CN105036155B - The refining technique of by-product salt on a kind of glyphosate production route - Google Patents
The refining technique of by-product salt on a kind of glyphosate production route Download PDFInfo
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Abstract
The invention belongs to environmental technology field, relate to the refining technique of by-product salt on a kind of glyphosate production route, be applied particularly to glycine glyphosate mother solution waste water and process, PMIDA mother solution, iminodiacetic acid (salt) acid mother liquor, the process of by-product salt in trimethyl phosphate mother solution and chlor-alkali industry；Solid abraum salt on Process Technologies of Producing Glyphosate is due to containing substantial amounts of Organic substance so that solid abraum salt cannot be applied, and processes only as industrial waste salt.And use this process, most Organic substance in solid salt can be removed, reach the purpose of purifying solid salt, and can by the solid salt of purification or refined after saline be used for other industry such as chlor-alkali production, production of caustic soda etc., achieve changing waste into resources to utilize, there is the highest economic and social benefit.
Description
Technical field
The invention belongs to environmental technology field, relate to the process for refining side of by-product salt on a kind of glyphosate production route
Method, is applied particularly to glycine glyphosate mother solution waste water and processes, PMIDA mother solution, iminodiacetic acid (salt) acid mother liquor,
The process of by-product salt in trimethyl phosphate mother solution and chlor-alkali industry.
Background technology
It is all to be succeeded in developing by U.S. Meng Shan for 1971 at glyphosate, is mainly used in the field of transgenic crop.
Its mechanism of action is to reach to kill the mesh of plant by the activity of photophosphorylation and ATP enzyme in suppression plant
's.The transgenic crop in the whole world mainly has Semen sojae atricolor and Semen Maydis, accounts for whole world transgenic crop cultivated area
78%.
Glyphosate waste water discharge capacity is very big, often produces 1t glyphosate and can produce 17t waste water, and damage ratio is more serious.
Containing organic matter raw material used on substantial amounts of process route and the by-product of generation in waste water, its composition is very
Complexity, such as sodium phosphite, sodium phosphate, methyl glyphosate, nitroso-group glyphosate, glyphosine, aminomethyl
Phosphoric acid, methylol phosphoric acid, glycine, triacetamide, Iminodiacetate and the sodium chloride of high concentration
(NaCl concentration is up to more than 10%) etc..
Glyphosate waste water total phosphorus (Total Phosphorus is called for short TP) can reach more than 5000mg/L；Total organic carbon
(Total Organic Carbon is called for short TOC) is up to about 8000mg/L；(Total Nitrogen is called for short total nitrogen
TN) can reach more than 1200mg/L；And the salt content of high concentration makes glyphosate waste water biodegradability poor, one
As carry out a biological disposal upon and be difficult to.
The Chinese invention patent of Application No. 201310318538.2 discloses the process side of a kind of glyphosate waste water
Method, comprises the following steps: (1) adjusts pH to about 1.0 with dense HCl, then obtains clear by absorption method
Filtrate；(2) add calcium chloride, isolate organic calcium precipitate；(3) palm fibre is filtered out with iron hydroxide particle
Yellow solid precipitate；(4) adding transition metal ion, the grass after being had been fully processed by chelating resin is sweet
Phosphine waste water.Phosphorus content is less than 1.0mg/L, and carbon content is less than 100mg/L, and nitrogen content is less than 20mg/L, COD
Less than 200mg/L, but this waste water still needs to be further processed.
The Chinese invention patent of Application No. 201210350157.8 discloses a kind of glyphosate production wastewater catalysis
Wet oxidation preprocess method, comprises the following steps: (1) regulation wastewater pH is 8～10；(2) addition is many
Component homogeneous catalyst, with air as oxidant, uses continuous catalysis wet oxidation reaction device to Organic substance
Carry out oxidative degradation；It is 210～230 DEG C that its oxidizing temperature controls, and reaction pressure is 2～4MPa, during reaction
Between 0.3～2h.This method is the highest to the requirement of reaction unit, and cost investment is higher.
