CN102503014B - Treatment method of glycerin wastewater containing salt - Google Patents
Treatment method of glycerin wastewater containing salt Download PDFInfo
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- CN102503014B CN102503014B CN 201110373337 CN201110373337A CN102503014B CN 102503014 B CN102503014 B CN 102503014B CN 201110373337 CN201110373337 CN 201110373337 CN 201110373337 A CN201110373337 A CN 201110373337A CN 102503014 B CN102503014 B CN 102503014B
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 78
- 239000002351 wastewater Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 26
- 150000003839 salts Chemical class 0.000 title claims abstract description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000000605 extraction Methods 0.000 claims abstract description 36
- 239000012074 organic phase Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 13
- 238000002425 crystallisation Methods 0.000 claims abstract description 9
- 230000008025 crystallization Effects 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 31
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 21
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 16
- 239000011780 sodium chloride Substances 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 7
- 239000003225 biodiesel Substances 0.000 abstract description 3
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 239000012071 phase Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 238000012824 chemical production Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011268 retreatment Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 238000002156 mixing Methods 0.000 description 11
- 239000013078 crystal Substances 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 3
- 210000000689 upper leg Anatomy 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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Abstract
The invention discloses a treatment method of glycerin wastewater containing salt. Glycerin waste water containing salt produced during different production processes is added in normal butanol with the amount being 1.3 to 3.3 times of wastewater quantity; with the addition of normal butanol, under the normal pressure and the temperature of 30 to 70 DEG C, salt in glycerin wastewater containing salt is separated out by crystallization, the liquid phase is divided into an upper organic phase and a lower water phase; the upper organic phase contains 0.3 percent of salt, and is rectified, normal butanol is recovered, and water is removed at the same time, so that 99.9 percent of pure glycerin serving as a product is obtained; and the lower water phase is filtered, filtrate flows back to an extraction tower for retreatment, and crystallized sodium chloride is washed and recovered. The treatment method has the advantages of simple and convenient process flow, easiness in operation and control, and environmental friendliness; and glycerin and sodium chloride in wastewater can be recycled, so that the production cost can be reduced effectively. The invention is especially suitable for byproducts in epoxide resin production, glycerin byproducts in oil and glycerin chemical production and wastewater treatment of glycerin byproducts in biodiesel production.
Description
Technical field
The present invention relates to a kind for the treatment of process of waste water, be specifically related to a kind for the treatment of process of saliferous Glycerol Wastewater.
Background technology
In recent years, along with the growth of epoxy resin and production of biodiesel, the production wastewater treatment amount that contains by-product glycerol sharply rises.Contain a large amount of salts in this Glycerol Wastewater.The raw glycerine purifying process will through operations such as concentrated, distillation, absorption and ion-exchanges, could obtain high-quality refining glycerine at present.Yet, because the salt that contains in raw glycerine makes the system elevation of boiling point, not only will consume a large amount of heat energy in concentrated and distillation, and the salt deposition of separating out along with the moisture evaporation causes operation and equipment loss etc. additionally to bear.Therefore, traditional glycerine purifying technique cost is very high.
Summary of the invention
The object of the present invention is to provide a kind for the treatment of process of saliferous Glycerol Wastewater, its technical process is simple, efficient is high, and is little to equipment loss, can reduce the processing cost of saliferous Glycerol Wastewater, and the uniform glycerol product of available quality, thereby can reduce production costs.
The technical solution adopted for the present invention to solve the technical problems is:
The processing step of the method is:
1) will add from the saliferous Glycerol Wastewater that produces in different production processes the propyl carbinol of 1.3 ~ 3.3 times of wastewater flow rates;
2) along with the adding of propyl carbinol, at normal pressure, temperature is 30 ~ 70 ℃, and the salt in the saliferous Glycerol Wastewater can crystallization, and liquid phase is divided into the organic phase that the upper strata contains 0.3% salt, and lower floor's water;
3) upper organic phase through rectifying, reclaims propyl carbinol, simultaneously except anhydrating, and obtains 99.9% pure glycerin as product; Lower floor's water filters, and filtrate is back in extraction tower and processes, the sodium-chlor washing and recycling of crystallization.
