CN114573442A - Treatment method of reaction waste liquid in polyphenyl ether synthesis process - Google Patents
Treatment method of reaction waste liquid in polyphenyl ether synthesis process Download PDFInfo
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- CN114573442A CN114573442A CN202011373411.7A CN202011373411A CN114573442A CN 114573442 A CN114573442 A CN 114573442A CN 202011373411 A CN202011373411 A CN 202011373411A CN 114573442 A CN114573442 A CN 114573442A
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- reaction
- waste liquid
- calcium
- citric acid
- reaction waste
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 84
- 239000007788 liquid Substances 0.000 title claims abstract description 77
- 239000002699 waste material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229920013636 polyphenyl ether polymer Polymers 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 90
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 claims abstract description 39
- 239000001354 calcium citrate Substances 0.000 claims abstract description 39
- 235000013337 tricalcium citrate Nutrition 0.000 claims abstract description 39
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 32
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 32
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000292 calcium oxide Substances 0.000 claims abstract description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000012673 precipitation polymerization Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- 238000005406 washing Methods 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 26
- 239000012065 filter cake Substances 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 229920001955 polyphenylene ether Polymers 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 238000004821 distillation Methods 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 9
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 8
- 239000005750 Copper hydroxide Substances 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- -1 alkaline earth metal salt Chemical class 0.000 abstract description 13
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 3
- 150000001340 alkali metals Chemical class 0.000 abstract description 2
- 230000002572 peristaltic effect Effects 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000003756 stirring Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 8
- 229910001431 copper ion Inorganic materials 0.000 description 8
- 238000005485 electric heating Methods 0.000 description 8
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 229920006380 polyphenylene oxide Polymers 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention belongs to the field of treatment of chemical reaction waste liquid, and particularly relates to a treatment method of reaction waste liquid in a polyphenyl ether synthesis process, which comprises the following steps: one or two of calcium hydroxide or calcium oxide is/are added into reaction waste liquid generated when polyphenyl ether is prepared by a precipitation polymerization method, and citric acid in the reaction waste liquid is converted into calcium citrate to be removed. The invention discovers that the reason for increasing the viscosity of the polyphenyl ether reaction waste liquid is the alkali metal or partial alkaline earth metal salt of citric acid for the first time, so that the problem that the reaction waste liquid is easy to block a pipeline and damage a pump bearing is solved by removing the citric acid in the reaction waste liquid by adding calcium hydroxide or calcium oxide.
Description
Technical Field
The invention belongs to the field of treatment of chemical reaction waste liquid, and particularly relates to a treatment method of reaction waste liquid in a polyphenyl ether synthesis process.
Background
The polyphenyl ether is a material with high molecular chain rigidity, excellent mechanical strength, high modulus, and outstanding creep resistance and water resistance. The glass transition temperature (Tg) is about 210 ℃, the upper limit of the continuous use temperature is 120 ℃, the melting temperature is about 300 ℃, and the decomposition occurs above 350 ℃. Light weight, no toxicity, low hydroscopicity, fire resistance and self extinguishing. The polyphenyl ether is formed by oxidative coupling of 2, 6-xylenol under the action of a catalyst and oxygen. The polymerization method of polyphenylene ether is classified into two methods, precipitation polymerization and solution polymerization. The precipitation method is that 2, 6-xylenol reacts in aromatic compound or alcohol solvent under the condition that cuprous salt, cupric halide salt and organic amine react to generate copper-amine complex or cupric-amine complex is used as catalyst to generate polyphenyl ether. After the reaction is finished, adding the copper in the complexing reactants such as citric acid, EDTA, acetic acid and the like to terminate the reaction. The mother liquor of the reaction and the materials for washing the polyphenyl ether contain residual unreacted 2, 6-xylenol, organic amine, water generated by the process, copper complex, halogen ions and the like.
