CN207933534U - A kind of purification devices of abraum salt - Google Patents

Abstract

The utility model is related to a kind of purification devices of abraum salt, more particularly to sodium chloride abraum salt embrane method purification process and device.Including：Salt dissolving groove, the NaCl waste salt dregs for will be obtained in pesticide synthesis are dissolved in water；NF membrane is connected to salt dissolving groove, for the brine obtained in salt dissolving groove to be filtered；Except cation impurity device, it is connected to the per-meate side of NF membrane, cation impurity is removed in the penetrating fluid for obtaining NF membrane；Chelating resin column, is connected to except cation impurity device, and salt treatment is removed using resin for the production water to being obtained except cation impurity device；Ion-exchange membrane electrolyzer is connected to chelating resin column, carries out electrolysis processing for the production water to chelating resin column, obtains caustic soda and chlorine.The problem of purification process and device of the abraum salt of the utility model can efficiently solve abraum salt ion-exchange membrane tank pressure caused by being applied in chlorine industry with organic pollution and increase, and electrolytic efficiency is low, and abraum salt can not use.

Description

A kind of purification devices of abraum salt

Technical field

The utility model is related to a kind of purification devices of abraum salt, more particularly to a kind of sodium chloride abraum salt film applied to pesticide Method purification devices belong to pesticide industry technical field.

Background technology

In pesticide industry, abraum salt can only be used as dangerous waste to dispose due to containing organic matter, form the waste of resource.Mesh Before, abraum salt processing method is in common pesticide industry：Recrystallization method etc. after burning method, multistage washing method, landfill method, dissolving absorption Deng.Each method has the practicality, but there is also its drawbacks.Burning method has that cost of investment is high, operating cost is high；It is multistage Washing method generates large amount of sewage, forms secondary pollution, and by it was verified that abraum salt is still difficult to industrial applications；Landfill method It is economical but there are hidden danger；Recrystallization method organic matter removal is not thorough after dissolving absorption, and effluent brine is into can cause to be electrolysed after ionic membrane Slot tank voltage increases, and electrolytic efficiency reduces even last damage ionic membrane.

The utility model of patent CN105293531A discloses a kind of fine purification treatment process of by-product Nacl, by " molten The process route of solution-absorption-spray drying-medium temperature calcination-dissolving-Ultrafiltration-Concentration " obtains pure white salt, process route it is long and The follow-up outlet of salt is not known.The utility model of patent CN104649495A discloses amino phenylate, p-nitrophenol production is useless Simultaneously evaporative crystallization obtains solid sodium chloride salt refining method for water absorption, is obtained using " high-temperature calcination-dissolving-evaporative crystallization " high-quality The solid sodium chloride salt of amount, technology investment is of high cost, operating cost is high and abraum salt subsequent processing thinking and be not known.Based on above-mentioned Situation makes the application.

Utility model content

The purpose of this utility model is：It is handled as dangerous waste for the pesticide industry abraum salt for containing organic pollution, it can not The present situation used proposes a kind of technical solution carrying out purification process to abraum salt, mainly handles organics removal by nanofiltration Afterwards, then cation impurity removal in abraum salt is carried out, realizes that abraum salt enters electrolysis with ion-exchange film after purification, improves electrolysis with ion-exchange film effect Rate.

Technical solution is：

The first aspect of the utility model, provides：

A kind of purification process of abraum salt, includes the following steps：

The NaCl waste salt dregs obtained in pesticide synthesis are dissolved in water by the 1st step；

The brine that 1st step obtains is sent into NF membrane and is filtered by the 2nd step；

3rd step removes cation impurity to the filtrate that the 2nd step obtains using the precipitation method；

4th step, the brine obtained to the 3rd step further decrease cation impurity levels using chelating resin；

The NaCl brine after purification that 4th step obtains is sent into ion film caustic soda electrolytic cell and is carried out at electrolysis by the 5th step Reason.

