CN112608235A - PGMEA recovery method - Google Patents
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- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000011084 recovery Methods 0.000 title claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 96
- 239000002699 waste material Substances 0.000 claims abstract description 90
- 238000010992 reflux Methods 0.000 claims abstract description 38
- 238000002474 experimental method Methods 0.000 claims abstract description 22
- 238000009835 boiling Methods 0.000 claims abstract description 21
- 239000012528 membrane Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001704 evaporation Methods 0.000 claims abstract description 17
- 230000008020 evaporation Effects 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000004064 recycling Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 8
- 238000005374 membrane filtration Methods 0.000 claims abstract description 8
- 238000004587 chromatography analysis Methods 0.000 claims description 20
- 238000004821 distillation Methods 0.000 claims description 11
- 229920002545 silicone oil Polymers 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000011027 product recovery Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000002347 injection Methods 0.000 description 9
- 239000007924 injection Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229920002120 photoresistant polymer Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000005265 energy consumption Methods 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000004401 flow injection analysis Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012994 industrial processing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a PGMEA recycling method, which is suitable for PGMEA waste liquid generated by a liquid crystal display array process, and comprises the following steps: organic membrane filtration: filtering the PGMEA waste liquid through an organic membrane to remove water in the PGMEA waste liquid; true boiling point evaporation experiment: simulating and measuring the tower top temperature, the tower kettle temperature and the reflux liquid temperature of the rectifying tower, and obtaining a first-stage fraction and a second-stage fraction; and (3) rectification: taking a certain volume of PGMEA waste liquid to a gap type rectifying tower for heating, controlling the reflux ratio, and collecting front fraction, middle fraction and rear fraction at different reflux liquid temperatures. The recovery method has the advantages of low production cost, high product recovery rate, high purity, easy industrial treatment and good social and economic benefits.
Description
Technical Field
The invention relates to the technical field of waste liquid recovery, in particular to a PGMEA (polymer generated mea) recovery method.
Background
Liquid crystal displays (TFT-LCDs) have been rapidly developed from the 90 s of the 20 th century and gradually matured, and have been widely used in home appliances, computers and communication products because of their advantages of high definition, good image color, environmental protection, power saving, light weight, portability, and the like. The liquid crystal display array process generates a large amount of PGMEA (propylene glycol methyl ether acetate) waste liquid, and if the PGMEA waste liquid is directly discharged, the ecological environment is polluted and resources are wasted. Meanwhile, PGMEA is an important high-grade solvent, has strong dissolving capacity to polar and non-polar substances, and is widely applied to the fields of paint, printing ink, printing and dyeing, pesticide and the like. Therefore, the PGMEA can be separated and purified from the PGMEA waste liquid to realize resource regeneration, and the current circular economy development concept is met.
The current method for purifying PGMEA from PGMEA waste liquid mainly comprises extraction, adsorption, rectification and the like. However, the above methods all have certain disadvantages, such as: the extraction effect is not obvious, the consumption of PGMEA is too large during adsorption, and the load of the adsorbent is large and easy to damage.
Disclosure of Invention
In view of the above, there is a need to provide a method for recovering PGMEA from PGMEA waste liquid generated from liquid crystal display array process, which has high product recovery rate, high purity and easy industrial processing.
The invention provides a PGMEA recycling method, which comprises the following steps: organic membrane filtration: filtering the PGMEA waste liquid through an organic membrane to remove water in the PGMEA waste liquid; true boiling point evaporation experiment: heating the PGMEA waste liquid filtered by the organic membrane in a container, obtaining a first section of fraction when heating to a first temperature, continuously heating to a second temperature to obtain a second section of fraction, and respectively measuring the temperature above the PGMEA waste liquid, the temperature of the PGMEA waste liquid and the branch temperature of a Kjeldahl distillation head connected with the container when obtaining the first section of fraction and the second section of fraction so as to simulate and measure the tower top temperature, the tower kettle temperature and the reflux liquid temperature of the rectifying tower; and (3) rectification: adding the PGMEA waste liquid filtered by the organic membrane into a rectifying tower for heating, setting the tower kettle temperature of the rectifying tower as the measured tower kettle temperature, controlling the reflux ratio, and collecting front fraction, middle fraction and rear fraction at different reflux liquid temperatures. Wherein, the organic membrane filtration operation can reduce the water content in the PGMEA waste liquid to 0.5 percent, can greatly shorten the total reflux time in the subsequent rectification operation, and saves the energy consumption.