In order to recover the useful materials in the reaction mother liquor and the washing liquid materials, an alkaline solution is added to effectively recover the useful materials. The alkaline solution may be soluble alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, etc. In the production, the mixed liquid of the mother liquid and the washing liquid is often precipitated in the form of crystals on the wall of the heater during the heating distillation treatment, which is easy to cause the blockage of the reboiler pipeline. During the conveying process of the mechanical pump, pipeline blockage and pump bearing damage are easily caused. Causing material leakage and environmental pollution. The equipment maintenance frequency is increased, the equipment needs to be maintained for 3-4 days generally, the maintenance cost of the equipment is high, and how to solve the problems is not an effective method in the prior art.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for treating mother liquor and washing waste liquor generated in the process of producing polyphenylene oxide by a precipitation method.
The method comprises the following steps: one or two of calcium hydroxide or calcium oxide is/are added into reaction waste liquid generated when polyphenyl ether is prepared by a precipitation polymerization method, and citric acid in the reaction waste liquid is converted into calcium citrate to be removed.
The present inventors have unexpectedly found that, although addition of an alkaline material such as sodium hydroxide, potassium hydroxide or sodium carbonate to a mixed system of a mother liquor of polyphenylene ether and a washing liquid can remove materials such as citric acid and organic amine, the resultant sodium citrate or potassium citrate cannot be effectively separated from the above-mentioned organic system, and tends to increase the viscosity of the waste liquid system. And calcium hydroxide or calcium oxide can generate suspended matters immediately after reacting with citric acid, is easy to separate from an organism system, and cannot cause the viscosity of the system to increase, so that the calcium oxide or the calcium oxide is added into the system to remove the citric acid in the system during the waste liquid removing process so as to reduce the influence on the operation of equipment.
Preferably, the reaction waste liquid is a mixed liquid of a reaction mother liquid and a washing liquid of polyphenylene ether.
Preferably, the reaction mother liquor and the washing solution of polyphenylene ether are obtained by the following steps: the synthesis method of the polyphenyl ether is characterized in that a mixed solution of methanol and toluene is used as a reaction solvent, a copper-amine complex is used as a catalyst, and the polyphenyl ether is prepared by polymerization reaction; after the reaction is finished, adding citric acid for end capping, and stopping the reaction; separating the polyphenyl ether to obtain reaction mother liquor;
washing the polyphenylene ether with methanol to obtain a washing solution of the polyphenylene ether.
Preferably, the amount of the calcium hydroxide or calcium oxide added is based on the removal of all materials to be treated which can react with the calcium hydroxide or calcium oxide in the reaction solution. The reaction waste liquid to be treated usually contains morpholine and other components, and other materials to be treated can be removed together by adding sufficient calcium hydroxide or calcium oxide, so that the treatment process can be simplified.
Preferably, the temperature of the reaction system is controlled to be 60-70 ℃ in the process of removing the citric acid. At the above temperature, a sufficient reaction of citric acid with calcium hydroxide or calcium oxide can be achieved.
As a preferable operation mode, the invention further provides a treatment method of the reaction waste liquid, specifically, the reaction waste liquid is treated in a distillation mode, calcium hydroxide or calcium oxide is firstly added into a distillation reactor, then part of the waste liquid to be treated is added into the distillation reactor, the temperature of the reactor is raised to 60-70 ℃, and the reaction waste liquid is distilled.
Preferably, the residues of the reaction are centrifuged to obtain a filter cake, the filter cake is washed by toluene to remove residual low molecular polyether and organic matters, then the filter cake is washed by deionized water to remove soluble bromine salt, and finally the filter cake is washed by a citric acid solution to remove calcium hydroxide and copper hydroxide, so that the calcium citrate meeting the discharge requirement is obtained. Through the treatment, organic matters and other materials which are adhered to the surface of the calcium citrate and do not meet the requirement of environmental emission can be sufficiently removed, so that the calcium citrate meets the requirement of environmental emission, and can be prepared into citric acid after being acidified for recycling.
