CN103880209A - Processing method of sodium sulfate wastewater - Google Patents

Processing method of sodium sulfate wastewater Download PDF

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Publication number
CN103880209A
CN103880209A CN201410090322.XA CN201410090322A CN103880209A CN 103880209 A CN103880209 A CN 103880209A CN 201410090322 A CN201410090322 A CN 201410090322A CN 103880209 A CN103880209 A CN 103880209A
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sodium
sulfate
zinc
treatment process
process according
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CN103880209B (en
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罗宏波
马访中
甄利军
罗章志
刘敏
顾湘
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Guangdong Yuxing Fire-Retardant New Materials Co ltd
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GUANGDONG YUXING FIRE-RETARDANT NEW MATERIALS Co Ltd
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Abstract

The invention discloses a processing method of sodium sulfate wastewater. The processing method comprises the following steps: adding a chemical precipitator into the sodium sulfate wastewater, and filtering reaction liquid, so as to obtain sulfate precipitates and a sodium dihydrogen phosphate solution; adding zinc-containing substances into the sodium dihydrogen phosphate solution, reacting for 2-24 hours, and filtering the reaction liquid, so as to obtain sodium zinc phosphate precipitates and filter liquid. According to the processing method, the sulfate precipitates and the high-additional-value sodium zinc phosphate can be obtained, and the recovery rates of sulfate ions and sodium ions can reach above to 99.3%.