Described upper organic phase is through rectifying, the idiographic flow that reclaims propyl carbinol and pure glycerin is: the topper stream of extraction tower enters the first rectification under vacuum tower through the first preheater, the first rectification under vacuum tower tower bottoms, enter the 3rd further rectifying separation purification of glycerol of rectification under vacuum tower through the second preheater, tower top distillates solvent cycle to extraction tower; The first rectification under vacuum column overhead distillates azeotropic liquid, with distillate azeotropic liquid from the second rectification under vacuum column overhead and be mixed into standing demix in decanting vessel, the decanting vessel topper flows back to and flows into the first rectification under vacuum tower and continue rectifying, and the logistics of decanting vessel lower floor enters the second rectification under vacuum tower; The second rectification under vacuum tower tower reactor distillates the pure water logistics, and tower top distillates azeotropic liquid.
The beneficial effect that the present invention has is:
It is easy that method of the present invention has technical process, easy handling and control, environmental friendliness; Glycerine in waste water and sodium-chlor all can be recycled, effectively Decrease production cost.The present invention is specially adapted to the wastewater treatment in epoxy resin production glycerin by-products, oil and fat chemical production glycerin by-products and production of biodiesel glycerin by-products.
Description of drawings
Accompanying drawing is saliferous Glycerol Wastewater processing technological flow figure.
In accompanying drawing:
R1, extraction tower, R2, crystallizer, F1, strainer, C1, the first rectification under vacuum tower, C2, the second rectification under vacuum tower, C3, the 3rd rectification under vacuum tower, D1, decanting vessel, H1, the first preheater, H2, the second preheater, H3, the 3rd preheater, H4, the 4th preheater, H5, pre-cooler, P1, solvent pump, M1, the first mixing tank, M2, the second mixing tank, M3, the 3rd mixing tank;
1, the waste water circulation mixture, 2, the propyl carbinol recycle stream, 3, the logistics of extraction tower lower floor, 4, the logistics of extraction tower upper strata, 5, the crystallizer logistics, 6, filtrate, 7, the sodium chloride crystal logistics, 8, the first rectification under vacuum tower charging, 9, the first rectification under vacuum tower top distillates azeotropic liquid, 10, the first rectification under vacuum tower tower bottoms, 11, the 3rd rectification under vacuum tower charging, 12, the propyl carbinol returned logistics, 13, the glycerol product logistics, 14, two tower azeotrope mixture flow, 15, the logistics of decanting vessel lower floor, 16, the logistics of decanting vessel upper strata, 17, the preheating logistics of decanting vessel lower floor, 18, the second rectification under vacuum tower charging, 19, the second rectification under vacuum tower top distillates azeotropic liquid, 20, the second rectification under vacuum tower reactor pure water logistics, 21, the propyl carbinol phegma, 22, wastewater feed, 23, waste water, solvent liquid.
Embodiment
The present invention is further illustrated below in conjunction with drawings and Examples.
As shown in drawings, the processing step of the method is:
1) will add from the saliferous Glycerol Wastewater that produces in different production processes the propyl carbinol of 1.3 ~ 3.3 times of wastewater flow rates;
2) along with the adding of propyl carbinol, at normal pressure, temperature is under the condition of 30 ~ 70 ℃, and the salt in the saliferous Glycerol Wastewater can crystallization, and liquid phase is divided into the organic phase that the upper strata contains 0.3% salt, and lower floor's water;
3) upper organic phase through rectifying, reclaims propyl carbinol, simultaneously except anhydrating, and obtains 99.9% pure glycerin as product; Lower floor's water filters, and filtrate is back in extraction tower and processes, the sodium-chlor washing and recycling of crystallization.