The invention has the following beneficial effects:
1) the invention firstly discovers that the reason for causing the viscosity increase of the polyphenyl ether reaction waste liquid is that the alkali metal salt or alkaline earth metal salt of citric acid reacts with the citric acid in the solution to generate calcium citrate after being added with calcium oxide or calcium hydroxide, and the calcium citrate belongs to insoluble matters in methanol and toluene solution and is suspended in the solution after being added, so that calcium citrate crystals cannot be separated out along with the evaporation of the solution in the distillation process, thereby providing a scheme for removing the citric acid in the solution by adding the calcium hydroxide or the calcium oxide and solving the problems of easy pipeline blockage and pump bearing damage in the reaction waste liquid treatment process in the industrial production process.
2) Aiming at the generated calcium citrate precipitate, the invention further extracts a purification method, can obtain pure calcium citrate, and is beneficial to the cyclic utilization of citric acid and the environment-friendly industrial production.
3) For the equipment operation period, the calcium hydroxide or calcium oxide is used as a precipitator, so that the lower equipment utilization rate caused by other alkali metals or alkaline earth metals is avoided. In addition, calcium hydroxide or calcium oxide is added as a precipitator, so that the cost of the precipitator and the consumption of the solvent recovery steam of the device can be reduced.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The reaction waste liquid in the embodiment is prepared by a precipitation method using methanol and toluene as solvents and using a copper-amine complex as a catalyst. And after the polymerization is finished, adding citric acid for end capping, terminating the reaction, and separating the polyphenyl ether to obtain a mother solution. Then, the polyphenylene ether obtained after washing was filtered with methanol several times, and then the washing liquid was mixed with the reaction mother liquor to obtain a reaction waste liquid.
Example 1
The embodiment relates to a method for treating reaction waste liquid in polyphenylene ether synthesis, which comprises the following steps:
the reaction waste liquid related to this example had the composition shown in Table 1 a:
TABLE 1a
| Item | Water (W) | Methanol | Morpholine | Toluene | Citric acid | Bromine ion | Copper ion |
| Content (wt.) | 2.63％ | 61.52％ | 0.21％ | 35.62％ | 0.11％ | 0.053％ | 0.03％ |
The three-necked flask was placed in an electric heating mantle with strong stirring, 7.5 g of purified calcium hydroxide was added, 1500ml of a polyphenylene ether reaction solution and the washed mixture were charged into a 2000ml three-necked flask by a peristaltic pump, and heated and distilled with stirring. The temperature was controlled to 70 ℃ or lower, and the reaction solution was replenished with a peristaltic pump.
And keeping the liquid level of the three-neck flask, continuously adding 8.8L of the solvent by using a peristaltic pump, keeping the original liquid level after the addition is finished, and stopping heating. The contents of the three-neck flask were poured out and centrifuged to obtain 58.0g of filter cake, and the walls of the three-neck flask were cleaned of the adhesive.
Washing the obtained filter cake with toluene for three times in a centrifugal machine, wherein the amount of the toluene used for each time is 100ml, and washing the low-molecular polyphenyl ether and organic matters in the filter cake; then 100ml of deionized water is used for washing out soluble bromine salt by three times; and finally, washing the calcium citrate by using 20ml of 10% citric acid for three times, washing to remove calcium hydroxide and copper hydroxide, filtering the washed calcium citrate to obtain 50.3g of calcium citrate, and drying the washed and filtered calcium citrate at 120 ℃ for 5 hours to obtain 24.8 g of calcium citrate with the content of 99.2%.
