CN115368628B - Desalination regeneration method of salt-containing polyethylene glycol waste liquid - Google Patents
Desalination regeneration method of salt-containing polyethylene glycol waste liquid Download PDFInfo
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- CN115368628B CN115368628B CN202210992406.7A CN202210992406A CN115368628B CN 115368628 B CN115368628 B CN 115368628B CN 202210992406 A CN202210992406 A CN 202210992406A CN 115368628 B CN115368628 B CN 115368628B
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- 229920001223 polyethylene glycol Polymers 0.000 title claims abstract description 129
- 239000002202 Polyethylene glycol Substances 0.000 title claims abstract description 127
- 239000007788 liquid Substances 0.000 title claims abstract description 122
- 239000002699 waste material Substances 0.000 title claims abstract description 111
- 238000010612 desalination reaction Methods 0.000 title claims abstract description 30
- 238000011069 regeneration method Methods 0.000 title claims abstract description 27
- 150000003839 salts Chemical class 0.000 title claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000706 filtrate Substances 0.000 claims abstract description 55
- 239000002253 acid Substances 0.000 claims abstract description 34
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 27
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 27
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000002639 sodium chloride Nutrition 0.000 claims description 39
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 38
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- 150000003841 chloride salts Chemical class 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 20
- -1 fluoride ions Chemical class 0.000 claims description 19
- 239000001103 potassium chloride Substances 0.000 claims description 19
- 235000011164 potassium chloride Nutrition 0.000 claims description 19
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 18
- 239000011591 potassium Substances 0.000 claims description 18
- 229910052700 potassium Inorganic materials 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- 239000011737 fluorine Substances 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 9
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 9
- 230000001105 regulatory effect Effects 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 37
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 20
- 238000000926 separation method Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 6
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 19
- 238000006115 defluorination reaction Methods 0.000 description 10
- 229910001415 sodium ion Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/10—Compounds containing silicon, fluorine, and other elements
- C01B33/103—Fluosilicic acid; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/22—Fluorides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/44—Separation; Purification; Stabilisation; Use of additives by treatments giving rise to a chemical modification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/02—Polyalkylene oxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Sustainable Development (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a desalination and regeneration method of a salt-containing polyethylene glycol waste liquid. The desalination regeneration method comprises the following steps: (1) Adding calcium hydroxide into polyethylene glycol waste liquid, adjusting the pH value, stirring for reaction, filtering for separation, and respectively collecting filter residues 1 and filtrate 1; (2) Adding fluosilicic acid into the filtrate 1, stirring for reaction, filtering and separating, and respectively collecting filter residues 2 and filtrate 2; (3) And concentrating the filtrate 2 in vacuum to obtain hydrochloric acid and polyethylene glycol regenerated liquid. The calcium hydroxide may be replaced with an aluminum salt. The invention simplifies the process and realizes the separation of inorganic salt in polyethylene glycol waste liquid, the desalination rate is more than 98.1 percent, and chloride ions, potassium ions and the like are respectively recovered in the form of products, so that secondary waste is not generated in the process.
Description
Technical Field
The invention relates to the technical field of waste liquid recovery, in particular to a desalination and regeneration method of a salt-containing polyethylene glycol waste liquid.
Background
Polyethylene glycol has good water solubility, compatibility, lubricity, adhesiveness and thermal stability, and the product is nontoxic and nonirritating, so that the polyethylene glycol has been widely applied to medicines and the like. In the using process, a part of waste polyethylene glycol solution is generated, and the main components of the solution comprise polyethylene glycol, water, potassium chloride or sodium chloride, potassium fluoride or sodium fluoride, ether substitutes, impurity alcohols and the like.
Polyethylene glycol is relatively high in market value, for example polyethylene glycol 400, and has a market value of about 10000 yuan/ton. Therefore, the recycling of the waste polyethylene glycol has a larger economic value space.