Description

A kind for the treatment of process of sodium sulfate wastewater
Technical field
The invention belongs to field of waste water treatment, be specifically related to a kind for the treatment of process of sodium sulfate wastewater.
Background technology
Contains sodium sulfate waste water is a kind of source of pollution common in multiple industries, if be directly discharged in physical environment without purifying treatment, can cause the salinity of water body and soil to raise, spoiled soil structure, cause soil compaction, be unfavorable for vegeto-animal growth, to environment.The treatment process of sodium sulfate wastewater roughly has two kinds at present: the one, and add liming to make it to generate calcium sulfate precipitation and sodium hydroxide solution; The 2nd, it is carried out to condensing crystal, extract sodium sulfate.Obviously, these two kinds of methods all can only obtain low value-added Industrial products; Prepare the product of dry state if want, energy consumption is very high again.The fundamental drawback of these two kinds of methods is: the rate of recovery of sulfate ion and sodium ion is lower, and in water after treatment, the concentration of sodium ion is still very high.
Summary of the invention
For solving the shortcoming and defect part of prior art, the object of the present invention is to provide a kind for the treatment of process of sodium sulfate wastewater, can under high conversion, make sulfate radical and sodium ion separate from water in the mode of precipitation respectively by the method.
For achieving the above object, the present invention adopts following technical scheme:
A treatment process for sodium sulfate wastewater, comprises the following steps:
(1) in sodium sulfate wastewater, add chemical precipitation agent, then by reacting liquid filtering, obtain sulfate precipitation and sodium dihydrogen phosphate;
(2) zinc-containing substance is joined in the sodium dihydrogen phosphate that step (1) obtains, reaction 4~24h, then by reacting liquid filtering, obtains sodium-zinc-phosphate throw out and filtrate.
After the inventive method is processed, in sodium sulfate wastewater, the rate of recovery of sulfate ion and sodium ion can be up to more than 99.3%.
Preferably, the chemical equivalent of the sodium sulfate in sodium sulfate wastewater, chemical precipitation agent and zinc-containing substance is respectively 1 part, 1 part and 2 parts.
Preferably, the chemical precipitation agent described in step (1) be sulfate ion precipitation agent and, phosphoric acid or react a kind of combination in the compound that only generates phosphoric acid with water; The specific operation process of step (1) is as follows:
(a) sulfate ion precipitation agent is added in sodium sulfate wastewater, reaction 4~24h, obtains mixed solution; Then filter, obtain sulfate precipitation and sodium hydroxide solution;
(b) react the compound that only generates phosphoric acid by phosphoric acid or with water and add in the sodium hydroxide solution that step (a) obtains, generate sodium dihydrogen phosphate.
Preferred, described sulfate ion precipitation agent is with, phosphoric acid or reacting the compound that only generates phosphoric acid is respectively 1 part and 2 parts with water according to the chemical equivalent of sulfate ion precipitation agent and phosphoric.
Preferred, described sulfate ion precipitation agent is the one in calcium oxide, calcium hydroxide, barium oxide or hydrated barta.
Preferred, described react the compound that only generates phosphoric acid with water be the one in phosphoric anhydride, metaphosphoric acid or polyphosphoric acid.
Preferred, the sulfate precipitation that step (a) obtains is through 1~2 post-drying of spray washing, and leacheate and sodium hydroxide solution are mixed into next operation steps.
Preferably, the described chemical precipitation agent of step (1) is barium dihydrogen phosphate or monocalcium phosphate; The specific operation process of step (1) is as follows: barium dihydrogen phosphate or monocalcium phosphate are added in sodium sulfate wastewater, and reaction 4~24h, then filters, and obtains sulfate precipitation and sodium dihydrogen phosphate.
Preferably, the described zinc-containing substance of step (2) is at least one in metallic zinc, zinc oxide, zinc hydroxide and zinc carbonate.
Preferably, the sodium-zinc-phosphate throw out that step (2) obtains is through 1~2 post-drying of spray washing.
Principle of the present invention is: in the sodium sulfate wastewater of concentration known, add successively chemical precipitation agent and zinc-containing substance, and the throw out that each step is obtained separates, washs and is dried, thereby obtain the sodium-zinc-phosphate that sulfate precipitation thing and added value are higher, and the rate of recovery of sulfate ion and sodium ion can be up to more than 99.3%.Above method can represent with following chemical equation:
Na 2SO 4+CaO+H 2O=CaSO 4↓+2NaOH
NaOH+H 3PO 4=NaH 2PO 4+H 2O
NaH 2PO 4+ZnO=NaZnPO 4↓+H 2O
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) treatment process of sodium sulfate wastewater of the present invention can make sulfate ion and sodium ion separate from water in the mode of precipitation respectively, obtains sulfate precipitation thing and sodium-zinc-phosphate, and the rate of recovery of sulfate ion and sodium ion is up to more than 99.3%.
(2) the present invention does not need condensing crystal just the sodium element in waste water can be precipitated, and energy consumption is low, and sodium-zinc-phosphate is as a kind of novel macroporous catalyst, has high added value.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A treatment process for sodium sulfate wastewater, comprises the following steps:
(1) get the sodium sulfate wastewater that 1L concentration is 1.25mol/L, in sodium sulfate wastewater, add 70g calcium oxide, reaction 24h, then filters, and obtains calcium sulfate precipitation and sodium hydroxide solution; By 2 post-dryings of calcium sulfate precipitation drip washing, obtain calcium sulphate solid 167g, theoretical yield is 98.23%, after conversion, the rate of recovery of sulfate ion reaches 98.23%;
(2) after leacheate mixes with sodium hydroxide solution, be 85% phosphoric acid to adding 283g massfraction in mixed solution, obtain sodium dihydrogen phosphate;
(3) 200g zinc oxide is joined in the sodium dihydrogen phosphate that step (2) obtains, reaction 4h, then filters, and obtains sodium-zinc-phosphate throw out and filtrate; By 1 post-drying of sodium-zinc-phosphate throw out drip washing, obtain sodium-zinc-phosphate solid 450g, theoretical yield is 98.15%, after conversion, the rate of recovery of sodium ion reaches 98.15%.
Embodiment 2
A treatment process for sodium sulfate wastewater, comprises the following steps:
(1) get the sodium sulfate wastewater that 1L concentration is 1.25mol/L, in sodium sulfate wastewater, add 214g hydrated barta, reaction 4h, then filters, and obtains barium sulfate precipitate and sodium hydroxide solution; By 2 post-dryings of barium sulfate precipitate drip washing, obtain barium sulfate solid 290g, theoretical yield is 99.57%, after conversion, the sulfate ion rate of recovery reaches 99.57%;
(2) after leacheate mixes with sodium hydroxide solution, in mixed solution, add 200g metaphosphoric acid, obtain sodium dihydrogen phosphate;
(3) 312g zinc carbonate is joined in the sodium dihydrogen phosphate that step (2) obtains, reaction 16h, then filters, and obtains sodium-zinc-phosphate throw out and filtrate; By 1 post-drying of sodium-zinc-phosphate throw out drip washing, obtain sodium-zinc-phosphate solid 454g, theoretical yield is 99.23%, after conversion, the rate of recovery of sodium ion reaches 99.23%.
Embodiment 3
A treatment process for sodium sulfate wastewater, comprises the following steps:
(1) get the sodium sulfate wastewater that 1L concentration is 1.25mol/L, in sodium sulfate wastewater, add 292g monocalcium phosphate, reaction 24h, then filters, and obtains calcium sulfate precipitation and sodium dihydrogen phosphate; By 2 post-dryings of calcium sulfate precipitation drip washing, obtain calcium sulphate solid 166g, theoretical yield is 97.65%, after conversion, the sulfate ion rate of recovery reaches 97.65%; Leacheate mixes with sodium dihydrogen phosphate, enters next step;
(2) 243g zinc hydroxide is joined in the sodium dihydrogen phosphate that step (1) obtains, reaction 8h, then filters, and obtains sodium-zinc-phosphate throw out and filtrate; By 1 post-drying of sodium-zinc-phosphate throw out drip washing, obtain sodium-zinc-phosphate solid 447g, theoretical yield is 97.49%, after conversion, the rate of recovery of sodium ion reaches 97.49%.
Embodiment 4
A treatment process for sodium sulfate wastewater, comprises the following steps:
(1) get the sodium sulfate wastewater that 1L concentration is 1.25mol/L, in sodium sulfate wastewater, add 414g barium dihydrogen phosphate, reaction 4h, then filters, and obtains barium sulfate precipitate and sodium dihydrogen phosphate; By 2 post-dryings of barium sulfate precipitate drip washing, obtain barium sulfate solid 288.4g, theoretical yield is 99%, after conversion, the sulfate ion rate of recovery reaches 99%; Leacheate mixes with sodium dihydrogen phosphate, enters next step;
(2) 163g metallic zinc is joined in the sodium dihydrogen phosphate that step (1) obtains, reaction 24h, then filters, and obtains sodium-zinc-phosphate throw out and filtrate; By 1 post-drying of sodium-zinc-phosphate throw out drip washing, obtain sodium-zinc-phosphate solid 453g, theoretical yield is 99%, after conversion, the rate of recovery of sodium ion reaches 99%.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.