In one embodiment, contain organic matter in the NaCl waste salt dregs in the 1st step.

In one embodiment, the brine that the 1st step obtains refers to the brine for mainly containing NaCl；In the brine COD ranges are 1~1000ppm；1~100ppm of TOC ranges in the brine.

In one embodiment, the nanofiltration 100~500Da of retaining molecular weight, nanofiltration membrane material are selected from acetic acid One or several kinds of combinations in cellulosic polymer, polyamide, polyester, polyimides or polyvinyl etc.； Nanofiltration technique preferred parameter is：Operating pressure is 2.5~3.5MPa, and circular flow is 2.0~3.0m3/h, cycles of concentration is 3~ 6 times.

In one embodiment, cation impurity is selected from Ca²⁺、Mg²⁺、Cs⁺Or Ni⁺Ion；The precipitation method removal sun from Sub- impurity refers to：CO is added in effluent brine₃ ^2-And/or OH^-Ion is carried out as the cation impurity in precipitating reagent, with brine Sediment is generated after precipitation reaction, then is filtered by seperation film, sediment is removed, after seperation film per-meate side obtains processing Brine.

In one embodiment, the cation in precipitating reagent is identical as the cation of main component in brine；It is heavy to be added Shallow lake agent is selected from NaOH, Na₂CO₃In one or several kinds of mixtures, the addition of each precipitating reagent both greater than precipitates miscellaneous completely Matter cation aequum.

In one embodiment, the seperation film of use refers to ceramic filtration membrane；Filter membrane be average pore size be 0.005 μm~ 0.5 μm or molecular cut off are 5000~1000000Da.

In one embodiment, chelating resin model refers to S-930 or D463.

In one embodiment, ion film caustic soda electrolytic cell is bipolar slot, and diaphragm is cation-exchange membrane.

The second aspect of the utility model, provides：

A kind of purification devices of abraum salt, including：

Salt dissolving groove, the NaCl waste salt dregs for will be obtained in pesticide synthesis are dissolved in water；

NF membrane is connected to salt dissolving groove, for the brine obtained in salt dissolving groove to be filtered；

Except cation impurity device, it is connected to the per-meate side of NF membrane, is carried out in the penetrating fluid for obtaining NF membrane Remove cation impurity；

Chelating resin column is connected to except cation impurity device, for the production hydromining to being obtained except cation impurity device Salt treatment is removed with resin；

Ion-exchange membrane electrolyzer is connected to chelating resin column, carries out electrolysis processing for the production water to chelating resin column, obtains Caustic soda and chlorine.

In one embodiment, 100~500Da of molecular cut off of NF membrane.

In one embodiment, it is sub- to be selected from cellulose acetate Type of Collective object, polyamide, polyester, polyamides for nanofiltration membrane material One or several kinds of combinations in amine or polyvinyl etc..

In one embodiment, except cation impurity device includes that reaction tank and precipitating reagent add tank, precipitating reagent is thrown Add tank for precipitating reagent to be added into reaction tank, reaction tank is connected to the per-meate side of NF membrane, is used for the penetrating fluid of permeable membrane Precipitation reaction is carried out with precipitating reagent；Equipment for separating liquid from solid is connected to reaction tank, for carrying out solid-liquid to the feed liquid after precipitation reaction Separation；The per-meate side of equipment for separating liquid from solid is connect with chelating resin column.

In one embodiment, precipitating reagent, which adds, is equipped with NaOH and/or Na in tank₂CO₃。

In one embodiment, equipment for separating liquid from solid refers to ceramic filtration membrane；Filter membrane be average pore size be 0.005 μm~ 0.5 μm or molecular cut off are 5000~1000000Da.

In one embodiment, chelating resin model refers to S-930 or D463.

Advantageous effect

The pesticide industry sodium chloride abraum salt purification process of the utility model can be efficiently solved with organic pollution Sodium chloride abraum salt is applied to cause the problem of electrolysis with ion-exchange film efficiency is low, slot pressure increases, ionic membrane damage in chlorine industry.