Comparative example 1
This comparative example differs from example 1 only in that the waste liquid is treated by adding sodium hydroxide, and the reaction waste liquid involved in this example has the composition shown in Table 1 b:
TABLE 1b
| Item | Water (W) | Methanol | Morpholine | Toluene | Citric acid | Bromine ion | Copper ion |
| Content (c) of | 2.63％ | 61.52％ | 0.21％ | 35.62％ | 0.11％ | 0.053％ | 0.03％ |
The three-necked flask was placed in an electric heating mantle with strong stirring, 7.5 g of purified sodium hydroxide was added, 1500ml of a polyphenylene ether reaction solution and the washed mixture were charged into a 2000ml three-necked flask by a peristaltic pump, and heated and distilled with stirring. The temperature was controlled to 70 ℃ or lower, and the reaction solution was replenished with a peristaltic pump.
The liquid level of the three-necked flask was maintained, 8.8L of the above solvent was continuously added by a peristaltic pump, and after the addition was completed, the heating was stopped. The contents of the three-necked flask were poured out, and only 18.3g of a cake was obtained by separation with a centrifuge. The viscosity of the supernatant is high during the centrifugal separation process, and the centrifugal time is long. The wall of the three-neck flask is adhered with a large amount of adhesive. Under the condition of a laboratory, the process of treating the reaction waste liquid by using the sodium hydroxide can be seen, a large amount of materials are adhered to the wall of a container, and the viscosity of a material system is easy to increase.
Example 2
The embodiment relates to a method for treating reaction waste liquid in polyphenylene oxide synthesis, which comprises the following steps:
the components of the reaction waste liquid related to this example are shown in table 2:
TABLE 2
| Item | Water (W) | Methanol | Morpholine | Toluene | Citric acid | Bromine ion | Copper ion |
| Content (wt.) | 2.63％ | 61.52％ | 0.21％ | 35.62％ | 0.11％ | 0.053％ | 0.03％ |
A2000 ml three-necked flask was placed in an electric heating mantle with strong stirring, 7.5 g of purified calcium hydroxide was added, 1500ml of a reaction solution of polyphenylene ether and the washed mixture were charged into the three-necked flask by a peristaltic pump, and heated and distilled with stirring. The reaction solution was replenished with a peristaltic pump by controlling the temperature to 70 ℃ or lower.
And keeping the liquid level of the three-neck flask, continuously adding 8.8L of the solvent by using a peristaltic pump, keeping the original liquid level after the addition is finished, and stopping heating. The contents of the three-necked flask were poured out and separated by a centrifuge to obtain 55.2g of a cake. The three-neck flask wall was clean of stickies.
Washing the obtained filter cake with toluene for three times in a centrifugal machine, wherein the amount of toluene used for each time is 80ml, and subjecting low-molecular polyphenyl ether and organic matters in the filter cake to washing; then 100ml of deionized water is used for washing out soluble bromine salt by three times; and finally, washing the calcium citrate by using 20ml of 10 percent citric acid for three times, washing to remove calcium hydroxide and copper hydroxide, washing and filtering the calcium citrate to obtain 46.8g of calcium citrate, and drying the washed and filtered calcium citrate for 5 hours at 120 ℃ to obtain 23.5 g of calcium citrate with the content of 99.2 percent.
Comparative example 2
This comparative example differs from example 1 only in that the waste liquid was treated by adding sodium hydroxide, and the reaction waste liquid involved in this example had the composition shown in Table 2 a:
TABLE 2a
| Item | Water (W) | Methanol | Morpholine | Toluene | Citric acid | Bromine ion | Copper ion |
| Content (wt.) | 2.63％ | 61.52％ | 0.21％ | 35.62％ | 0.11％ | 0.053％ | 0.03％ |
The three-necked flask was placed in an electric heating mantle with strong stirring, 7.5 g of purified potassium hydroxide was added, and 1500ml of a polyphenylene ether reaction solution and the washed mixture were charged into a 2000ml three-necked flask by a peristaltic pump, followed by heating and distillation with stirring. The temperature was controlled to 70 ℃ or lower, and the reaction solution was replenished with a peristaltic pump.