The most critical issue in the recovery of polyethylene glycol is how to separate the organic phase and the inorganic salts. Common methods include rectification, gravity layering and microwave. The rectification method collects polyethylene glycol in a light phase mode through high temperature and high negative pressure, can separate organic phases and inorganic salts, and simultaneously realizes separation of polyethylene glycol and other impurity organic phases, but the boiling point of the polyethylene glycol is higher than 250 ℃, and the rectification method has higher energy consumption. The gravity layering method utilizes polyethylene glycol to generate turbidity when heated to a cloud point temperature, the specific gravity is different from that of a salt solution to be layered (reversible process, mutual dissolution after cooling), and the light phase is collected in a layered manner. Microwave methods emit a microwave field at a specific frequency and power intensity to the PEG-rich phase. The PEG-rich phase will separate from the aqueous phase after exposure to the microwave field, which is simple to operate, does not use additional chemicals, but is relatively small in disposal.
Disclosure of Invention
Aiming at the problems of the prior art in polyethylene glycol waste liquid treatment, the invention aims to realize the separation of inorganic salts in polyethylene glycol waste liquid while simplifying the process, and can realize the full utilization of resources in the separation process. Therefore, the invention provides a desalination and regeneration method of the salt-containing polyethylene glycol waste liquid. The invention realizes the removal of inorganic salt in polyethylene glycol waste liquid by calcium hydroxide or aluminum salt defluorination, fluosilicic acid desalination and concentration deacidification, the polyethylene glycol treated by the process can reach the desalination rate of more than 98.1 percent, and chloride ions and potassium ions can be respectively recovered in the form of products without secondary waste in the process.
The technical scheme of the invention is as follows:
the invention aims to provide a desalination and regeneration method of a salt-containing polyethylene glycol waste liquid, which specifically comprises the following steps:
(1) Adding calcium hydroxide into polyethylene glycol waste liquid, adding hydrochloric acid to adjust the pH value, stirring and reacting for 20-60 min, filtering and separating, and respectively collecting filter residues 1 and filtrate 1;
(2) Adding fluosilicic acid into the filtrate 1, stirring and reacting for 10-30 min, filtering and separating, and respectively collecting filter residues 2 and filtrate 2;
(3) And concentrating the filtrate 2 in vacuum to obtain hydrochloric acid and polyethylene glycol regenerated liquid.
Further, in the step (1), the concentration of fluoride ions in the polyethylene glycol waste liquid is more than 0.2g/L, and the concentration of chloride ions is more than 0.1g/L; the polyethylene glycol waste liquid contains chloride salt, wherein the chloride salt is one or two of potassium chloride and sodium chloride; the burning residue of the glycol waste liquid is more than 0.5 percent.
Further, in the step (1), the molar quantity of the calcium hydroxide added is 0.5-1 times of the molar quantity of the fluoride ions in the polyethylene glycol waste liquid.
Further, in the step (1), the step of adjusting the pH value means adjusting the pH value to 5-12; the mass concentration of the hydrochloric acid is 10-38%.
Further, in the step (1), the filter residue 1 is calcium fluoride; the filtrate 1 is an intermediate solution containing polyethylene glycol.
Further, in the step (2), the mass concentration of the fluosilicic acid is 30-32%; the molar quantity of the fluosilicic acid added is 0.45-0.55 times of the molar quantity of the chloride salt in the polyethylene glycol waste liquid; the chloride salt is one or two of potassium chloride and sodium chloride;
further, when the chloride salt contained in the polyethylene glycol waste liquid is potassium chloride, the molar quantity of the fluosilicic acid added is K in the polyethylene glycol waste liquid + 0.45 to 0.55 times of the molar weight; when the chloride salt contained in the polyethylene glycol waste liquid is sodium chloride, the molar quantity of the fluosilicic acid added is Na in the polyethylene glycol waste liquid + 0.45 to 0.55 times of the molar weight; when the chloride salt contained in the polyethylene glycol waste liquid is potassium chloride and sodium chloride, the molar quantity of the fluosilicic acid added is K in the polyethylene glycol waste liquid + And Na (Na) + 0.45 to 0.55 times of the total molar amount.