In one embodiment, the reflux ratio is 1 to 3: 1.
In one embodiment, the reflux ratio is 2: 1.
In one embodiment, the column bottom temperature is 126 ℃ to 148 ℃.
In one embodiment, the step of the real boiling point evaporation experiment comprises: taking a certain volume of PGMEA waste liquid filtered by the organic membrane into a three-neck flask, heating by adopting high-temperature heat-conducting silicone oil, connecting the three-neck flask with the Kjeldahl distillation head, and respectively placing three thermometers in the PGMEA waste liquid, above the PGMEA waste liquid and at a branch opening of the Kjeldahl distillation head so as to simulate and measure the temperature of a tower kettle, the temperature of a tower top and the temperature of reflux liquid of the rectifying tower.
In one embodiment, after the step of the real boiling point evaporation experiment and before the step of the rectification, the method further comprises the step of performing chromatographic analysis on the first-stage fraction and the second-stage fraction to determine the components contained in the first-stage fraction and the second-stage fraction and the content of the components.
In one embodiment, the step of filtering the organic membrane further comprises a step of performing chromatography on the waste PGMEA solution to determine the components and the content thereof contained in the waste PEMEA solution. After chromatographic analysis, the PGMEA waste liquid is detected to contain 8% of H by mass percent2O, 70% by mass of PGMEA, and 22% by mass of photoresist, wherein the photoresist comprises photosensitive resin.
In one embodiment, the step of chromatographing PGMEA effluent is preceded by a pre-treatment step: and (3) allowing the PGMEA waste liquid to stand and settle after passing through a filter so as to remove solid impurities.
In one possible embodiment, the recovery process recovers PGMEA at a recovery rate of 60-70% and recovered PGMEA at a purity of 95-98%.
The PGMEA recycling method provided by the invention is suitable for PGMEA waste liquid generated by a liquid crystal display array process, and the recycling method has the advantages of low production cost, high product recycling rate, high purity, easiness in industrial treatment and good social benefit and economic benefit.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the present invention belong. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of embodiments of the invention.
The invention provides a PGMEA recycling method, which comprises the following steps: organic membrane filtration: filtering the PGMEA waste liquid through an organic membrane to remove water in the PGMEA waste liquid; true boiling point evaporation experiment: heating the PGMEA waste liquid filtered by the organic membrane in a container, obtaining a first section of fraction when heating to a first temperature, continuously heating to a second temperature to obtain a second section of fraction, and respectively measuring the temperature above the PGMEA waste liquid, the temperature of the PGMEA waste liquid and the branch temperature of a Kjeldahl distillation head connected with the container when obtaining the first section of fraction and the second section of fraction so as to simulate and measure the tower top temperature, the tower kettle temperature and the reflux liquid temperature of the rectifying tower; and (3) rectification: adding the PGMEA waste liquid filtered by the organic membrane into a rectifying tower for heating, setting the tower kettle temperature of the rectifying tower as the measured tower kettle temperature, controlling the reflux ratio, and collecting front fraction, middle fraction and rear fraction at different reflux liquid temperatures.
The organic membrane filtration operation can reduce the water content in the PGMEA waste liquid to 0.5 percent, can greatly shorten the total reflux time in the subsequent rectification operation, and saves energy consumption. And (3) carrying out chromatographic analysis on the first-stage fraction and the second-stage fraction obtained in the real boiling point evaporation experiment, wherein the obtained physical property data can judge whether the rectification operation can be carried out to separate PGMEA. In addition, the actual boiling point evaporation experiment can determine the actual boiling point of the main components such as PGMEA in the waste liquid, and the measured temperature of the PGMEA waste liquid can be set as the temperature of the tower bottom of the rectifying tower, so that exact process parameters are provided for the subsequent amplified rectifying operation.