Description of the drawings

Fig. 1 is installation drawing provided by the utility model.

Wherein, 1, salt dissolving groove；2, NF membrane；3, cation impurity device is removed；4, chelating resin column；5, electrolysis with ion-exchange film Slot；31, precipitating reagent adds tank；32, reaction tank；33, equipment for separating liquid from solid.

Specific implementation mode

The utility model is described in further detail below by specific implementation mode.But those skilled in the art will Understand, the following example is merely to illustrate the utility model, and should not be regarded as limiting the scope of the utility model.In embodiment not Particular technique or condition person are indicated, (such as is write with reference to Xu Nan equalitys according to technology described in document in the art or condition 's《Inorganic membrane separation technique and application》, Chemical Industry Press, 2003) or carry out according to product description.Agents useful for same Or production firm person is not specified in instrument, being can be with conventional products that are commercially available.

Approximate language used herein can be used for modifying in entire disclosure and claims any quantity statement, can Permit being changed under conditions of not causing its relevant basic function to change.Therefore, it is repaiied by term such as " about " The value of decorations is not limited to specified exact value.In at least some cases, approximate language can be with the instrument for measuring the value Precision it is corresponding.Unless being indicated otherwise in context or sentence, otherwise range limit can be combined and/or exchange, and And this range is confirmed as and includes all subranges contained herein.In addition in the operation embodiment or elsewhere In indicate except, the number of the amounts of all expression compositions used in specification and claims, reaction condition etc. or Expression shall be construed as the modification by word " about " in all cases.

The value expressed using range format should be interpreted as not only in a flexible way including clearly enumerating as range The numerical value of limit value, but also include all single numbers or the subinterval covered in the range, like each numerical value and sub-district Between be expressly recited out.For example, the concentration range of " about 0.1% to about 5% " should be understood as including not only clearly enumerating The concentration of about 0.1% to about 5% further includes the single concentration in how（Such as, 1%, 2%, 3% and 4%）The subinterval and（Example Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%）.

" removal " in this specification includes not only the case where completely removing target substance, further includes that part removal (is reduced The amount of the substance) the case where." purification " in this specification, including remove arbitrary or specific impurity.

Word "include", "comprise" used herein, " having " or its any other variant are intended to cover non-exclusionism Including.E.g., including technique, method, article or the equipment for listing element are not necessarily limited by those elements, but may include it He is not explicitly listed or belongs to this technique, method, article or the intrinsic element of equipment.It should be understood that when an element When being mentioned with another element " connection ", it can be connected directly with other elements or is indirectly connected with other elements, and Inserted with element between them.Percentage described in the utility model refers to quality percentage in the case of no special instruction Than.

Method provided by the utility model can not be used or be used primarily directed to pesticide industry sodium chloride abraum salt The problem of electrolysis with ion-exchange film efficiency is low, slot pressure increases, ionic membrane damage is caused in chlorine industry, common brine passes through deionization After the processing of impurity, you can it is applied to electrolysis with ion-exchange film, but for some contain the brine of organic pollution, it can shadow It rings to the efficiency during electrolysis with ion-exchange film, usually performance, which is these brine, has a certain amount of COD, TOC.In the prior art Through disclosing the more method for removing COD, TOC in water removal, when finding to handle it using NF membrane in the utility model, Have the advantages that more, on the one hand can be effectively reduced in brine organic pollution, while not introducing it into brine again Its chemical composition, and due to by complete except in cation impurity treated brine still a certain amount of unreacted can be carried Full cation impurity, NF membrane can play the role of while depth removal cation impurity.What the utility model used receives Filter membrane is filtered processing to pesticide abraum salt, can be effectively removed the ion of organic matter therein and divalent or more.This practicality The concentration range of main component in the crude brine refined conducted in novel is not particularly limited, but anti-in order to improve precipitation Answer efficiency and membrane filtration efficiency, main component generally essence can be being reacted and filtered close under solubility saturated conditions System, for example, the concentration of NaCl can be between 200~360g/L.