Further, in the step (2), the filter residue 2 is potassium fluosilicate and/or sodium fluosilicate; the filtrate 2 is an intermediate solution containing polyethylene glycol.
Further, in the step (3), the temperature of the vacuum concentration is 80-100 ℃ and the pressure is-0.005 to-0.1 MPa.
A desalination and regeneration method for a salt-containing polyethylene glycol waste liquid uses aluminum salt to replace calcium hydroxide, and specifically comprises the following steps:
(1) Adding aluminum salt into polyethylene glycol waste liquid, regulating the pH value to 6-8, stirring and reacting for 20-60 min, filtering and separating, and respectively collecting fluorine-containing flocs and polyethylene glycol-containing intermediate solution;
(2) Adding fluosilicic acid into the intermediate solution containing polyethylene glycol, stirring and reacting for 10-30 min, filtering and separating, and respectively collecting filter residues 2 and filtrate 2;
(3) Concentrating the filtrate 2 in vacuum to obtain hydrochloric acid and polyethylene glycol regenerated liquid;
further, in the step (1), the aluminum salt is polyaluminum chloride; the adding amount of the polyaluminum chloride is 0.1-50 kg of polyaluminum chloride in each ton of polyethylene glycol waste liquid;
further, in the step (2), the filter residue 2 is potassium fluosilicate and/or sodium fluosilicate; the filtrate 2 is an intermediate solution containing polyethylene glycol.
Further, in the step (3), the temperature of the vacuum concentration is 80-100 ℃ and the pressure is-0.005 to-0.1 MPa.
The invention further aims to provide a pretreatment process of the salt-containing polyethylene glycol waste liquid, which can obtain polyethylene glycol solution with lower salt content while realizing full utilization of resources through pretreatment, can be combined with processes such as rectification and the like, and can avoid the problems of excessively high cost, complex process and the like of a method such as rectification or gravity layering and the like which are singly used, thereby saving the time and economic cost of waste liquid treatment.
The invention solves the following technical problems:
firstly, optimizing a defluorination process of polyethylene glycol waste liquid: when calcium hydroxide is used for removing fluorine in an aqueous solution conventionally, the fluorine removal is realized without additional pH adjustment operation, but in a polyethylene glycol solution, calcium hydroxide cannot be well dissolved in water to react with fluorine due to relatively less water in the system, so that the normal fluorine removal effect is not achieved. According to the invention, after calcium hydroxide is added, the pH is regulated by adding hydrochloric acid, so that on one hand, the water content in the system is increased, and on the other hand, the hydrochloric acid dissolves part of the calcium hydroxide, so that the calcium hydroxide and fluorine are easier to react, and a similar defluorination effect as that in the aqueous solution is achieved.
Second, the first one is a first one,the salt in the waste liquid is recycled and fully utilized: generally, if the rectification method is directly used, a relatively pure polyethylene glycol product can be obtained, but there are two problems in the process, namely, salt in the waste liquid is remained in a distillation still in the form of a mixture, the mixed salt requires additional treatment cost, and the disposal efficiency is very affected because the salt in the waste liquid is relatively high, which means that the cleaning of the still is required frequently. And secondly, because the solution contains fluorine, the rectification needs high temperature, and the material requirement on equipment is high. The invention reduces the material requirement of the process on equipment by pre-defluorination, the solid-liquid separation of each step is realized by adopting conventional filter pressing, the disposal efficiency is higher, and most importantly, the scheme is adopted to finish K in the solution + And/or Na + 、Cl - And F - Are sold or reused in the form of calcium fluoride, potassium fluosilicate and/or sodium fluosilicate, hydrochloric acid, etc.