Further, the reflux ratio is 1-3: 1. Further, the reflux ratio was 2: 1. The reflux ratio is the ratio of the volume of the steam condensate returning to the tower bottom to the volume of the discharged steam condensate. The reflux ratio is too small, the distilled PGMEA water content is too high, and the industrial grade standard cannot be met; the reflux ratio is too large, the yield in the rectification process is too small, and the energy consumption is too high. Therefore, it is necessary to control the appropriate reflux ratio so that it can meet the industrial-grade standard and reduce the energy consumption.
In some embodiments, the column bottom temperature is 126 ℃ to 148 ℃.
In some embodiments, the step of the real boiling point evaporation experiment comprises: 200mL of PGMEA waste liquid filtered by the organic membrane is taken to be placed in a 500mL three-neck flask, high-temperature heat-conducting silicone oil is adopted for heating, the three-neck flask is connected with the Kjeldahl distillation head, and three thermometers are respectively placed in the PGMEA waste liquid, above the PGMEA waste liquid and at a branch opening of the Kjeldahl distillation head so as to simulate and measure the temperature of a tower kettle, the temperature of a tower top and the temperature of reflux liquid of the rectifying tower.
In some embodiments, after the step of the real boiling point evaporation experiment and before the step of the rectification, the method further comprises a step of performing chromatographic analysis on the first-stage fraction and the second-stage fraction to determine components contained in the first-stage fraction and the second-stage fraction and contents of the components. The chromatographic condition parameters are as follows: a polyethylene glycol quartz capillary chromatography column of 3m × 0.25mm × 1 μm; a hydrogen flame ionization detector; hydrogen flow 25mL/min, air flow 160mL/min, nitrogen flow 22 mL/min; the injection inlet temperature is 250 ℃, the detection chamber temperature is 240 ℃, the column temperature is 110 ℃, the split-flow injection is not carried out, the injection amount is 0.4 mu l, and the solvent is ethanol.
In some embodiments, the step of filtering the organic membrane further comprises a step of performing chromatography on the PGMEA waste liquid, wherein the chromatographic analysis condition parameters are as follows: a polyethylene glycol quartz capillary chromatography column of 3m × 0.25mm × 1 μm; a hydrogen flame ionization detector; hydrogen flow 25mL/min, air flow 160mL/min, nitrogen flow 22 mL/min; the injection inlet temperature is 250 ℃, the detection chamber temperature is 240 ℃, the column temperature is 110 ℃, the split-flow injection is not carried out, the injection amount is 0.4 mu l, and the solvent is ethanol. After chromatographic analysis, the PGMEA waste liquid is detected to contain 8% of H by mass percent2O, 70% by mass of PGMEA, and 22% by mass of photoresist, wherein the photoresist comprises photosensitive resin.
In some embodiments, the step of chromatographing PGMEA effluent is preceded by a pretreatment step: and (3) allowing the PGMEA waste liquid to stand and settle after passing through a filter so as to remove solid impurities.
In some embodiments, the recovery process recovers PGMEA at a recovery rate of 60-70% and recovered PGMEA at a purity of 95-98%.
The method for recovering PGMEA of the present invention will be explained below by means of specific examples.
Example 1
A pretreatment step: taking 20L of PGMEA waste liquid generated by the liquid crystal display array process, standing and settling for 1-2h, and then transferring to a filter for filtering to remove large-particle solid waste.
And (4) carrying out chromatographic analysis on the PGMEA waste liquid after the pretreatment step so as to measure the components and the content thereof in the PGMEA waste liquid. The chromatographic parameters were: a polyethylene glycol quartz capillary chromatography column of 3m (length) × 0.25mm (inner diameter) × 1 μm (film thickness); a hydrogen flame ionization detector; the hydrogen flow is 25mL/min, the air flow is 160mL/min, and the nitrogen flow is 22 mL/min; the injection port temperature is 250 ℃, the detection chamber temperature is 240 ℃, and the column temperature is 110 ℃; the sample is injected without shunting, the sample injection amount is 0.4 mu l, and the solvent is ethanol. Wherein, the non-shunting sample injection means that all samples enter a chromatographic column, and has higher analysis sensitivity.