Processing glyphosate waste water at present, conventional method is to be concentrated through film separation system by glyphosate mother solution
To reclaim glyphosate, but for the high salt concentration in eluting mother solution, need to use the nanofiltration eluting work of 3～4 grades
Skill, it is estimated that often process 1 ton of mother solution and can produce the light liquid of nanofiltration of more than 1.4 tons；And by glyphosate waste water
Its content of organics of the sodium chloride that evaporative crystallization obtains is high, shows as total organic carbon TOC, total nitrogen TN and total
Phosphorus TP content is the highest, it is difficult to does raw materials for production for other industry and uses, only as fixed-end forces, its
Substantial amounts of sodium chloride resource is wasted.Though by-product salt being carried out high temperature sintering can remove major part Organic substance,
But calcination cost is the highest, the requirement to equipment is the most high, the most remaining substantial amounts of phosphorus-containing compound in solid salt,
Its total phosphorus content is the highest.
Summary of the invention
The purpose of the present invention is contemplated to overcome the solid salt of above-mentioned evaporative crystallization to apply a limited difficult problem, it is proposed that
On a kind of glyphosate production route, the refining technique of by-product salt, reaches the purpose of purifying solid salt, and can
By the solid salt of purification or refined after saline be used for other industry such as chlor-alkali production, production of caustic soda etc., reality
Show changing waste into resources utilization, there is the highest economic and social benefit.
The present invention solves above-mentioned technical problem and be employed technical scheme comprise that and provide a kind of glyphosate production route
The refining technique of upper by-product salt, the method is to the pair of effluent brine evaporative crystallization gained in glyphosate industry
Produce salt to refine, specifically include following steps:
Step one, being cleaned pending solid abraum salt abluent, scavenging period is 10～60min, cleans
Agent consumption is 1～10 times of solid salt quality, and cleaning temperature is 5～60 DEG C, carries out solid-liquid separation after cleaning；
Step 2, in the solid salt that step obtains after a separation add pure water, being made into NaCl content is
The solution of 200-310g/L, is 6～12 with NaOH regulation pH；
Step 3, the saline nanofiltration membrane separation that step 2 is prepared, control into the pressure of film be 1.0～
4.0MPa, temperature is 5～40 DEG C, and nanofiltration cycles of concentration by mass is 4～15 times；
Step 4, NF membrane light liquid NaOH or HCl obtained by step 3 adjust pH to 2～12, then
Adding oxidant to aoxidize, oxidant concentration is 100～5000mg/L, and oxidizing temperature is 5～60 DEG C, oxygen
The change time is 1～5 hour；
Step 5, phosphate eliminating flocculant after the solution oxide in step 4, will be added, continues low rate mixing reaction,
Reaction temperature 5～60 DEG C, the response time is 0.5～2 hour；
Step 6, by step 5 solution NaOH or HCl regulate pH to 7～8, standing sedimentation,
Sedimentation time is 0.5～6h；
Step 7, saline step 6 obtained and precipitating sludge carry out solid-liquid separation, filtrate i.e. refined brine.
Preferably, the abluent in the refining technique step one of by-product salt on described glyphosate production route
For NaCl, HCl, NaOH, methanol, the aqueous solution of one or more compositions of ethanol.
Preferably, on described glyphosate production route, the solid-liquid separation in the refining technique of by-product salt includes
The combination of one or more among centrifugation, sucking filtration, sedimentation filtration, filter pressing, microfiltration, ultrafiltration.
Preferably, on described glyphosate production route, the NF membrane in the refining technique of by-product salt is to sulfur
Rejection >=98.0% of acid magnesium, the NF membrane to sodium chloride rejection≤20.0%.
Preferably, the oxidation in the step 4 of the refining technique of by-product salt on described glyphosate production route
Agent is sodium hypochlorite, H2O2, chlorine dioxide, one or more combination in Na2Fe04 and sodium peroxydisulfate,
Sodium hypochlorite concentration is with free chlorine meter, H2O2Oxidant concentration is with H2O2Meter, chlorine dioxide in terms of chlorine dioxide,
Na2Fe04 is with Fe6+Meter, sodium peroxydisulfate are in terms of persulfate, and mixed oxidization agent concentration is that respective oxidant is dense
Degree summation.
Preferably, described glyphosate production route flocculates in the step 5 of the refining technique of by-product salt and removes
The concentration of phosphorus agent is 10～1000mg/L, and flocculation dephosphorization agent is FeSO4、FeCl3、AlCl3、CaO、PAC、
The aqueous solution of one or more combinations among PAM.
Preferably, institute in the step 7 of the refining technique of by-product salt on described a kind of glyphosate production route
The saline stated separates with precipitating sludge and includes centrifugation, sucking filtration, sedimentation filtration, ultrafiltration, filter pressing, microfiltration
In the combination of one or more.