Thirdly, the fluosilicic acid has better use effect in a polyethylene glycol system: in water, the solubility of potassium fluosilicate is 1-3 g/L at normal temperature, namely, after fluosilicic acid is used, part of potassium fluosilicate still remains in water, hydrochloric acid is generated in the reaction process of fluosilicic acid, and the solubility of potassium fluosilicate in hydrochloric acid is larger. However, in this embodiment, K in polyethylene glycol waste liquid is used + 0.45 to 0.55 times of the molar quantity of fluosilicic acid, so that K in the solution can be obtained + If the concentration of sodium ions is reduced to below 0.1g/L, or potassium ions and sodium ions are contained simultaneously, the total concentration of sodium ions or potassium ions and sodium ions in the solution can be reduced to below 0.1g/L, and the method has better effect in a polyethylene glycol system.
The beneficial technical effects of the invention are as follows:
(1) According to the invention, after calcium hydroxide is added, the pH is regulated by adding hydrochloric acid, so that on one hand, the water content in the system is increased, and on the other hand, part of calcium hydroxide is dissolved by hydrochloric acid, so that the calcium hydroxide and fluorine are easier to react, a similar defluorination effect as that in an aqueous solution is achieved, and the insufficient reaction caused by directly using the calcium hydroxide is avoided. In addition, the material requirement of the process on equipment is reduced by pre-defluorination, and the solid-liquid separation of each step adopts conventional filter pressingNamely, the treatment efficiency is higher, and the K in the solution + And/or Na + 、Cl - And F - The method is sold or secondarily utilized in the forms of calcium fluoride, potassium fluosilicate and/or sodium fluosilicate and hydrochloric acid respectively, so that comprehensive utilization of resources is realized.
(2) The invention realizes the removal of inorganic salt in polyethylene glycol waste liquid by calcium hydroxide or aluminum salt defluorination, fluosilicic acid desalination and concentration deacidification, and the polyethylene glycol treated by the process can reach the desalination rate>98%, and can convert Cl - And chloride ion (K) + And/or Na + ) The waste is recovered in the form of products respectively, and no secondary waste is generated in the process.
(3) The method can be used as a pretreatment process of the salt-containing polyethylene glycol waste liquid, is combined with processes such as rectification and the like, avoids the problems of excessively high cost, complex process and the like of a method such as single use of rectification or neutral layering and the like, and saves the time and economic cost of waste liquid treatment.
Drawings
Fig. 1 is a diagram of a desalination and regeneration process for treating a salt-containing polyethylene glycol waste liquid by calcium hydroxide.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples.
The desalination and regeneration method of the salt-containing polyethylene glycol waste liquid, when calcium hydroxide is used for treatment, the technological process is shown in figure 1, and specifically comprises the following steps:
defluorination: the polyethylene glycol waste liquid (the concentration of fluoride ions in the polyethylene glycol waste liquid is more than 0.2g/L, the concentration of chloride ions in the polyethylene glycol waste liquid is more than 0.1g/L, the polyethylene glycol waste liquid contains chloride salt, the chloride salt is one or two of potassium chloride and sodium chloride, and the burning residue of the ethylene glycol waste liquid is more than 0.5%), and a large amount of fluoride salt such as potassium fluoride is contained. Adding calcium hydroxide according to the fluorine content in the waste liquid, wherein the specific adding amount of the calcium hydroxide is 0.5-1 time of the molar amount of fluorine ions in the polyethylene glycol waste liquid, regulating the pH value to be 5-12 by using hydrochloric acid with the mass concentration of 10-38%, stirring for 20-60 min at normal temperature, filtering and separating, respectively collecting filtrate 1 and filter residue 1, wherein the filter residue 1 is calcium fluoride, and the filtrate 1 is filtrate 1 qualified in defluorination. When the waste liquid contains potassium ions, the reactions involved in the process are shown in the following formulas (1) - (2), and similarly, when the waste liquid contains sodium ions, calcium fluoride precipitates and sodium chloride can be generated.