Claims (10)

1. a treatment process for sodium sulfate wastewater, is characterized in that, comprises the following steps:
(1) in sodium sulfate wastewater, add chemical precipitation agent, then by reacting liquid filtering, obtain sulfate precipitation and sodium dihydrogen phosphate;
(2) zinc-containing substance is joined in the sodium dihydrogen phosphate that step (1) obtains, reaction 2~24h, then by reacting liquid filtering, obtains sodium-zinc-phosphate throw out and filtrate.
2. treatment process according to claim 1, is characterized in that, the chemical equivalent of sodium sulfate, chemical precipitation agent and zinc-containing substance in sodium sulfate wastewater is respectively 1 part, 1~2 part and 1 part.
3. treatment process according to claim 1, is characterized in that, the chemical precipitation agent described in step (1) be sulfate ion precipitation agent and, phosphoric acid or react a kind of combination in the compound that only generates phosphoric acid with water; The specific operation process of step (1) is as follows:
(a) sulfate ion precipitation agent is added in sodium sulfate wastewater, reaction 4~24h, obtains mixed solution; Then filter, obtain sulfate precipitation and sodium hydroxide solution;
(b) react the compound that only generates phosphoric acid by phosphoric acid or with water and add in the sodium hydroxide solution that step (a) obtains, generate sodium dihydrogen phosphate.
4. treatment process according to claim 3, is characterized in that, described sulfate ion precipitation agent and, phosphoric acid or the stoichiometric ratio of reacting the compound that only generates phosphoric acid with water is 1:1.
5. treatment process according to claim 3, is characterized in that, described sulfate ion precipitation agent is the one in calcium oxide, calcium hydroxide, barium oxide or hydrated barta.
6. treatment process according to claim 3, is characterized in that, described react the compound that only generates phosphoric acid with water be the one in phosphoric anhydride, metaphosphoric acid or polyphosphoric acid.
7. treatment process according to claim 3, is characterized in that, the sulfate precipitation that step (a) obtains is through 1~2 post-drying of spray washing, and leacheate and sodium hydroxide solution are mixed into next operation steps.
8. treatment process according to claim 1, is characterized in that, the described chemical precipitation agent of step (1) is barium dihydrogen phosphate or monocalcium phosphate; The specific operation process of step (1) is as follows: barium dihydrogen phosphate or monocalcium phosphate are added in sodium sulfate wastewater, and react 4~24h, then filter, obtain sulfate precipitation and sodium dihydrogen phosphate.
9. treatment process according to claim 1, is characterized in that, the described zinc-containing substance of step (2) is at least one in metallic zinc, zinc oxide, zinc hydroxide and zinc subcarbonate.
10. treatment process according to claim 1, is characterized in that, the sodium-zinc-phosphate throw out that step (2) obtains is through 1~2 post-drying of spray washing.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104150456A (en) * 2014-08-13 2014-11-19 连云港市德邦精细化工有限公司 Method for producing calcium phosphate salt and sodium phosphate salt by using sodium sulfate wastewater
CN104445721A (en) * 2014-11-19 2015-03-25 南通新邦化工科技有限公司 Combined treatment method for stearate wastewater
CN104891465A (en) * 2015-05-29 2015-09-09 湖北三宁化工股份有限公司 Method for preparing potassium dihydrogen phosphate from industrial monoammonium phosphate mother solution
CN104998611A (en) * 2015-07-17 2015-10-28 河海大学 Preparation method and application of barium-based modified bentonite
CN105776466A (en) * 2016-03-14 2016-07-20 湖北徐风环保科技有限公司 Purification method of sodium sulphate waste water
CN109704897A (en) * 2018-12-19 2019-05-03 安徽节源环保科技有限公司 A kind of waste water recycling method based on dimethyl suflfate
CN113029852A (en) * 2021-02-22 2021-06-25 天津钢管制造有限公司 Method for detecting content of sodium sulfate in oxide removing agent
CN114524545A (en) * 2022-03-03 2022-05-24 盛隆资源再生(无锡)有限公司 Method for recycling wastewater containing sodium sulfate
CN116443837A (en) * 2023-02-28 2023-07-18 贵州胜威福全化工有限公司 Method for preparing sodium hexametaphosphate from sodium sulfate and phosphoric acid