Described upper organic phase is through rectifying, the idiographic flow that reclaims propyl carbinol and pure glycerin is: the topper stream of extraction tower enters the first rectification under vacuum tower C1 through the first preheater H1, the first rectification under vacuum tower C1 tower bottoms, enter the 3rd further rectifying separation purification of glycerol of rectification under vacuum tower C3 through the second preheater H2, it is cooling through pump P1 supercharging and pre-cooler H5 that tower top distillates solvent, is circulated in extraction tower R1; The first rectification under vacuum tower C1 tower top distillates azeotropic liquid, with distillate azeotropic liquid from the second rectification under vacuum tower C2 tower top and be mixed into standing demix in decanting vessel D1, the 3rd preheater H3 preheating of flowing through of decanting vessel D1 topper passes back into the first rectification under vacuum tower C1 and continues rectifying, and logistics the 4th preheater H4 preheating of decanting vessel D1 lower floor enters the second rectification under vacuum tower C2; The second rectification under vacuum tower C2 tower reactor distillates the pure water logistics, and tower top distillates azeotropic liquid.
The saliferous Glycerol Wastewater that produces during the present invention produces is thick liquid through evaporation concentration, contains by analysis 28 ~ 32% glycerine, 50% ~ 54% water, the sodium-chlor of 18% left and right and a small amount of impurity.Waste water circulation mixture 1 is mixed in the 3rd mixing tank M3 with propyl carbinol recycle stream 2, and formation waste water, solvent liquid 23 enter extraction tower R1.Operational condition is normal pressure, and temperature range is 30 ~ 70 ℃.Solvent extraction part water and glycerine enter organic phase, and the sodium-chlor of aqueous phase is because the minimizing of water-content is separated out.The water that enters organic phase can carry micro-sodium-chlor and enter organic phase, and content accounts for 4.8 ~ 5.2 % of total sodium-chlor.Because salts contg in organic phase is lower, can adopt rectifying to reclaim solvent, extract glycerine.Solubleness reduces crystallization to the sodium-chlor of aqueous phase due to the increase of solvent simultaneously.Therefore utilize the solvent extraction crystallization, can avoid or reduce the ebullioscopic impact of salt pair solution.
Through after extraction tower, mixed solution splits into liquid-liquid-solid three-phase.The upper strata is the organic phase that contains water, glycerine and micro-sodium-chlor.Lower floor is the water that contains a small amount of solvent and partial glycerol and sodium-chlor.Solid phase is the sodium chloride crystal of separating out.Reclaim solvent and extract glycerine from extraction tower upper strata logistics 4, passing into strainer after the logistics 3 of extraction tower lower floor forms crystallizer logistics 5 through crystallizers, filtrate 6 is back to extraction tower, and sodium chloride crystal logistics 7.Solvent recuperation and glycerin extraction be through three vacuum distillation towers, the first rectification under vacuum tower C1, the second rectification under vacuum tower C2, the 3rd rectification under vacuum tower C3, and wherein the first rectification under vacuum tower and the second rectification under vacuum tower consist of the heterogeneous azeotropic rectification system of solvent recuperation.Extraction tower upper strata logistics 4 becomes the first rectification under vacuum tower charging 8 through the first preheater H1 and enters the first rectification under vacuum tower, working pressure 0.3bar ~ 0.5bar.The first rectification under vacuum tower tower bottoms 10 is propyl carbinol and glycerine mixed solution, be that the 3rd rectification under vacuum tower charging 11 enters the 3rd rectification under vacuum tower rectifying through the second preheater H2 preheating, tower top obtains propyl carbinol returned logistics 12, become propyl carbinol phegma 21 and be cooled to propyl carbinol recycle stream 2 through pre-cooler through pump P1 supercharging and be back to extraction tower, output glycerol product logistics 13 at the bottom of tower.The first rectification under vacuum tower top distillates azeotropic liquid 9 and is water and propyl carbinol azeotrope, and the mass fraction of water is 0.38.This distillate distillates azeotropic liquid 19 with the second rectification under vacuum tower top to be mixed through the first mixing tank M1, enters decanting vessel through overcooling.In decanting vessel, two tower azeotrope mixture flow 14 are layered as decanting vessel lower floor's logistics 15 and decanting vessel upper strata logistics 16, wherein decanting vessel upper strata logistics 16 becomes decanting vessel lower floor preheating logistics 17 through the 3rd preheater H3, decanting vessel lower floor logistics 15 is preheated to the second rectification under vacuum tower charging 18 through the 4th preheater and enters the second rectification under vacuum tower, distillate the second rectification under vacuum tower top at tower top and distillate azeotropic liquid 19, the mass fraction of water is 0.38.The second rectification under vacuum tower top distillates azeotropic liquid 19 backflows and enters decanting vessel; Output the second rectification under vacuum tower reactor pure water logistics 20 at the bottom of tower.