2KF+Ca(OH) 2 ＝CaF 2 ↓+2KOH (1)
KOH+HCl＝KCl+H 2 O (2)
Removing potassium: after defluorination, the inorganic salt mainly contained in the filtrate 1 is potassium chloride and/or sodium chloride and a small amount of calcium ions. According to the content of potassium ions and/or sodium ions in the waste liquid, fluosilicic acid is added into the filtrate 1, and the mass concentration of the fluosilicic acid is 30-32%; when the chloride salt contained in the polyethylene glycol waste liquid is potassium chloride, the molar quantity of the fluosilicic acid added is K in the polyethylene glycol waste liquid + 0.45 to 0.55 times of the molar weight; when the chloride salt contained in the polyethylene glycol waste liquid is sodium chloride, the molar quantity of the fluosilicic acid added is Na in the polyethylene glycol waste liquid + 0.45 to 0.55 times of the molar weight; when the chloride salt contained in the polyethylene glycol waste liquid is potassium chloride and sodium chloride, the molar quantity of the fluosilicic acid added is K in the polyethylene glycol waste liquid + And Na (Na) + 0.45 to 0.55 times of the total molar amount; stirring and reacting for 10-30 min at normal temperature, filtering and separating solid and liquid phases, and respectively collecting filtrate 2 and filter residue 2; the filter residue 2 is potassium fluosilicate and/or sodium fluosilicate; the filtrate 2 is an intermediate solution containing polyethylene glycol. Namely, qualified polyethylene glycol regeneration liquid for removing potassium and/or sodium. Taking potassium ion as an example, the reaction involved in this process is shown in the following formula (3), and similarly when sodium ion is contained, hydrochloric acid and sodium fluosilicate may also be produced by reaction with fluosilicic acid.
H 2 SiF 6 +2KCl＝K 2 SiF 6 ↓+2HCl (3)
Concentrating: after potassium removal, the main components in the filtrate 2 are polyethylene glycol, hydrochloric acid and water. Concentrating the filtrate 2 in vacuum to obtain hydrochloric acid fraction and polyethylene glycol regenerated liquid. The acidity of hydrochloric acid depends on the content of potassium chloride in the waste liquid.
The content of potassium ions (sodium ions when sodium is contained and the sum of potassium ions and sodium ions when both ions are contained) in the polyethylene glycol regenerated liquid obtained through the treatment of the steps is less than 0.6g/L, and the desalination rate is more than 98.1%.
According to the invention, aluminum salt (polyaluminum chloride) can be used for replacing calcium hydroxide, waste liquid regeneration is realized by limiting and controlling the addition amount of polyaluminum, the fluorine removal step in the step of polyaluminum regeneration is different from that of calcium hydroxide, the rest steps are the same (the subsequent potassium and/or sodium removal does not leave calcium ions), and the steps of polyaluminum fluorine removal are as follows:
adding polyaluminium chloride (polyaluminium chloride) into polyethylene glycol waste liquid, regulating the pH value to 5-8, stirring and reacting for 20-60 min, filtering and separating, and respectively collecting intermediate solutions containing fluorine flocs and polyethylene glycol; the adding amount of the polyaluminum chloride is 0.1-50 kg of polyaluminum chloride in each ton of polyethylene glycol waste liquid; in this process, the intermediate product of the coordination and hydrolysis of aluminum ions and fluorine ions and finally the amorphous Al (OH) formed 3(am) The fluorine ion concentration is gradually reduced by the adsorption and rolling scanning of the flocs on the fluorine ions.
Example 1
A desalination and regeneration method of a salt-containing polyethylene glycol waste liquid specifically comprises the following steps:
(1) Adding calcium hydroxide with the molar quantity being 1 times of the molar quantity of fluoride ions in the polyethylene glycol waste liquid into 500mL of the polyethylene glycol waste liquid, adding hydrochloric acid with the mass concentration being 38%, adjusting pH to be 11.5, stirring for reaction for 60min, filtering and separating, and respectively collecting filter residues 1 and filtrate 1, wherein the filter residues 1 are calcium fluoride, and F in the filtrate 1 - ＝0.18g/L，K + =64.7 g/L; the concentration of fluoride ions in the polyethylene glycol waste liquid is 14.3g/L, and the concentration of chloride ions is about 35g/L; the polyethylene glycol waste liquid contains potassium chloride; 11.0% of burned residues of polyethylene glycol waste liquid.