The present invention compared with the existing technology has the following advantages and effect: the solid on Process Technologies of Producing Glyphosate
Abraum salt is due to containing substantial amounts of Organic substance so that solid abraum salt cannot be applied, and processes only as industrial waste salt.
And use this process, it is possible to remove most Organic substance in solid salt, reach the purpose of purifying solid salt,
And can by the solid salt of purification or refined after saline be used for other industry such as chlor-alkali production, production of caustic soda etc.,
Achieve changing waste into resources to utilize, there is the highest economic and social benefit.
Compared with prior art, processing cost of the present invention is relatively low, and reaction condition is gentleer, Jing Guoben
The higher solid sodium chloride of purity or refined brine can be obtained so that solid salt or purified salt after PROCESS FOR TREATMENT
Water can overcome by-product salt on Process Technologies of Producing Glyphosate be difficult to process as raw material for other industry
Problem, it is achieved that recycling.
Accompanying drawing explanation
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment
Or the required process chart used is briefly described in description of the prior art, it should be apparent that below,
Process chart in description is only some embodiments of the present invention.
Fig. 1 is the process flow diagram of the present invention.
Detailed description of the invention
Below in conjunction with the technological process of embodiment Yu this invention of accompanying drawing 1, the present invention is described in further detail,
Following example are explanation of the invention and the invention is not limited in following example.
Embodiment 1
Take the by-product salt 5kg obtained by preparing glyphosate by glycin method production line, clean with abluent, control
Abluent consumption processed is 1:1 with the mass ratio of solid salt, and scavenging period is 30min, and wash number is 1 time,
Then carry out vacuum filtration, obtain solid salt.Solid salt is configured to the solution that NaCl content is 300g/L again,
Surveying its total organic carbon TOC is 158.6mg/L, total nitrogen TN be 29.05mg/L, TP be 93.2mg/L.
The NaOH of the saline 1mol/L prepared is adjusted pH to 10, then carries out nanofiltration membrane separation, control
Entering film pressure is 2.0MPa, and temperature is 13.1 ± 2 DEG C, when NF membrane cycles of concentration is 5 times by mass
Stop nanofiltration membrane separation.The total organic carbon TOC recording the light liquid of NF membrane is 26.29mg/L, and total nitrogen TN is
8.07mg/L, TP are 2.74mg/L.
The NaOH of light for NF membrane liquid 1mol/L is adjusted pH to 10.42, adds oxidizing, control
Oxidant concentration is 1000mg/L, adds phosphate eliminating flocculant, control at temperature 13.7 DEG C after stirring reaction 2.5h
Phosphate eliminating flocculant concentration processed is 100mg/L, continues low rate mixing reaction 0.5h.Then with the NaOH of 1mol/L
Solution adjusts pH to 7, and standing sedimentation, the standing sedimentation time is 5h.After sedimentation, supernatant ultrafiltration was carried out
Filter, ultra-filtration filters pressure is 0.2MPa, and temperature is 13.7 ± 2 DEG C, and filtrate is refined brine, its key index
Total organic carbon is 8.8mg/L, total nitrogen TN be 2.26mg/L, TP be 0.003mg/L.
Embodiment 2:
Take the by-product salt 5kg obtained by preparing glyphosate by glycin method production line, clean with abluent, control
Abluent consumption processed is 7:5 with the mass ratio of solid salt, and scavenging period is 20min, and wash number is 1 time,
Then carrying out vacuum filtration, vacuum obtains solid salt after draining.It is 300g/L that solid salt is configured to NaCl content again
Solution, surveying its total organic carbon TOC is 301.45mg/L, and total nitrogen TN is that 53.97mg/L, TP are
185mg/L。
The NaOH of the saline 1mol/L prepared is adjusted pH to 10, then carries out nanofiltration membrane separation, control
Entering film pressure is 2.6MPa, and temperature is 14.7 ± 2 DEG C, when NF membrane cycles of concentration is 5 times by mass
Stop nanofiltration membrane separation.The total organic carbon TOC recording the light liquid of NF membrane is 59.39mg/L, and total nitrogen TN is
15.76mg/L, TP are 7.47mg/L.
The NaOH of light for NF membrane liquid 1mol/L is adjusted pH to 9.83, adds oxidizing, control oxygen
Agent concentration is 1500mg/L, adds phosphate eliminating flocculant, control at temperature 26.4 DEG C after stirring reaction 2.5h
Phosphate eliminating flocculant concentration is 101mg/L, continues low rate mixing reaction 0.5h.Then with the NaOH of 1mol/L
Solution adjusts pH to 7, and standing sedimentation, the standing sedimentation time is 0.5h.After sedimentation, supernatant filter paper is carried out
Filtering, filtrate is refined brine, and its key index total organic carbon is 36.61mg/L, and total nitrogen TN is 2.52mg/L,
TP is 0.007mg/L.