Embodiment 1:
This routine propyl carbinol consumption is 2.5 times of factory effluent.According to the accompanying drawing Establishing process, concrete logistics connects the introduction referring to technical process in summary of the invention.Wastewater feed 22 (flow 1395.2kg/hr, water accounts for 56%, glycerine accounts for 26%, sodium-chlor accounts for 18%) with filter F 1 in filtrate 6 (flow 1668.8kg/hr, water accounts for 55%, glycerine accounts for 27%, sodium-chlor accounts for 15%, propyl carbinol accounts for 3%) be mixed into waste water circulation mixture 1 (flow 3064kg/hr), (flow 7500kg/hr) mixes in the 3rd mixing tank M3 with propyl carbinol recycle stream 2, and formation waste water, solvent liquid 23 (flow 10564kg/hr) enter extraction tower R1.At normal pressure, temperature is operation under 30 ℃.In extractor R1, (flow is 1921.7kg/hr in output extraction tower lower floor logistics 3, water accounts for 55%, glycerine accounts for 27%, and sodium-chlor accounts for 15%, and propyl carbinol accounts for 3%) (flow is 8588.29kg/hr with extraction tower upper strata logistics 4, water accounts for 9.1%, glycerine accounts for 4.2%, and propyl carbinol accounts for 86.7%), and precipitated sodium chloride crystal 2 52.9kg/hr.
extraction tower upper strata logistics 4 is heated to 74 ℃ through preheater H1, form the first rectification under vacuum tower charging 8 and enter the first rectification under vacuum tower C1 at second column plate place, the overhead condenser working pressure is 0.5bar, the first rectification under vacuum tower top distillates azeotropic liquid 9, and (flow is 2916.6kg/hr, water accounts for 38.2%, propyl carbinol accounts for 61.8%) (flow is 407.4kg/hr with distillating azeotropic liquid 19 from the second rectification under vacuum tower top of the second rectification under vacuum tower C2, water accounts for 39.4%, propyl carbinol accounts for 60.6%) be mixed into two tower azeotrope mixture flow 14 through the first mixing tank M1 and enter decanting vessel D1.Two tower azeotrope mixture flow 14 layerings in D1, (flow is 1188.8kg/hr in decanting vessel lower floor logistics 15, water accounts for 79.2%, propyl carbinol accounts for 20.8%) be heated to 70 ℃ through preheater H4 and become the second rectification under vacuum tower charging 18 and enter C2, the overhead condenser working pressure is 0.5bar, the second rectification under vacuum tower top distillates azeotropic liquid 19 and returns in decanting vessel, the second rectification under vacuum tower reactor pure water logistics 20 (flow is 781.5kg/hr, and water accounts for 99.99%).Decanting vessel upper strata logistics 16 (flow is 2135.3kg/hr, and water accounts for 15.6%, and propyl carbinol accounts for 84.4%) is heated to 74 ℃ through preheater H3 to be become decanting vessel lower floor preheating logistics 17 and is back in C1.The first rectification under vacuum tower tower bottoms 10 (flow is 7806.9kg/hr, and glycerine accounts for 4.6%, and propyl carbinol accounts for 95.4%) is heated to 88 ℃ through preheater H2 to be become the 3rd rectification under vacuum tower charging 11 and enters the 3rd rectification under vacuum tower C3.The overhead condenser working pressure is 0.3bar.(flow is 7446.1kg/hr to propyl carbinol returned logistics 12, propyl carbinol purity is 99.99%) be pressurised into propyl carbinol phegma 21 through pump P1, and be cooled to propyl carbinol recycle stream 2 through pre-cooler and return to extraction tower R1 recycle, glycerol product logistics 13 (flow is 360.9kg/hr, and glycerine purity is 99.91%) is product glycerine.The flow of each stream thigh is asked for an interview table 1.