The chromatographic analysis shows that the waste PGMEA solution contains H2O, PGMEA and photoresist, wherein the mass percent of each component is as follows: h2The content of O was 8%, the content of PGMEA was 70%, and the content of photoresist was 22%. The moisture determination adopts SKRS-07 volumetric method moisture determination instrument. The photoresist mainly comprises photosensitive resin. The photosensitive resin refers to a non-silver photosensitive material that produces an image by utilizing the property that some polymers have photodecomposition or the property that some monomers have photopolymerization or photocrosslinking.
Organic membrane filtration: the pretreated 20L PGMEA waste solution was filtered using an organic membrane from Nanjing Tian Membrane. After filtration, most of the water in the PGMEA waste liquid can be removed, and the water is reduced from 8% to 0.5%.
True boiling point evaporation experiment: taking 200mL of PGMEA waste liquid filtered by an organic membrane to a 500mL three-neck flask, heating by adopting high-temperature heat-conducting silicone oil, connecting the three-neck flask with a Kjeldahl head, and respectively placing three thermometers above (for example, 1cm above) the PGMEA waste liquid, in the PGMEA waste liquid and at a branch opening of the Kjeldahl head to simulate and measure the tower top temperature, the tower kettle temperature and the reflux liquid temperature of the rectifying tower; the first fraction was collected at a temperature of 98 c above the PGMEA effluent (i.e., the first temperature) and the second fraction was collected at a temperature of 143 c above the PGMEA effluent (i.e., the second temperature).
The actual boiling point evaporation experiment can determine the actual boiling points of the main components such as PGMEA in the waste liquid, and the measured temperature of the PGMEA waste liquid can be set as the temperature of the tower bottom of the rectifying tower, so that exact technological parameters are provided for the subsequent amplified rectifying operation. The rectification operation generally requires the temperature of the top of the column, the temperature of the bottom of the column and the temperature of the reflux liquid, which respectively correspond to the temperature above the PGMEA waste liquid, the temperature of the PGMEA waste liquid and the temperature of the branch opening of the kreb distillation head in the real boiling point evaporation experiment. The data for the true boiling point evaporation experiments are shown in table 1.
TABLE 1
The first and second fractions are distinguished by boiling point (i.e. temperature above PGMEA waste), the first fraction is 98 ℃ which evaporates first, the subsequent temperature begins to rise and no liquid is produced, and the second fraction is evaporated at 143 ℃. The yield of the first-stage fraction was 6.8%, i.e., the volume of the first-stage fraction was 13.6 mL; the yield of the second fraction was 90%, i.e., the volume of the second fraction was 180 mL. As can be seen from the data in Table 1, the column bottom temperature can be set within the range of 126 ℃ to 148 ℃ as a reference in the subsequent rectification operation.
And carrying out chromatographic analysis on the first-stage fraction and the second-stage fraction, wherein the chromatographic analysis condition parameters are as follows: a polyethylene glycol quartz capillary chromatography column of 3m × 0.25mm × 1 μm; a hydrogen flame ionization detector; the hydrogen flow is 25mL/min, the air flow is 160mL/min, and the nitrogen flow is 22 mL/min; the injection port temperature is 250 ℃, the detection chamber temperature is 240 ℃, and the column temperature is 110 ℃; the sample is injected without shunting, the sample injection amount is 0.4 mu l, and the solvent is ethanol. The chromatographic analysis is utilized to obtain the main component of the first-stage fraction which is water and contains a small amount of PGMEA, and the PGMEA is known to generate azeotropy with the water; the main component of the second-stage fraction is PGMEA. From the physical properties of PGMEA, it is found that PGMEA has a solubility in water of 18% and can be separated from water. The chromatographic analysis of the PGMEA waste liquid shows that the water content of the PGMEA waste liquid is 8%, and the water content of the PGMEA waste liquid is reduced to 0.5% after the PGMEA waste liquid is filtered by an organic membrane. From this, it was found that the separation of water, photoresist and PGMEA was achieved by rectification. Therefore, the PGMEA waste liquid can be subjected to rectification operation of the rectification column for subsequent amplification.