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US5055201A (en) * 1989-08-04 1991-10-08 Tiegel Manufacturing Company Process for removing dissolved contaminants from aqueous solutions using reversibly dispersible getters
US5346620A (en) * 1993-08-31 1994-09-13 Basf Corporation Process for waste water treatment by removal of sodium sulfate
CN100448789C (en) * 2006-12-05 2009-01-07 攀枝花钢企瑞通制冷设备有限公司 Technique for treating industrial wastewater of containing sodium sulfate
CN102241448B (en) * 2010-12-29 2012-11-28 厦门紫金矿冶技术有限公司 Comprehensive utilization method of sodium sulfate wastewater

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5055201A (en) * 1989-08-04 1991-10-08 Tiegel Manufacturing Company Process for removing dissolved contaminants from aqueous solutions using reversibly dispersible getters
US5346620A (en) * 1993-08-31 1994-09-13 Basf Corporation Process for waste water treatment by removal of sodium sulfate
CN100448789C (en) * 2006-12-05 2009-01-07 攀枝花钢企瑞通制冷设备有限公司 Technique for treating industrial wastewater of containing sodium sulfate
CN102241448B (en) * 2010-12-29 2012-11-28 厦门紫金矿冶技术有限公司 Comprehensive utilization method of sodium sulfate wastewater

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104150456B (en) * 2014-08-13 2016-06-08 连云港市德邦精细化工有限公司 The method producing synthos and sodium ascorbyl phosphate with sodium sulfate wastewater
CN104150456A (en) * 2014-08-13 2014-11-19 连云港市德邦精细化工有限公司 Method for producing calcium phosphate salt and sodium phosphate salt by using sodium sulfate wastewater
CN104445721A (en) * 2014-11-19 2015-03-25 南通新邦化工科技有限公司 Combined treatment method for stearate wastewater
CN104891465A (en) * 2015-05-29 2015-09-09 湖北三宁化工股份有限公司 Method for preparing potassium dihydrogen phosphate from industrial monoammonium phosphate mother solution
CN104998611B (en) * 2015-07-17 2017-03-08 河海大学 A kind of barium base method for preparing modified bentonite and application
CN104998611A (en) * 2015-07-17 2015-10-28 河海大学 Preparation method and application of barium-based modified bentonite
CN105776466A (en) * 2016-03-14 2016-07-20 湖北徐风环保科技有限公司 Purification method of sodium sulphate waste water
CN105776466B (en) * 2016-03-14 2018-06-15 湖北徐风环保科技有限公司 A kind of purification method of sodium sulfate wastewater
CN109704897A (en) * 2018-12-19 2019-05-03 安徽节源环保科技有限公司 A kind of waste water recycling method based on dimethyl suflfate
CN109704897B (en) * 2018-12-19 2020-07-03 安徽节源环保科技有限公司 Wastewater recycling method based on dimethyl sulfate
CN113029852A (en) * 2021-02-22 2021-06-25 天津钢管制造有限公司 Method for detecting content of sodium sulfate in oxide removing agent
CN114524545A (en) * 2022-03-03 2022-05-24 盛隆资源再生(无锡)有限公司 Method for recycling wastewater containing sodium sulfate
CN116443837A (en) * 2023-02-28 2023-07-18 贵州胜威福全化工有限公司 Method for preparing sodium hexametaphosphate from sodium sulfate and phosphoric acid

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