Table
: the propyl carbinol consumption is that 2.5 times of calculation result of wastewater flow rate gather
Embodiment 2:
This routine propyl carbinol consumption is 1.3 times of factory effluent.According to the accompanying drawing Establishing process, concrete logistics connects the introduction referring to technical process in summary of the invention.Wastewater feed 22 (flow 792.1kg/hr, water accounts for 56%, glycerine accounts for 24%, sodium-chlor accounts for 20%) with filter F 1 in filtrate 6 (flow 2297.9kg/hr, water accounts for 55%, glycerine accounts for 27%, sodium-chlor accounts for 15%, propyl carbinol accounts for 3%) be mixed into waste water circulation mixture 1 (flow 3090kg/hr) and mix in the 3rd mixing tank M3 with propyl carbinol recycle stream 2 (flow 3911.5kg/hr), form waste water, solvent liquid 23 (flow 7010kg/hr) enters extraction tower R1.At normal pressure, temperature is operation under 50 ℃.In extractor R1, (flow is 2443.5kg/hr in output extraction tower lower floor logistics 3, water accounts for 51%, and glycerine accounts for 25%, and sodium-chlor accounts for 21%, propyl carbinol accounts for 3%) (flow is 4566.49kg/hr with extraction tower upper strata logistics 4, water accounts for 10%, and glycerine accounts for 4%, and propyl carbinol accounts for 85.7%, sodium-chlor accounts for 0.3%), and precipitated sodium chloride crystal 158.6kg/hr.
extraction tower upper strata logistics 4 is heated to 72 ℃ through preheater H1, form the first rectification under vacuum tower charging 8 and enter the first rectification under vacuum tower C1 at second column plate place, the overhead condenser working pressure is 0.5bar, the first rectification under vacuum tower top distillates azeotropic liquid 9, and (flow is 1577.69kg/hr, water accounts for 39%, propyl carbinol accounts for 61%) (flow is 230.14kg/hr with distillating azeotropic liquid 19 from the second rectification under vacuum tower top of the second rectification under vacuum tower C2, water accounts for 39%, propyl carbinol accounts for 61%) be mixed into two tower azeotrope mixture flow 14 through the first mixing tank M1 and enter decanting vessel D1.Two tower azeotrope mixture flow 14 layerings in D1, (flow is 671.62kg/hr in decanting vessel lower floor logistics 15, water accounts for 79.2%, propyl carbinol accounts for 20.8%) be heated to 70 ℃ through preheater H4 and become the second rectification under vacuum tower charging 18 and enter C2, the overhead condenser working pressure is 0.5bar, the second rectification under vacuum tower top distillates azeotropic liquid 19 and returns in decanting vessel, the second rectification under vacuum tower reactor pure water logistics 20 (flow is 441.48kg/hr, and water accounts for 99.99%).Decanting vessel upper strata logistics 16 (flow is 1136.11kg/hr, and water accounts for 15.6%, and propyl carbinol accounts for 84.4%) is heated to 74 ℃ through preheater H3 to be become decanting vessel lower floor preheating logistics 17 and is back in C1.The first rectification under vacuum tower tower bottoms 10 (flow is 4111.9kg/hr, and glycerine accounts for 5%, and propyl carbinol accounts for 95%) is heated to 88 ℃ through preheater H2 to be become the 3rd rectification under vacuum tower charging 11 and enters the 3rd rectification under vacuum tower C3.The overhead condenser working pressure is 0.3bar.(flow is 3918.1kg/hr to propyl carbinol returned logistics 12, propyl carbinol purity is 99.99%) be pressurised into propyl carbinol phegma 21 through pump P1, and be cooled to propyl carbinol recycle stream 2 through pre-cooler and return to extraction tower R1 recycle, glycerol product logistics 13 (flow is 192.1kg/hr, and glycerine purity is 99.99%) is product glycerine.The flow of each stream thigh is asked for an interview table 2.