And (3) rectification: pumping 20L PGMEA waste liquid filtered by the organic membrane into a 20L clearance type rectifying tower by using a vacuum pump, fully refluxing for 0.5-1h, controlling the reflux ratio to be 2:1 when the gas-liquid mass transfer of the rectifying tower is balanced, and obtaining front fraction, middle fraction and back fraction at different reflux liquid temperatures. The reflux ratio is the ratio of the volume of the steam condensate returning to the tower bottom to the discharge volume of the steam condensate, and is too small, so that the distilled PGMEA has too high water content and cannot meet the industrial standard; the reflux ratio is too large, the yield in the rectification process is too small, and the energy consumption is too high. Therefore, the reflux ratio is properly controlled to be 2:1, so that the industrial standard can be met, and the energy consumption can be reduced. Because the organic membrane filtration operation can reduce the moisture in the waste liquid to 0.5%, the total reflux time in the rectification operation can be greatly reduced, and the energy consumption is saved. The experimental data of the rectification are shown in table 2.
TABLE 2
At different reflux temperatures, the front, middle and back fractions were collected. It can be understood that in the actual rectification operation, the condenser is arranged at the top of the rectification tower, the temperature of the top of the rectification tower cooled by the circulating cooling water is no longer the boiling point of the waste liquid (namely, the temperature above the PGMEA waste liquid), and the temperature of the top of the rectification tower in the actual rectification operation is greatly different from the temperature above the PGMEA waste liquid obtained in the actual boiling point evaporation experiment due to the fluctuation of the cooling water flow. The reason why the temperature of the reflux liquid in the distillation experiment was 40-44 ℃ which is greatly different from the branch temperature (104-.
The volume of the front cut was 2L and the yield was 10% (i.e. the volume ratio of front cut to PGMEA waste liquor). The content of PGMEA in the 2L front cut fraction is 20.00%, and the volume is 0.4L; the water content was 80.00% by volume, 1.6L. The volume of middle distillate was 6L and the yield was 30% (i.e. volume ratio of middle distillate to PGMEA waste liquor). In the 6L middle distillate, the content of PGMEA is 96.80%, and the volume is 5.808L; the water content was 3.20% by volume, 0.192L. The volume of the latter fraction was 6L and the yield was 30% (i.e. the volume ratio of the latter fraction to the waste PGMEA solution). In the 6L post-fraction, the content of PGMEA is 99.46%, and the volume is 5.968L; the water content was 0.54% by volume 0.032L. The total volume of recovered PGMEA was 12.176L with a recovery of 61%.
The results show that the recovery method can realize the separation and purification of the PGMEA waste liquid, the recovery rate can reach 61 percent, and the purity of the recovered PGMEA is measured to be 98 percent.
Comparative example 1
Extraction experiment: benzene, toluene, xylene, cyclohexane, methyl isobutyl ketone, ethanol and petroleum ether are selected as extracting agents. The experimental process is as follows, a proper amount of extracting agent is measured by using a measuring cylinder, then 100mL of PGMEA waste liquid is measured, the extracting agent and the waste liquid are moved to a 250mL separating funnel, the extracting agent and the waste liquid are fully mixed by shaking, the mixture is kept stand for 30 minutes, and after the solution is layered, the supernatant is taken to analyze the amount of PGMEA. Among them, benzene, toluene, xylene, ethanol and petroleum ether are poor in extraction effect, and cyclohexane and methyl isobutyl ketone are preferable, and the results are shown in table 3.
TABLE 3
As can be seen from table 3, the extraction rate of cyclohexane is 10.8%, and the extraction rate of methyl isobutyl ketone with good effect is only 20.4%, so the extraction method is not suitable for separating and purifying PGMEA from PGMEA waste liquid.