And (3) keeping the liquid level of the three-neck flask, continuously adding 8.8L of the solvent by using a peristaltic pump, keeping the original liquid level after the addition is finished, and stopping heating. The contents of the three-necked flask were poured out and separated by a centrifuge to obtain 20.0g of a cake. The viscosity of the supernatant is high during the centrifugal separation process, and the centrifugal time is long. The wall of the three-neck flask is adhered with a large amount of adhesive. Under the condition of a laboratory, the process of treating the reaction waste liquid by using the sodium hydroxide can show that a large amount of materials are adhered to the wall of a container and the viscosity of a material system is easy to increase.
Example 3
The embodiment relates to a method for treating reaction waste liquid in polyphenylene oxide synthesis, which comprises the following steps:
the reaction waste liquid involved in this example had the composition shown in Table 3:
TABLE 3
| Item | Water (W) | Methanol | Morpholine | Toluene | Citric acid | Bromine ion | Copper ion |
| Content (wt.) | 2.63％ | 61.52％ | 0.21％ | 35.62％ | 0.11％ | 0.053％ | 0.03％ |
The three-neck flask was placed in a vigorously stirred electric heating mantle, and 7.5 grams of refined calcium hydroxide was added. 1500ml of the reaction mixture of polyphenylene ether and the washed mixture was charged into a 2000ml three-necked flask by a peristaltic pump, and heated and distilled with stirring. The reaction solution was replenished with a peristaltic pump by controlling the temperature to 70 ℃ or lower.
And keeping the liquid level of the three-neck flask, continuously adding 8.8L of the solvent by using a peristaltic pump, keeping the original liquid level after the addition is finished, and stopping heating. The contents of the three-necked flask were poured out and separated by a centrifuge to obtain 55.5g of a cake. The three-neck flask wall was clean of stickies.
Washing the obtained filter cake with toluene for three times in a centrifugal machine, wherein the amount of the toluene used for each time is 100ml, and washing the low-molecular polyphenyl ether and organic matters in the filter cake; then washing with 100ml deionized water to remove soluble bromine salt; and finally, washing the calcium citrate by using 20ml of 10 percent citric acid for three times to remove calcium hydroxide and copper hydroxide, wherein the weight of the washed and filtered calcium citrate is 48.5g, and drying the washed and filtered calcium citrate for 5 hours at 120 ℃ to obtain 24.5 g of calcium citrate with the content of 99.15 percent.
Example 4
The embodiment relates to a method for treating reaction waste liquid in polyphenylene oxide synthesis, which comprises the following steps:
the components of the reaction waste liquid related to this example are shown in table 4:
TABLE 4
| Item | Water (W) | Methanol | Morpholine | Toluene | Citric acid | Bromide ion | Copper ion |
| Content (c) of | 2.63％ | 61.52％ | 0.21％ | 35.62％ | 0.11％ | 0.053％ | 0.03％ |
The three-necked flask was placed in an electric heating mantle with strong stirring, 8.0g of refined calcium hydroxide was added, 1500ml of a polyphenylene ether reaction solution and the washed mixture were charged into a 2000ml three-necked flask by a peristaltic pump, and heated and distilled with stirring. The reaction solution was replenished with a peristaltic pump by controlling the temperature to 70 ℃ or lower.
And (3) keeping the liquid level of the three-neck flask, continuously adding 8.8L of the solvent by using a peristaltic pump, keeping the original liquid level after the addition is finished, and stopping heating. The contents of the three-necked flask were poured out and separated by a centrifuge to obtain 58.0g of a cake. The wall of the three-neck flask is clean and free from adhesive substances.
Washing the obtained filter cake with toluene for three times in a centrifugal machine, wherein the amount of the toluene used for each time is 100ml, and washing the low-molecular polyphenyl ether and organic matters in the filter cake; then 100ml of deionized water is used for washing out soluble bromine salt by three times; and finally, washing the calcium citrate by using 20ml of 5% citric acid for three times, washing to remove calcium hydroxide and copper hydroxide, washing and filtering to obtain 50.8g of calcium citrate, and drying the washed and filtered calcium citrate at 120 ℃ for 5 hours to obtain 24.6 g of calcium citrate with the content of 99.3%.