(2) Adding fluosilicic acid (the mass fraction is 30-32%) into the filtrate 1, wherein the molar quantity of the added fluosilicic acid is 1 time of the potassium ion concentration in the polyethylene glycol waste liquid (namely 0.5 time of the molar quantity of potassium ions), stirring and reacting for 10min, filtering and separating, respectively collecting filter residues 2 and filtrate 2, wherein the filter residues 2 are potassium fluosilicate, and K in the filtrate 2 + ＝0.062g/L；
(3) Vacuum concentrating the filtrate 2 at 90 deg.c and-0.1 MPa to obtain hydrochloric acid fraction and regenerated polyglycol liquid.
Example 2
A desalination and regeneration method of a salt-containing polyethylene glycol waste liquid specifically comprises the following steps:
(1) Adding calcium hydroxide with the molar quantity being 1 time of the molar quantity of fluoride ions in the polyethylene glycol waste liquid into 100mL of the polyethylene glycol waste liquid, adding hydrochloric acid with the mass concentration being 38%, adjusting pH to be 10, stirring for reaction for 30min, filtering and separating, and respectively collecting filter residues 1 and filtrate 1, wherein the filter residues 1 are calcium fluoride, and F in the filtrate 1 - ＝0.09g/L，K + =65.7 g/L; the concentration of fluoride ions in the polyethylene glycol waste liquid is 14.3g/L, and the concentration of chloride ions is about 35g/L; the polyethylene glycol waste liquid contains potassium chloride; the burning residue of the glycol waste liquid>11.0％。
(2) Adding fluosilicic acid (the mass fraction is 30-32%) into the filtrate 1, wherein the molar quantity of the added fluosilicic acid is 1.05 times of the potassium ion concentration in the polyethylene glycol waste liquid (namely 0.53 times of the molar quantity of the potassium ion), stirring and reacting for 30min, filtering and separating, respectively collecting filter residues 2 and filtrate 2, wherein the filter residues 2 are potassium fluosilicate, and K in the filtrate 2 + ＝0.065g/L；
(3) Vacuum concentrating the filtrate 2 at 100 deg.c and-0.08 MPa to obtain hydrochloric acid fraction and regenerated polyglycol liquid.
Example 3
A desalination and regeneration method of a salt-containing polyethylene glycol waste liquid specifically comprises the following steps:
(1) Adding calcium hydroxide with the molar quantity being 0.6 times of the molar quantity of fluoride ions in the polyethylene glycol waste liquid into 100mL of the polyethylene glycol waste liquid, adding hydrochloric acid with the mass concentration being 10%, adjusting pH to be 8, stirring for reaction for 40min, filtering and separating, and respectively collecting filter residues 1 and filtrate 1, wherein the filter residues 1 are calcium fluoride, and F in the filtrate 1 - ＝0.1g/L，K + =55.0 g/L; the concentration of fluoride ions in the polyethylene glycol waste liquid is 14.3g/L, and the concentration of chloride ions is about 35g/L; the polyethylene glycol waste liquid contains potassium chloride; 11% of burning residues of the ethylene glycol waste liquid.
(2) Fluosilicic acid (mass fraction) was added to the filtrate 130-32 percent), the molar quantity of the fluosilicic acid added is 1.05 times of the potassium ion concentration in the polyethylene glycol waste liquid (namely 0.53 times of the molar quantity of the potassium ion), after stirring and reacting for 20min, filtering and separating, and respectively collecting filter residue 2 and filtrate 2, wherein the filter residue 2 is potassium fluosilicate, and K in the filtrate 2 + ＝0.097g/L；
(3) Vacuum concentrating the filtrate 2 at 100 deg.c and-0.06 MPa to obtain hydrochloric acid fraction and regenerated polyglycol liquid.
