purity includes an organic acid impurity content of no greater than 40 ppm.
8. Refining process according to any one of claims 5-7, further comprising filtering the collected first fluid with a nanofiltration membrane, preferably having a molecular weight cut-off of 200 and 500, to obtain glycolic acid product.
9. The refining method according to any one of claims 5 to 8, further comprising, during the electrodialysis in step (b), collecting the first wastewater discharged from the concentration chamber and adjusting the pH of the first wastewater to neutrality to obtain a second wastewater;
preferably, the second wastewater is subjected to reverse osmosis treatment, preferably, the reverse osmosis operation pressure is 1-5MPa, and fresh water is obtained;
preferably, the fresh water is recycled to the concentration compartment in the electrodialysis device.
10. The purification process according to any one of claims 5 to 9, wherein the glycolic acid raw material contains 10 to 70% by mass of glycolic acid, 0.5 to 2% by mass of oxalic acid, and 0.1 to 0.5% by mass of acetic acid; the mass fraction of the metal ions was 100-500 ppm.
11. An electrodialysis system, comprising:
at least one electrodialysis unit, said electrodialysis unit being an electrodialysis unit according to any one of claims 1 to 4;
at least one neutralization unit for adjusting the first wastewater discharged from the concentration chamber to be neutral to obtain second wastewater, and the outlet of the concentration chamber is communicated with the concentration chamber;
at least one reverse osmosis unit for purifying the second wastewater, in communication with the neutralization unit; and
at least one nanofiltration unit for purifying a first fluid, communicating with the electrodialysis device through a feed compartment outlet;
preferably, the electrodialysis system further comprises at least one first fluid storage device located between the electrodialysis device and the nanofiltration unit.
12. A method of refining a glycolic acid feedstock using the system of claim 11, comprising:
(a) feeding glycolic acid raw material, electrode chamber solution and deionized water to an electrodialysis unit in an electrodialysis device for electrodialysis, and circulating the glycolic acid raw material, the electrode chamber solution and the deionized water;
(b) detecting the purity of the first fluid flowing out of the outlet of the raw material chamber, stopping the circulation of the glycolic acid raw material when the first fluid flowing out of the outlet of the raw material chamber has a preset purity, and collecting the first fluid; detecting the concentration of first wastewater discharged from an outlet of a concentration chamber, stopping the circulation of deionized water when the concentration of organic acid of the first wastewater discharged from the outlet of the concentration chamber reaches a set concentration, and collecting the first wastewater;
(c1) introducing the collected first fluid into a nanofiltration unit, and carrying out nanofiltration membrane filtration treatment to obtain a glycolic acid product and a concentrated solution;
(c2) introducing the collected first wastewater into a neutralization unit and a reverse osmosis unit in sequence, adjusting the pH of the first wastewater to be neutral in the neutralization unit to obtain second wastewater, and performing reverse osmosis treatment on the second wastewater in the reverse osmosis unit to obtain fresh water and concentrated water;
(d) circulating the concentrated solution to a feed compartment of an electrodialysis unit and circulating the fresh water to a concentration compartment of the electrodialysis unit.
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