Example 5
The embodiment relates to a method for treating reaction waste liquid in polyphenylene oxide synthesis, which comprises the following steps:
the components of the reaction waste liquid related to this example are shown in table 5:
TABLE 5
| Item | Water (W) | Methanol | Morpholine | Toluene | Citric acid | Bromine ion | Copper ion |
| Content (wt.) | 2.63％ | 61.52％ | 0.21％ | 35.62％ | 0.11％ | 0.053％ | 0.03％ |
The three-necked flask was placed in a vigorously stirred electric heating mantle, and 8.0g of refined calcium hydroxide was added. 1500ml of the reaction mixture of polyphenylene ether and the washed mixture was charged into a 2000ml three-necked flask by a peristaltic pump, and heated and distilled with stirring. The reaction solution was replenished by a peristaltic pump with the temperature controlled at 70 or below.
And (3) keeping the liquid level of the three-neck flask, continuously adding 8.8LL of the solvent by using a peristaltic pump, keeping the original liquid level after the addition is finished, and stopping heating. The contents of the three-necked flask were poured out and separated by a centrifuge to obtain 58.0g of a cake. The three-neck flask wall was clean of stickies.
Washing the obtained filter cake with toluene for three times in a centrifugal machine, wherein the amount of the toluene used for each time is 100ml, and washing the low-molecular polyphenyl ether and organic matters in the filter cake; then 100ml deionized water is used for washing off soluble bromine salt; and finally, washing the calcium citrate by using 30ml of 5% citric acid for three times to remove calcium hydroxide and copper hydroxide, wherein the calcium citrate after washing and filtering is 56.0g, and drying the calcium citrate after washing and filtering at 120 ℃ for 5 hours to obtain 23.6 g of calcium citrate with the content of 99.1%.
Example 6
The embodiment relates to a method for treating reaction waste liquid in polyphenylene oxide synthesis, which comprises the following steps:
the components of the reaction waste liquid related to this example are shown in table 6:
TABLE 6
| Item | Water (W) | Methanol | Morpholine | Toluene | Citric acid | Bromine ion | Copper ion |
| Content (wt.) | 2.63％ | 61.52％ | 0.21％ | 35.62％ | 0.11％ | 0.053％ | 0.03％ |
The three-necked flask was placed in a vigorously stirred electric heating mantle, and 8.0g of refined calcium hydroxide was added. 1500ml of the reaction mixture of polyphenylene ether and the washed mixture was charged into a 2000ml three-necked flask by a peristaltic pump, and heated and distilled with stirring. The reaction solution was supplemented with the above-mentioned reaction solution by a peristaltic pump through temperature control,
and keeping the liquid level of the three-neck flask, continuously adding 8.8L of the solvent by using a peristaltic pump, keeping the original liquid level after the addition is finished, and stopping heating. The contents of the three-neck flask were poured out and centrifuged to obtain 57.8g of filter cake, which was free of adhesive and had clean walls.
Washing the obtained filter cake with toluene for three times in a centrifugal machine, wherein the amount of the toluene used for each time is 100ml, and washing the low-molecular polyphenyl ether and organic matters in the filter cake; then washing the soluble bromine-dissolved salt by 80ml of deionized water for three times; and finally, washing the calcium citrate by using 10ml of 5% citric acid for three times, washing to remove calcium hydroxide and copper hydroxide, washing and filtering to obtain 56.8g of calcium citrate, and drying the washed and filtered calcium citrate at 120 ℃ for 5 hours to obtain 24.3 g of calcium citrate with the content of 99.3%. And (4) summarizing the results:
the examples show that the method of the present invention can directly react citric acid to generate calcium citrate precipitate by adding calcium hydroxide to the reaction waste liquid, and can directly remove the organic solvent by distillation while recovering citric acid without increasing the viscosity of the reaction system. In the examples, the effect of the present invention is described by a laboratory condition, and it is understood that the method of the present invention still has the effect of not causing clogging and not causing stickiness of the system in industrial production.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (7)
1. A method for treating reaction waste liquid in a polyphenyl ether synthesis process is characterized by comprising the following steps: one or two of calcium hydroxide or calcium oxide is/are added into reaction waste liquid generated when polyphenyl ether is prepared by a precipitation polymerization method, and citric acid in the reaction waste liquid is converted into calcium citrate to be removed.