In method provided by the utility model, the cation impurity removed in brine can be by well known in the art each The different method of kind, such as：Ion-exchange, absorption method, precipitation method etc., if can realize by the impurity sun in NaCl salt from Son removal, in a preferred embodiment, is very suitable for commercial Application, the precipitation method have main steps that using the precipitation method： First, CO is added in crude brine₃ ^2-And OH^-Ion, after reaction, CO₃ ^2-And OH^-Ion can make Ca²⁺、Mg²⁺Respectively It is changed into CaCO₃With Mg (OH)₂, when also containing Cs in crude brine⁺、Ni⁺When ion, CO₃ ^2-And OH^-Ion can also make its transformation For Cs₂CO₃With Ni (OH)₂, it is re-fed into seperation film and is filtered, the CaCO that these reactions generate can be got rid of₃、Mg(OH)₂、 Cs₂CO₃With Ni (OH)₂, obtain ceramic membrane clear liquid after purification.

Ca as impurity cationic²⁺、Mg²⁺、Cs⁺、Ni⁺The concentration range of ion is not particularly limited, and can be 0.01 The range of~50g/L, as long as selecting suitable precipitating reagent CO according to the concentration of impurity cationic₃ ^2-And OH^-The addition of ion, Impurity cationic can be converted to precipitation, CO₃ ^2-And OH^-The addition of ion can be by those skilled in the art according to change Metering balance is learned to be calculated.In order to which impurity cationic is fully converted to precipitation, precipitating reagent is added and is selected from NaOH、Na₂CO₃, KOH or K₂CO₃In one or several kinds of mixtures, the addition of each precipitating reagent is both greater than complete Precipitated impurities cation aequum, such as：NaOH, Na of addition₂CO₃, KOH or K₂CO₃Addition than complete precipitated impurities Cationic requirement all has more 0.2 ~ 0.3g/L." precipitation completely " described in the utility model refers to flat according to chemical reaction Weighing apparatus formula institute is calculated to need precipitation capacity, those skilled in the art that can be calculated according to chemical reaction molar ratio, not Foreign ion in real reaction is understood to be deposited completely.In the methods described above, the porous membrane material of composition ceramic membrane used Material, can suitably select from conventionally known ceramic material.It is, for example, possible to use aluminium oxide, zirconium oxide, magnesia, oxidation Silicon, titanium oxide, cerium oxide, yttrium oxide, the oxide materials such as barium titanate；Cordierite, mullite, forsterite, block are slided The combined oxidations species material such as stone, sialon, zircon, ferrite；Silicon nitride, aluminum nitride and other nitride class material；Carbon The carbon compounds material such as SiClx；The hydroxides composition material such as hydroxyapatite；The elements class material such as carbon, silicon；Or contain them Two or more inorganic composite materials etc..Natural minerals can also be used（Clay, clay mineral, grog, silica sand, pottery stone, length Stone, white sand）Or blast-furnace slag, flying dust etc..Wherein, it is preferably selected from aluminium oxide, zirconium dioxide, titanium oxide, magnesia, silica One kind or two or more, the ceramic powders more preferably constituted using aluminium oxide, zirconium dioxide or titanium oxide as main body.Wherein, " as main body " mentioned here indicates the 50wt% or more of ceramic powders totality（It is preferred that 75wt% or more, more preferable 80wt%~ 100wt%）For aluminium oxide or silica.For example, in the porous material, aluminium oxide is relatively inexpensive and operational excellent.Also, It is able to easily form the porous structure with the aperture for being suitable for liquid separation, therefore can be easily manufactured with excellent The ceramic separation film of liquid permeability.Also, in above-mentioned aluminium oxide, Alpha-alumina is particularly preferably used.Alpha-alumina has Stable and fusing point and high mechanical strength the characteristic in terms of chemistry.Therefore, by using Alpha-alumina, can manufacture can be Broad use（Such as industrial circle）The middle ceramic separation film utilized.