Example 4
A desalination and regeneration method of a salt-containing polyethylene glycol waste liquid specifically comprises the following steps:
(1) Adding 4g of polyaluminum chloride into 100mL of polyethylene glycol waste liquid, regulating pH to 7 by hydrochloric acid, stirring for reaction for 30min, filtering and separating, and respectively collecting fluorine-containing flocs and filtrate 1, wherein F in the filtrate 1 - ＝1g/L，K + =66.0 g/L; the concentration of fluoride ions in the polyethylene glycol waste liquid is 14.3g/L, and the concentration of chloride ions is 35g/L; the polyethylene glycol waste liquid contains potassium chloride; 11% of burning residues of the ethylene glycol waste liquid.
(2) Adding fluosilicic acid (the mass fraction is 30-32%) into the filtrate 1, wherein the molar quantity of the added fluosilicic acid is 1 time of the potassium ion concentration in the polyethylene glycol waste liquid (namely 0.5 time of the molar quantity of potassium ions), stirring and reacting for 20min, filtering and separating, respectively collecting filter residues 2 and filtrate 2, wherein the filter residues 2 are potassium fluosilicate, and K in the filtrate 2 + ＝0.1g/L；
(3) Vacuum concentrating the filtrate 2 at 100 deg.c and-0.1 MPa to obtain hydrochloric acid fraction and regenerated polyglycol liquid.
Test example:
the potassium ion content of the polyethylene glycol regeneration liquid obtained in examples 1 to 4 was measured using GB/T9741-2008. The results are shown in Table 1. The method for calculating the desalination rate comprises the following steps:
wherein: x is x 1 The unit is the burning residue amount of polyethylene glycol waste liquid; x is x 2 Is polyethylene glycolThe burning residue amount of the regenerated liquid is in unit percent.
Since the salt-free sample (i.e., the salt-free polyethylene glycol waste liquid) itself burns the residue generally <0.2%, the point value is calculated as 0.2% in the formula.
When the content of firing residue in polyethylene glycol waste liquid before desalting is 11%, and when the firing residue of the obtained polyethylene glycol regeneration liquid is 0.3%, the desalting rate= (11% - (0.3% -0.2%)) is 100%/11% = 99.1%.
TABLE 1 content of Potassium ions and firing residues in polyethylene glycol regeneration liquid and salt rejection
| Examples | K + Concentration of | Burning residues | Desalination rate |
| Original sample | 65g/L | 11.0％ | - |
| Example 1 | 0.25g/L | 0.30％ | 99.1％ |
| Example 2 | 0.26g/L | 0.31％ | 99.0％ |
| Example 3 | 0.32g/L | 0.35％ | 98.6％ |
| Example 4 | 0.31g/L | 0.40％ | 98.1％ |
As is clear from Table 1, the desalination and regeneration method of the salt-containing polyethylene glycol waste liquid according to the embodiment 1 of the present invention can achieve a desalination rate of 98.1% -99.1%, and can recover chlorine ions and potassium ions as products, respectively, without generating secondary waste in the process.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, and then should be considered as the scope of the description of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. It should be understood that those skilled in the art, based on the technical solutions provided by the present invention, can obtain technical solutions through logical analysis, reasoning or limited experiments, all fall within the protection scope of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.
Claims (6)
1. The desalination and regeneration method for the salt-containing polyethylene glycol waste liquid is characterized by comprising the following steps of:
(1) Adding calcium hydroxide into polyethylene glycol waste liquid, adjusting the pH value, stirring and reacting for 20-60 min, filtering and separating, and respectively collecting filter residues 1 and filtrate 1;
(2) Adding fluosilicic acid into the filtrate 1, stirring for reaction for 10-30 min, filtering and separating, and respectively collecting filter residues 2 and filtrate 2;
(3) Concentrating the filtrate 2 in vacuum to obtain hydrochloric acid and polyethylene glycol regenerated liquid;
in the step (1), the concentration of fluoride ions in the polyethylene glycol waste liquid is more than 0.2g/L, and the concentration of chloride ions is more than 0.1g/L; the polyethylene glycol waste liquid contains chloride salt, wherein the chloride salt is one or two of potassium chloride and sodium chloride; the burning residue of the glycol waste liquid is more than 0.5 percent;
in the step (1), the added molar quantity of the calcium hydroxide is 0.5-1 time of the molar quantity of the fluoride ions in the polyethylene glycol waste liquid;
in the step (1), the pH value is adjusted by hydrochloric acid, and the mass concentration of the hydrochloric acid is 10-38%;
in the step (1), the step of adjusting the pH value refers to adjusting the pH value to 5-12;
in the step (2), the mass concentration of the fluosilicic acid is 30-32%; the molar quantity of the fluosilicic acid added is 0.45-0.55 times of the molar quantity of the chloride salt in the polyethylene glycol waste liquid; the chloride salt is one or two of potassium chloride and sodium chloride.