Embodiment 3:
Take the by-product salt 5kg obtained by preparing glyphosate by glycin method production line, clean with abluent, control
Abluent consumption processed is 3:1 with the mass ratio of solid salt, and scavenging period is 10min, and wash number is 1 time,
Then carrying out vacuum filtration, vacuum obtains solid salt after draining.It is 300g/L that solid salt is configured to NaCl content again
Solution, surveying its total organic carbon TOC is 301.45mg/L, and total nitrogen TN is that 53.97mg/L, TP are
185mg/L。
The NaOH of the saline 1mol/L prepared is adjusted pH to 10, then carries out nanofiltration membrane separation, control
Entering film pressure is 2.6MPa, and temperature is 14.7 ± 2 DEG C, and NF membrane cycles of concentration is to stop when 5 times by mass
Only nanofiltration membrane separation.The total organic carbon TOC recording the light liquid of NF membrane is 59.39mg/L, and total nitrogen TN is
15.76mg/L, TP are 7.47mg/L.
The NaOH of light for NF membrane liquid 1mol/L is adjusted pH to 10.42, adds oxidizing, control
Oxidant concentration is 1000mg/L, adds phosphate eliminating flocculant, control at temperature 10.2 DEG C after stirring reaction 2.5h
Phosphate eliminating flocculant concentration processed is 110mg/L, continues low rate mixing reaction 1.0h.Then with the NaOH of 1mol/L
Solution adjusts pH to 7, and standing sedimentation, the standing sedimentation time is 0.5h.Supernatant vacuum filtration after sedimentation
Filtering, filtrate is refined brine, and its key index total organic carbon is 26.61mg/L, and total nitrogen TN is
3.25mg/L, TP are 0.005mg/L.
Embodiment 4:
Take the by-product salt 5kg obtained by preparing glyphosate by glycin method production line, clean with abluent, control
Abluent consumption processed is 4:1 with the mass ratio of solid salt, and scavenging period is 10min, and wash number is 1 time,
Then carrying out vacuum filtration, vacuum obtains solid salt after draining.It is 289g/L that solid salt is configured to NaCl content again
Solution, surveying its total organic carbon TOC is 198.2mg/L, total nitrogen TN be 41.7mg/L, TP be 143.9mg/L.
The NaOH of the saline 1mol/L prepared is adjusted pH to 10, then carries out nanofiltration membrane separation, control
Entering film pressure is 2.0MPa, and temperature is 20 ± 2 DEG C, when NF membrane cycles of concentration is 10 times by mass
Stop nanofiltration membrane separation.The total organic carbon TOC recording the light liquid of NF membrane is 93.5mg/L, and total nitrogen TN is
20.67mg/L, TP are 13.21mg/L.
The NaOH of light for NF membrane liquid 1mol/L is adjusted pH to 9.83, adds oxidizing, control oxygen
Agent concentration is 1800mg/L, adds phosphate eliminating flocculant, control at temperature 26.4 DEG C after stirring reaction 2.5h
Phosphate eliminating flocculant concentration is 150mg/L, continues low rate mixing reaction 0.5h.Then with the NaOH of 1mol/L
Solution adjusts pH to 7, and standing sedimentation, the standing sedimentation time is 0.5h.After sedimentation, supernatant filter paper is carried out
Filtering, filtrate is refined brine, and its key index total organic carbon is 31.38mg/L, and total nitrogen TN is 1.56mg/L,
TP is 0.3mg/L.
Embodiment 5:
Take the by-product salt 5kg obtained by trimethyl phosphate production line, clean with abluent, control abluent
Consumption is 5:1 with the mass ratio of solid salt, and scavenging period is 10min, and wash number is 1 time, then carries out
Vacuum filtration, vacuum obtains solid salt after draining.It is the molten of 308g/L that solid salt is configured to NaCl content again
Liquid, surveying its total organic carbon TOC is 325mg/L, total nitrogen TN be 47.8mg/L, TP be 420mg/L.