In manageable pesticide producing abraum salt, what is handled in following example 1~4 is formed in glyphosate production Abraum salt in glyphosate mother solution, wherein sodium chloride is mainly contained, after pure water dissolves, the main component NaCl in effluent brine 300 g/L, Mg²⁺0.1g/L, Ca²⁺0.06g/L, COD 32.3mg/L, TOC 21mg/L.By nanofiltration membrane, deionization Brine after device filtering, chelating resin absorption, which is sent into ion-exchange membrane electrolyzer, to be electrolysed, 80 DEG C of bath temperature, operation electric current density 3.0kA/m².The processing of embodiment 5~8 is the abraum salt obtained in metalaxyl production, and the production technology of metalaxyl is generally through passing through Esterification, amination, methoxylation, chloride, condensation, producing the organic matter contained in the waste salt dregs of metalaxyl includes：Methoxyl group second Acyl chlorides, methyl lactamine, metalaxyl, methanol etc., the water quality in following embodiment are：NaCl 280 g/L, Mg²⁺0.15g/L, Ca²⁺0.08g/L, COD 243.7mg/L, TOC 198mg/L, methoxyacetyl chloride 0.85g/L, methanol 0.32g/L.At one In embodiment, when handling metalaxyl abraum salt waste water, it can be handled in a manner of first to brine using Fe-C micro electrolysis, In the case of electrolysis, it can be effectively facilitated the hydrolysis of methoxyacetyl chloride, generate carboxylic acid and hydrogen chloride, then carry out Fenton Oxidation processes can be effectively facilitated since the hydrogen chloride that the hydrolysis of methoxyacetyl chloride obtains closes waste water in acidity at this time The progress of Fenton oxidation, due to during Fe-C micro electrolysis, more Fe can be also entered in brine²⁺And Fe³⁺Ion, these Ion can make NF membrane generate repulsive force to sodium chloride in the Interception process of NF membrane by charge balance Donnan effects, Improve transmitance of the NF membrane to sodium chloride；Meanwhile during the subsequent precipitation method remove impurity cationic, Fe²⁺With Fe³⁺Ion can generate floccule again, can be to preferably capture CaCO₃With Mg (OH)₂Precipitation is generated, precipitation particle is made to become larger, The small particles of pollution for reducing ceramic filtration membrane filtering, improves membrane flux.

Based on above method, the utility model additionally provides a kind of purification devices of abraum salt, including：

Salt dissolving groove 1, the NaCl waste salt dregs for will be obtained in pesticide synthesis are dissolved in water；

NF membrane 2 is connected to salt dissolving groove 1, for the brine obtained in salt dissolving groove 1 to be filtered；

Except cation impurity device 3, be connected to the per-meate side of NF membrane 2, in the penetrating fluid for obtaining NF membrane 2 into Row removal cation impurity；

Chelating resin column 4 is connected to except cation impurity device 3, for the production water to being obtained except cation impurity device 3 Salt treatment is removed using resin；

Ion-exchange membrane electrolyzer 5 is connected to chelating resin column 4, and electrolysis processing is carried out for the production water to chelating resin column 4, Obtain caustic soda and chlorine.

In one embodiment, 100~500Da of molecular cut off of NF membrane 2.

In one embodiment, it is sub- to be selected from cellulose acetate Type of Collective object, polyamide, polyester, polyamides for nanofiltration membrane material One or several kinds of combinations in amine or polyvinyl etc..