2. The method according to claim 1, wherein the reaction waste liquid is a mixed liquid of a reaction mother liquid and a washing liquid of polyphenylene ether.
3. The processing method as claimed in claim 1, wherein the reaction mother liquor and the washing solution of polyphenylene ether are obtained by the steps of:
taking a mixed solution of methanol and toluene as a reaction solvent, taking a copper-amine complex as a catalyst, and carrying out polymerization reaction to obtain polyphenyl ether; after the reaction is finished, adding citric acid for end capping, and stopping the reaction; separating polyphenyl ether to obtain reaction mother liquor;
washing the polyphenylene ether with methanol to obtain a washing solution of the polyphenylene ether.
4. The treatment method according to claim 1, wherein the amount of the calcium hydroxide or calcium oxide added is based on the amount of all the materials to be treated which can react with the calcium hydroxide or calcium oxide in the reaction waste liquid.
5. The treatment method according to claim 1, wherein the temperature of the reaction system is controlled to be 60-70 ℃ in the process of removing the citric acid.
6. The treatment method according to claim 1 or 5, characterized in that the reaction waste liquid is treated by distillation, calcium hydroxide or calcium oxide is added into a distillation reactor, then part of the waste liquid to be treated is added into the distillation reactor, the temperature of the reactor is raised to 60-70 ℃, and the rest of the materials to be treated are gradually added until the reaction is finished.
7. The treatment method according to claim 6, wherein after the reaction is completed, the residue of the reaction is centrifuged to obtain a filter cake, the filter cake is washed with toluene to remove residual low molecular polyether and organic matter, then the filter cake is washed with deionized water to remove soluble bromine salt, and finally the filter cake is washed with a citric acid solution to remove calcium hydroxide and copper hydroxide, so that purified calcium citrate is obtained.
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| CN102807673A (en) * | 2011-06-03 | 2012-12-05 | 第一毛织株式会社 | Polyarylene ether and method for preparing the same |
| US20130211068A1 (en) * | 2010-10-08 | 2013-08-15 | Kevin R. Anderson | Binder, composition for use in making the binder, and methods of making the same |
| CN105199097A (en) * | 2015-10-22 | 2015-12-30 | 南通星辰合成材料有限公司 | Method for producing polyphenol hydroxyl polyphenylene oxide resin |
| CN106146290A (en) * | 2015-04-02 | 2016-11-23 | 中粮生物化学（安徽）股份有限公司 | A kind of method producing calcium citrate salts |
| CN109721726A (en) * | 2017-10-27 | 2019-05-07 | 南通星辰合成材料有限公司 | A method of recycling poly (arylene ether) synthetic |
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| US20130211068A1 (en) * | 2010-10-08 | 2013-08-15 | Kevin R. Anderson | Binder, composition for use in making the binder, and methods of making the same |
| CN102807673A (en) * | 2011-06-03 | 2012-12-05 | 第一毛织株式会社 | Polyarylene ether and method for preparing the same |
| CN106146290A (en) * | 2015-04-02 | 2016-11-23 | 中粮生物化学（安徽）股份有限公司 | A kind of method producing calcium citrate salts |
| CN105199097A (en) * | 2015-10-22 | 2015-12-30 | 南通星辰合成材料有限公司 | Method for producing polyphenol hydroxyl polyphenylene oxide resin |
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