The NaOH of the saline 1mol/L prepared is adjusted pH to 9.5, then carries out nanofiltration membrane separation, control
Entering film pressure is 2.0MPa, and temperature is 12 ± 2 DEG C, stops when NF membrane cycles of concentration is 5 times by mass
Only nanofiltration membrane separation.The total organic carbon TOC now recording the light liquid of NF membrane is 43.6mg/L, and total nitrogen TN is
14.4mg/L, TP are 12.3mg/L.
The NaOH of light for NF membrane liquid 1mol/L is adjusted pH to 9.83, adds oxidizing, control oxygen
Agent concentration is 1000mg/L, adds phosphate eliminating flocculant, control at temperature 14.4 DEG C after stirring reaction 2.5h
Phosphate eliminating flocculant concentration is 101mg/L, continues low rate mixing reaction 0.5h.Then with the NaOH of 1mol/L
Solution adjusts pH to 7, and standing sedimentation, the standing sedimentation time is 4h.After sedimentation, supernatant ultrafiltration was carried out
Filter, ultra-filtration filters pressure is 0.2MPa, and temperature is 15.4 ± 2 DEG C, and filtrate is refined brine, its key index
Total organic carbon is 15.29mg/L, total nitrogen TN be 2.78mg/L, TP content be 0mg/L.
Furthermore, it is necessary to illustrate, the specific embodiment described in this specification, it is only this inventive method
Section Example, all equivalences done according to the principle described in inventional idea of the present invention or simple change, all wrap
Including in the protection domain of patent of the present invention, those skilled in the art can be to described
Specific embodiment make various amendment or supplement or use similar mode to substitute, without departing from this
Invention structure or surmount scope defined in the claims, protection scope of the present invention all should be belonged to.
Claims (8)
1. the refining technique of by-product salt on a glyphosate production route, it is characterised in that the method is right
In glyphosate industry, the by-product salt of effluent brine evaporative crystallization gained refines, and specifically includes following steps:
Step one, being cleaned pending solid abraum salt abluent, scavenging period is 10～60min, cleans
Agent consumption is 1～5 times of solid salt quality, and cleaning temperature is 5～60 DEG C, carries out solid-liquid separation after cleaning；
Step 2, in the solid salt that step obtains after a separation add pure water, being made into NaCl content is
The solution of 200-310g/L, is 6～12 with NaOH regulation pH；
Step 3, the saline nanofiltration membrane separation that step 2 is prepared, control into the pressure of film be 1.0～
4.0MPa, temperature is 5～40 DEG C, and nanofiltration cycles of concentration by mass is 4～15 times；
Step 4, NF membrane light liquid NaOH or HCl obtained by step 3 adjust pH to 2～12, then
Adding oxidant to aoxidize, oxidant concentration is 100～5000mg/L, and oxidizing temperature is 5～60 DEG C, oxygen
The change time is 1～5 hour；
Step 5, phosphate eliminating flocculant after the solution oxide in step 4, will be added, continues low rate mixing reaction,
Reaction temperature 5～60 DEG C, the response time is 0.5～2 hour；
Step 6, solution NaOH or HCl in step 5 is regulated pH to 7～8, standing sedimentation is heavy
The fall time is 0.5～6h；
Step 7, saline step 6 obtained and precipitating sludge carry out solid-liquid separation, filtrate i.e. refined brine.
The refining technique of by-product salt on glyphosate production route the most according to claim 1, it is special
Levy the abluent being in described step one be NaCl, HCl, NaOH, methanol, ethanol one or more
The aqueous solution of composition.
The refining technique of by-product salt on glyphosate production route the most according to claim 1, it is special
Levy and be that described solid-liquid separation includes among centrifugation, sucking filtration, sedimentation filtration, filter pressing, microfiltration, ultrafiltration
The combination of one or more.
The refining technique of by-product salt on glyphosate production route the most according to claim 1, it is special
Levy and be that described NF membrane is rejection >=98.0% to magnesium sulfate, receiving to sodium chloride rejection≤20.0%
Filter membrane.
The refining technique of by-product salt on glyphosate production route the most according to claim 1, it is special
Levying the oxidant being in described step 4 is sodium hypochlorite, H2O2, chlorine dioxide, Na2Fe04 and persulfuric acid
One or more combination in sodium, sodium hypochlorite concentration is with free chlorine meter, H2O2Oxidant concentration is with H2O2Meter,
Chlorine dioxide in terms of chlorine dioxide, Na2Fe04 is with Fe6+Meter, sodium peroxydisulfate in terms of persulfate, mixed oxidization
Agent concentration is respective oxidant concentration summation.