Table 2: the propyl carbinol consumption is that 1.3 times of calculation result of wastewater flow rate gather
Embodiment 3:
This routine propyl carbinol consumption is 3.3 times of factory effluent.According to the accompanying drawing Establishing process, concrete logistics connects the introduction referring to technical process in summary of the invention.Wastewater feed 22 (flow 1841.9kg/hr, water accounts for 56%, glycerine accounts for 18%, sodium-chlor accounts for 26%) with filter F 1 in filtrate 6 (flow 1208.1kg/hr, water accounts for 55%, glycerine accounts for 27%, sodium-chlor accounts for 15%, propyl carbinol accounts for 3%) be mixed into waste water circulation mixture 1 (flow 3050kg/hr) and mix in the 3rd mixing tank M3 with propyl carbinol recycle stream 2 (flow 9932.5kg/hr), form waste water, solvent liquid 23 (flow 13010kg/hr) enters extraction tower R1.At normal pressure, temperature is operation under 70 ℃.In extractor R1, (flow is 1533.0kg/hr in output extraction tower lower floor logistics 3, water accounts for 43%, and glycerine accounts for 21%, and sodium-chlor accounts for 33%, propyl carbinol accounts for 3%) (flow is 11512kg/hr with extraction tower upper strata logistics 4, water accounts for 9%, and glycerine accounts for 4%, and propyl carbinol accounts for 86.7%, sodium-chlor accounts for 0.3%), and precipitated sodium chloride crystal 3 24.9kg/hr.
extraction tower upper strata logistics 4 is heated to 74 ℃ through preheater H1, form the first rectification under vacuum tower charging 8 and enter the first rectification under vacuum tower C1 at second column plate place, the overhead condenser working pressure is 0.5bar, the first rectification under vacuum tower top distillates azeotropic liquid 9, and (flow is 3887.8kg/hr, water accounts for 38%, propyl carbinol accounts for 62%) (flow is 540.6kg/hr with distillating azeotropic liquid 19 from the second rectification under vacuum tower top of the second rectification under vacuum tower C2, water accounts for 39%, propyl carbinol accounts for 61%) be mixed into two tower azeotrope mixture flow 14 through the first mixing tank M1 and enter decanting vessel D1.Two tower azeotrope mixture flow 14 layerings in D1, (flow is 1577.5kg/hr in decanting vessel lower floor logistics 15, water accounts for 79.2%, propyl carbinol accounts for 20.8%) be heated to 70 ℃ through preheater H4 and become the second rectification under vacuum tower charging 18 and enter C2, the overhead condenser working pressure is 0.5bar, the second rectification under vacuum tower top distillates azeotropic liquid 19 and returns in decanting vessel, the second rectification under vacuum tower reactor pure water logistics 20 (flow is 1037kg/hr, and water accounts for 99.99%).Decanting vessel upper strata logistics 16 (flow is 2580.75kg/hr, and water accounts for 15.6%, and propyl carbinol accounts for 84.4%) is heated to 74 ℃ through preheater H3 to be become decanting vessel lower floor preheating logistics 17 and is back in C1.The first rectification under vacuum tower tower bottoms 10 (flow is 10439.94kg/hr, and glycerine accounts for 5%, and propyl carbinol accounts for 95%) is heated to 88 ℃ through preheater H2 to be become the 3rd rectification under vacuum tower charging 11 and enters the 3rd rectification under vacuum tower C3.The overhead condenser working pressure is 0.3bar.(flow is 9952.45kg/hr to propyl carbinol returned logistics 12, propyl carbinol purity is 99.99%) be pressurised into propyl carbinol phegma 21 through pump P1, and be cooled to propyl carbinol recycle stream 2 through pre-cooler and return to extraction tower R1 recycle, glycerol product logistics 13 (flow is 487.5kg/hr, and glycerine purity is 99.99%) is product glycerine.The flow of each stream thigh is asked for an interview table 3.