In one embodiment, except cation impurity device 3 includes that reaction tank 32 and precipitating reagent add tank 31, precipitation Agent adds tank 31 for precipitating reagent to be added into reaction tank 32, and reaction tank 32 is connected to the per-meate side of NF membrane 2, for that will permeate The penetrating fluid of film 2 carries out precipitation reaction with precipitating reagent；Equipment for separating liquid from solid 33 is connected to reaction tank 32, for precipitation reaction Feed liquid afterwards is separated by solid-liquid separation；The per-meate side of equipment for separating liquid from solid 33 is connect with chelating resin column 4.

In one embodiment, precipitating reagent, which adds, is equipped with NaOH and/or Na in tank 31₂CO₃。

In one embodiment, equipment for separating liquid from solid 33 refers to ceramic filtration membrane；Filter membrane be average pore size be 0.005 μm~ 0.5 μm or molecular cut off are 5000~1000000Da.

In one embodiment, chelating resin model refers to S-930 or D463.

Embodiment 1

Glyphosate abraum salt saturation effluent brine using molecular cut off 120Da polyamide nanofiltration membrane in be filtered processing, Operating pressure 3.5Mpa, 30 DEG C of temperature, cycles of concentration are 4 times, Na⁺、Ca²⁺、Mg²⁺, TOC, COD rejection be 10.4% respectively, 88.9%、87.9%、68.5%、69.8%.Go out liquid and NaOH 0.237g/L and Na is added₂CO₃0.219g/L, it is abundant by reactor After reaction, make Ca²⁺、Mg²⁺It is changed into CaCO respectively₃With Mg (OH)₂, enter back into ceramic membrane and be filtered, using flat The alumina ceramic membrane that equal aperture is 50nm, crossflow velocity 4m/s, operating pressure 0.3MPa, stable flux is 133.3L/ m²H can get rid of CaCO₃Precipitation and Mg (OH)₂Colloid, obtained ceramic membrane penetrating fluid ions content are：Mg²⁺Content 1.2 mg/L, Ca²⁺1 mg/L of content.Ceramic membrane penetrating fluid is sent into D463 type chelating resins.Resin water outlet is sent into electrolytic cell and is carried out Electrolysis generates Cl₂And NaOH, current efficiency 94.7%.

Embodiment 2

Glyphosate abraum salt saturation effluent brine using molecular cut off 150Da polyamide nanofiltration membrane in be filtered processing, Operating pressure 3.5Mpa, 30 DEG C of temperature, cycles of concentration are 3 times, Na⁺、Ca²⁺、Mg²⁺, TOC, COD rejection be 11.6% respectively, 88.8%、88%、67.5%、69.1%.Go out liquid and NaOH 0.23g/L and Na is added₂CO₃0.22g/L is fully reacted by reactor Later, make Ca²⁺、Mg²⁺It is changed into CaCO respectively₃With Mg (OH)₂, enter back into ceramic membrane and be filtered, using average hole Diameter is the alumina ceramic membrane of 200nm, and crossflow velocity 3m/s, operating pressure 0.3MPa, stable flux is 301.1L/m²· H can get rid of CaCO₃Precipitation and Mg (OH)₂Colloid, obtained ceramic membrane penetrating fluid ions content are：Mg²⁺Content 1.2 Mg/L, calcium ion content 1.8mg/L.Ceramic membrane penetrating fluid is sent into D463 type chelating resins.Resin water outlet is sent into electrolytic cell and is carried out Electrolysis generates Cl₂And NaOH, current efficiency 94.9%.

Embodiment 3

Glyphosate abraum salt saturation effluent brine using molecular cut off 200Da polyamide nanofiltration membrane in be filtered processing, Operating pressure 3.5Mpa, 30 DEG C of temperature, cycles of concentration are 5 times, Na⁺、Ca²⁺、Mg²⁺, TOC, COD rejection be 9.7% respectively, 88.2%、87.9%、67.5%、69%.Go out liquid and NaOH 0.23g/L and Na is added₂CO₃0.22g/L is fully reacted by reactor Later, make Ca²⁺、Mg²⁺It is changed into CaCO respectively₃With Mg (OH)₂, enter back into ceramic membrane and be filtered, using average hole Diameter is the alumina ceramic membrane of 200nm, and crossflow velocity 3m/s, operating pressure 0.3MPa, stable flux is 279.2L/m²· H can get rid of CaCO₃Precipitation and Mg (OH)₂Colloid, obtained ceramic membrane penetrating fluid ions content are：Mg²⁺Content 1.2 Mg/L, Ca²⁺Content 1.5mg/L.Ceramic membrane penetrating fluid is sent into S-930 type chelating resins.Resin water outlet is sent into electrolytic cell and carries out electricity Solution generates Cl₂And NaOH, current efficiency 93.5%.