The refining technique of by-product salt on glyphosate production route the most according to claim 1, it is special
Levying the concentration being in described step 5 to flocculate dephosphorization agent is 10～1000mg/L, and flocculation dephosphorization agent is FeSO4、
FeCl3、AlCl3, aqueous solutions of one or more combinations among CaO, PAC, PAM.
The refining technique of by-product salt on glyphosate production route the most according to claim 1, it is special
Levy and be that the saline described in described step 7 separates with precipitating sludge and include centrifugation, sucking filtration, settled
The combination of one or more in filter, ultrafiltration, filter pressing, microfiltration.
The refining technique of by-product salt on glyphosate production route the most according to claim 1, it is special
Levy and be that the method specifically includes following steps:
Step one, being cleaned pending solid abraum salt abluent, scavenging period is 10～60min, cleans
Agent consumption is 1～5 times of solid salt quality, and cleaning temperature is 10～30 DEG C, carries out solid-liquid separation after cleaning；
Step 2, in the solid salt that step obtains after a separation add pure water, being made into NaCl content is
The solution of 200-310g/L, is 9～11 with NaOH regulation pH；
Step 3, the saline nanofiltration membrane separation that step 2 is prepared, control into the pressure of film be 1.5～
3.0MPa, temperature is 10～20 DEG C, and nanofiltration cycles of concentration by mass is 4～8 times；
Step 4, NF membrane light liquid NaOH or HCl obtained by step 3 adjust pH to 2～12, then
Adding oxidant to aoxidize, oxidant concentration is 500～2000mg/L, and oxidizing temperature is 10～30 DEG C,
Oxidization time is 1～5 hour；
Step 5, phosphate eliminating flocculant after the solution oxide in step 4, will be added, continues low rate mixing reaction,
Reaction temperature 5～60 DEG C, the response time is 0.5～2 hour；
Step 6, solution NaOH or HCl in step 5 is regulated pH to 7～8, standing sedimentation is heavy
The fall time is 0.5～6h；
Step 7, saline step 6 obtained and precipitating sludge carry out solid-liquid separation, filtrate i.e. refined brine.
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| CN105692960A (en) * | 2016-03-04 | 2016-06-22 | 安徽国星生物化学有限公司 | Treatment method for glyphosate mother liquor |
| CN105836764B (en) * | 2016-03-24 | 2017-05-17 | 南京理工大学 | Recycling method of waste salt from salt-containing waste water in organic synthetic industry |
| CN110550794B (en) * | 2018-05-30 | 2022-02-11 | 杭州九清科技有限公司 | Method for separating phosphate-containing waste liquid |
| CN109848185B (en) * | 2019-03-11 | 2020-10-27 | 安徽华星化工有限公司 | Monosultap waste salt harmless treatment method |
| CN110451530A (en) * | 2019-08-16 | 2019-11-15 | 中国科学院过程工程研究所 | A kind of fine purification treatment process of industrial waste salt containing organic matter of desalinization of soil by flooding or leaching combination ex situ oxidation |
| CN110642270A (en) * | 2019-09-29 | 2020-01-03 | 中国科学院过程工程研究所 | Method for refining and treating industrial waste salt |
| CN111943230A (en) * | 2020-06-29 | 2020-11-17 | 杭州天创环境科技股份有限公司 | Recycling treatment method for industrial wastewater byproduct salt |
| CN111870862A (en) * | 2020-07-29 | 2020-11-03 | 沈阳有研矿物化工有限公司 | Harmless treatment method for waste salt in production of alkylxanthate beneficiation reagent |
| CN113751469B (en) * | 2021-09-14 | 2022-06-03 | 浙江海禹环保科技有限公司 | Resource treatment method and device for industrial waste salt |
| CN113896349B (en) * | 2021-10-11 | 2023-04-07 | 盐城工学院 | Phosphorus and impurity removal system and process for glyphosate byproduct high-salt waste salt |
| CN114230082A (en) * | 2021-12-28 | 2022-03-25 | 浙江万盛股份有限公司 | Method for purifying and refining industrial salt from phosphate flame retardant wastewater |
| CN114289478B (en) * | 2021-12-30 | 2023-05-16 | 连云港职业技术学院 | Method for recycling waste salt containing organic matters |
| CN116282079A (en) * | 2022-12-29 | 2023-06-23 | 河南红东方化工股份有限公司 | Method for directly using byproduct industrial salt in chlor-alkali industry |
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