Table 3: the propyl carbinol consumption is that 3.3 times of calculation result of wastewater flow rate gather
Claims (1)
1. the treatment process of a saliferous Glycerol Wastewater, is characterized in that, the processing step of the method is:
1) will add from the saliferous Glycerol Wastewater that produces in different production processes the propyl carbinol of 1.3 ~ 3.3 times of wastewater flow rates;
2) along with the adding of propyl carbinol, at normal pressure, temperature is 30 ~ 70 ℃, and the salt in the saliferous Glycerol Wastewater can crystallization, and liquid phase is divided into the organic phase that the upper strata contains 0.3% salt, and lower floor's water;
3) upper organic phase through rectifying, reclaims propyl carbinol, simultaneously except anhydrating, and obtains 99.9% pure glycerin as product; Lower floor's water filters, and filtrate is back in extraction tower and processes, the sodium-chlor washing and recycling of crystallization;
Described saliferous Glycerol Wastewater is thick liquid through evaporation concentration, contains 28 ~ 32% glycerine, 50% ~ 54% water, 18% sodium-chlor and a small amount of impurity;
Described upper organic phase is through rectifying, the idiographic flow that reclaims propyl carbinol and pure glycerin is: the topper stream of extraction tower (R1) enters the first rectification under vacuum tower (C1) through the first preheater (H1), the first rectification under vacuum tower (C1) tower bottoms, enter further rectifying separation purification of glycerol of the 3rd rectification under vacuum tower (C3) through the second preheater (H2), the 3rd rectification under vacuum tower (C3) tower top distillates propyl carbinol and is circulated in extraction tower (R1); The first rectification under vacuum tower (C1) tower top distillates propyl carbinol and water azeotropic liquid, with distillate azeotropic liquid from the second rectification under vacuum tower (C2) tower top and be mixed into standing demix in decanting vessel (D1), decanting vessel (D1) topper flows back to and flows into the first rectification under vacuum tower (C1) and continue rectifying, and the logistics of decanting vessel (D1) lower floor enters the second rectification under vacuum tower (C2); The second rectification under vacuum tower (C2) tower reactor distillates the pure water logistics, and tower top distillates azeotropic liquid.
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|---|---|---|---|---|
| CN102887604B (en) * | 2012-10-29 | 2014-01-01 | 杭州油脂化工有限公司 | Method for hydrolyzing sweet water through processing grease by using dissolved air flotation |
| CN104291523A (en) * | 2014-09-18 | 2015-01-21 | 波鹰(厦门)科技有限公司 | Method for recovering sodium chloride and glycerin from glycerin-containing high-salinity organic wastewater |
| CN104326872B (en) * | 2014-10-11 | 2016-06-08 | 波鹰(厦门)科技有限公司 | The recovery method of glycerol in highly salt containing organic waste water |
| PT108590A (en) | 2015-06-29 | 2016-12-29 | Univ Aveiro | CRUDE GLYCEROL PURIFICATION PROCESS |
| TWI636967B (en) | 2017-06-30 | 2018-10-01 | 國立清華大學 | System and method for treating salt-containing glycerin wastewater |
| CN107324577A (en) * | 2017-08-17 | 2017-11-07 | 长兴上拓环境科技有限公司 | A kind of epoxy resin production waste-water recycling treatment process |
| CN108298752B (en) * | 2018-01-17 | 2021-06-01 | 北京凯瑞英科技有限公司 | High-salt-content organic wastewater treatment system and wastewater treatment method |
| CN110229046B (en) * | 2018-03-05 | 2023-07-28 | 南通星辰合成材料有限公司 | Device and method for extracting glycerol and glycerol-like alcohol from epoxy wastewater evaporation mother liquor |
| CN109574801A (en) * | 2018-11-13 | 2019-04-05 | 南通新邦化工科技有限公司 | A kind of glycerol recovery process |
| CN109824191A (en) * | 2018-12-12 | 2019-05-31 | 张家港衡业特种树脂有限公司 | Glycerol is extracted in haline water in epoxy resin production process |
| CN110776030B (en) * | 2019-11-01 | 2020-12-08 | 西安交通大学 | Crystallization system for extracting NaCl aqueous solution by butanol injection flash evaporation and working method |
| CN115612559A (en) * | 2022-08-24 | 2023-01-17 | 东莞市新东欣环保投资有限公司 | Treatment method of glycerin residue |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4560812A (en) * | 1984-12-10 | 1985-12-24 | Shell Oil Company | Recovery of glycerine from saline waters |
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