Embodiment 4

0.5wt%FeCl is added in glyphosate abraum salt saturation effluent brine₃, using the polyamide nanofiltration of molecular cut off 200Da Processing is filtered in film, operating pressure 3.5Mpa, 30 DEG C of temperature, cycles of concentration is 5 times, Na⁺、Ca²⁺、Mg²⁺, TOC, COD Rejection is 5.6%, 86.5%, 86.3%, 65.1%, 66.3% respectively.Go out liquid and NaOH 0.30g/L and Na is added₂CO₃0.28g/L, After fully being reacted by reactor, make Ca²⁺、Mg²⁺It is changed into CaCO respectively₃With Mg (OH)₂, enter back into ceramic membrane and carried out Filter, using the alumina ceramic membrane that average pore size is 200nm, crossflow velocity 3m/s, operating pressure 0.3MPa are stable Flux is 322.6L/m²H can get rid of CaCO₃Precipitation and Mg (OH)₂Colloid, obtained ceramic membrane penetrating fluid intermediate ion contain Amount is：Mg²⁺Content 0.6mg/L, Ca²⁺Content 0.6mg/L.Ceramic membrane penetrating fluid is sent into S-930 type chelating resins.Resin is discharged It is sent into electrolytic cell to be electrolysed, generates Cl₂And NaOH, current efficiency 95.8%.

Embodiment 5

Metalaxyl abraum salt saturation effluent brine using molecular cut off 150Da polyamide nanofiltration membrane in be filtered processing, Operating pressure 3.0Mpa, 35 DEG C of temperature, cycles of concentration are 5 times, Na⁺、Ca²⁺、Mg²⁺, TOC, COD rejection be 12.3% respectively, 84.4%、85.5%、71.2%、72.8%.Go out liquid and NaOH 0.30g/L and Na is added₂CO₃0.28g/L is fully anti-by reactor After answering, make Ca²⁺、Mg²⁺It is changed into CaCO respectively₃With Mg (OH)₂, enter back into ceramic membrane and be filtered, using average Aperture is the alumina ceramic membrane of 50nm, and crossflow velocity 4m/s, stable flux is 173.8L/m²H, operating pressure 0.30MPa can get rid of CaCO₃Precipitation and Mg (OH)₂Colloid, obtained ceramic membrane penetrating fluid ions content are：Mg²⁺Contain Measure 1.9 mg/L, Ca²⁺Content 1.3mg/L.Ceramic membrane penetrating fluid is sent into S-930 type chelating resins.Electrolytic cell is sent into resin water outlet It is electrolysed, generates Cl₂And NaOH, current efficiency 93.1%.

Embodiment 6

Metalaxyl abraum salt saturation effluent brine using molecular cut off 300Da polyamide nanofiltration membrane in be filtered processing, Operating pressure 3.5Mpa, 30 DEG C of temperature, cycles of concentration are 4 times, Na⁺、Ca²⁺、Mg²⁺, TOC, COD rejection be 11.2% respectively, 82.4%、83.9%、72.5%、71.2%.Go out liquid and NaOH 0.24g/L and Na is added₂CO₃0.20g/L is fully anti-by reactor After answering, make Ca²⁺、Mg²⁺It is changed into CaCO respectively₃With Mg (OH)₂, enter back into ceramic membrane and be filtered, using average Aperture is the alumina ceramic membrane of 50nm, and crossflow velocity 4m/s, stable flux is 186.2L/m²H, operating pressure 0.25MPa can get rid of CaCO₃Precipitation and Mg (OH)₂Colloid, obtained ceramic membrane penetrating fluid ions content are：Mg²⁺Contain Measure 1.7 mg/L, Ca²⁺Content 1.8mg/L.Ceramic membrane penetrating fluid is sent into S-930 type chelating resins.Electrolytic cell is sent into resin water outlet It is electrolysed, generates Cl₂And NaOH, current efficiency 92.7%.