2. The desalination regeneration method of claim 1, wherein in step (1), the filter residue 1 is calcium fluoride; the filtrate 1 is an intermediate solution containing polyethylene glycol.
3. The desalination regeneration method of claim 1, wherein in step (2), the filter residue 2 is potassium fluosilicate and/or sodium fluosilicate; the filtrate 2 is an intermediate solution containing polyethylene glycol.
4. The desalination regeneration method according to claim 1, wherein in the step (3), the vacuum concentration is performed at a temperature of 80 to 100 ℃ and a pressure of-0.005 to-0.1 MPa.
5. The desalination and regeneration method for the salt-containing polyethylene glycol waste liquid is characterized by comprising the following steps of:
(1) Adding aluminum salt into polyethylene glycol waste liquid, regulating the pH value to 5-8, stirring and reacting for 20-60 min, and then filtering and separating to respectively collect intermediate solutions containing fluorine flocs and polyethylene glycol;
(2) Adding fluosilicic acid into the intermediate solution containing polyethylene glycol, stirring for reaction for 10-30 min, filtering and separating, and respectively collecting filter residues 2 and filtrate 2;
(3) Concentrating the filtrate 2 in vacuum to obtain hydrochloric acid and polyethylene glycol regenerated liquid;
in the step (1), the concentration of fluoride ions in the polyethylene glycol waste liquid is more than 0.2g/L, and the concentration of chloride ions is more than 0.1g/L; the polyethylene glycol waste liquid contains chloride salt, wherein the chloride salt is one or two of potassium chloride and sodium chloride; the burning residue of the glycol waste liquid is more than 0.5 percent; the aluminum salt is polyaluminum chloride; the addition amount of the polyaluminum chloride is 0.1-50 kg of polyaluminum chloride added into each ton of polyethylene glycol waste liquid;
in the step (2), the mass concentration of the fluosilicic acid is 30-32%; the molar quantity of the fluosilicic acid added is 0.45-0.55 times of the molar quantity of the chloride salt in the polyethylene glycol waste liquid; the chloride salt is one or two of potassium chloride and sodium chloride.
6. The desalination regeneration method according to claim 5, wherein in step (2), the filter residue 2 is potassium fluosilicate and/or sodium fluosilicate; the filtrate 2 is an intermediate solution containing polyethylene glycol;
in the step (3), the temperature of vacuum concentration is 80-100 ℃, and the pressure is-0.005 to-0.1 MPa.
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| CN113024796A (en) * | 2019-12-25 | 2021-06-25 | 辽宁奥克化学股份有限公司 | Refining method of polyethylene glycol |
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| JP2000015269A (en) * | 1998-04-27 | 2000-01-18 | Fujitsu Ltd | Treating method for fluorine-containing water |
| CN101817526A (en) * | 2010-04-08 | 2010-09-01 | 浙江源盛硅晶材料有限公司 | Method for recovering polyethylene glycol and silicon carbide from silicon crystal cutting waste liquid |
| CN106927550A (en) * | 2017-03-07 | 2017-07-07 | 广东省资源综合利用研究所 | A kind of recovery method of fluorine-containing industrial wastewater |
| CN113024796A (en) * | 2019-12-25 | 2021-06-25 | 辽宁奥克化学股份有限公司 | Refining method of polyethylene glycol |
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