Comparative example 2
Adsorption experiment: silica gel and 3A/4A molecular sieve are selected for adsorption experiments.
Choose small hole
Silica gel for adsorption experiment of waste PGMEA liquid with relatively large pore size
Besides water molecules, the adsorbent can adsorb PGMEA during adsorption, so that PGMEA loss is large, and meanwhile, the load of the adsorbent is increased. Silica gel is therefore unsuitable as an adsorbent.
A3A/4A molecular sieve is selected for carrying out an adsorption experiment on the PGMEA waste liquid, the 3A/4A molecular sieve can selectively adsorb moisture, moisture removal of the PGMEA waste liquid can be realized, but the solution is acidic, so that the molecular sieve is dissolved and damaged.
Therefore, the adsorption industry is not suitable for recovering and purifying the waste PGMEA solution.
The PGMEA recycling method provided by the invention is suitable for PGMEA waste liquid generated by a liquid crystal display array process, and the recycling method has the advantages of low production cost, high product recycling rate, high purity, easiness in industrial treatment and good social benefit and economic benefit.
Although the embodiments of the present invention have been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the embodiments of the present invention.
Claims (9)
1. A PGMEA recycling method is characterized in that the recycling method is suitable for PGMEA waste liquid generated by a liquid crystal display array process, and the recycling method comprises the following steps:
organic membrane filtration: filtering the PGMEA waste liquid through an organic membrane to remove water in the PGMEA waste liquid;
true boiling point evaporation experiment: heating the PGMEA waste liquid filtered by the organic membrane in a container, obtaining a first section of fraction when heating to a first temperature, continuously heating to a second temperature to obtain a second section of fraction, and respectively measuring the temperature above the PGMEA waste liquid, the temperature of the PGMEA waste liquid and the branch temperature of a Kjeldahl distillation head connected with the container when obtaining the first section of fraction and the second section of fraction so as to simulate and measure the tower top temperature, the tower kettle temperature and the reflux liquid temperature of the rectifying tower;
and (3) rectification: adding the PGMEA waste liquid filtered by the organic membrane into a rectifying tower for heating, setting the tower kettle temperature of the rectifying tower as the measured tower kettle temperature, controlling the reflux ratio, and collecting front fraction, middle fraction and rear fraction at different reflux liquid temperatures.
2. The method for recovering PGMEA according to claim 1, wherein the reflux ratio is 1 to 3: 1.
3. The PGMEA recovery process of claim 2, wherein the reflux ratio is 2: 1.
4. The PGMEA recovery process according to claim 1, wherein the column bottom temperature is from 126 ℃ to 148 ℃.
5. The PGMEA recovery process of claim 1, wherein the step of the real boiling point evaporation experiment comprises: taking a certain volume of PGMEA waste liquid filtered by the organic membrane into a three-neck flask, heating by adopting high-temperature heat-conducting silicone oil, connecting the three-neck flask with the Kjeldahl distillation head, and respectively placing three thermometers in the PGMEA waste liquid, above the PGMEA waste liquid and at a branch opening of the Kjeldahl distillation head so as to simulate and measure the temperature of a tower kettle, the temperature of a tower top and the temperature of reflux liquid of the rectifying tower.
6. The PGMEA recovery method according to claim 1, wherein after the step of the real boiling evaporation test and before the step of the rectification, the method further comprises a step of analyzing the first-stage fraction and the second-stage fraction by chromatography to determine the components contained in the first-stage fraction and the second-stage fraction and the contents thereof.
7. The method of claim 1, wherein the step of filtering the organic membrane further comprises subjecting the waste PGMEA solution to chromatography to determine the components and their contents contained in the waste PGMEA solution.
8. The method for PGMEA recovery as claimed in claim 7, wherein said step of chromatographing the PGMEA effluent is preceded by a pre-treatment step of: the PGMEA waste liquid is settled and then passes through a filter to remove solid impurities.
9. The PGMEA recovery process of claim 1, wherein the PGMEA recovery process has a PGMEA recovery of 60-70% and a PGMEA purity of 95-98%.
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