Embodiment 7

Metalaxyl abraum salt saturation effluent brine using molecular cut off 400Da polyamide nanofiltration membrane in be filtered processing, Operating pressure 2.5Mpa, 35 DEG C of temperature, cycles of concentration are 6 times, Na⁺、Ca²⁺、Mg²⁺, TOC, COD rejection be 9.7% respectively, 83.3%、81.2%、69.4%、67.6%.Go out liquid and NaOH 0.40g/L and Na is added₂CO₃0.30g/L is fully anti-by reactor After answering, make Ca²⁺、Mg²⁺It is changed into CaCO respectively₃With Mg (OH)₂, enter back into ceramic membrane and be filtered, using average Aperture is the alumina ceramic membrane of 50nm, and crossflow velocity 4m/s, stable flux is 171.4L/m²H, operating pressure 0.25MPa can get rid of CaCO₃Precipitation and Mg (OH)₂Colloid, obtained ceramic membrane penetrating fluid ions content are：Mg²⁺Contain Measure 2.4 mg/L, Ca²⁺Content 3.4mg/L.Ceramic membrane penetrating fluid is sent into S-930 type chelating resins.Electrolytic cell is sent into resin water outlet It is electrolysed, generates Cl₂And NaOH, current efficiency 91.1%.

Embodiment 8

Metalaxyl abraum salt saturation effluent brine, which is sent into Fe-C micro electrolysis tower, carries out microelectrolysis processing, adds H₂O₂It carries out fragrant Pause and aoxidize, liquid water pH is 4~5, Fe²⁺Concentration about 1.2g/L handles 20min at 40 DEG C, then using molecular cut off 400Da's Processing is filtered in polyamide nanofiltration membrane, operating pressure 2.5Mpa, 35 DEG C of temperature, cycles of concentration is 6 times, Na⁺、Ca²⁺、Mg²⁺、 The rejection of TOC, COD are 4.9%, 82.2%, 80.1%, 67.3%, 64.3% respectively.Go out liquid and NaOH 0.90g/L and Na is added₂CO₃ 0.90g/L makes Fe after fully being reacted by reactor³⁺、Ca²⁺、Mg²⁺It is changed into Fe (OH) respectively₂、CaCO₃With Mg (OH)₂, It enters back into ceramic membrane and is filtered, using the alumina ceramic membrane that average pore size is 50nm, crossflow velocity 4m/s, operation Stabilized flux is 204.9L/m²H, operating pressure 0.25MPa can get rid of CaCO₃Precipitation and Mg (OH)₂Colloid obtains Ceramic membrane penetrating fluid ions content is：Mg²⁺Content 1.1 mg/L, Ca²⁺Content 1.2mg/L.Ceramic membrane penetrating fluid is sent into S- 930 type chelating resins.Resin water outlet is sent into electrolytic cell and is electrolysed, and Cl is generated₂And NaOH, current efficiency 96.5%.

Claims (7)

1. a kind of purification devices of abraum salt, which is characterized in that including：

Salt dissolving groove（1）, the NaCl waste salt dregs for will be obtained in pesticide synthesis are dissolved in water；

NF membrane（2）, it is connected to salt dissolving groove（1）, it is used for salt dissolving groove（1）In obtained brine be filtered；

Except cation impurity device（3）, it is connected to NF membrane（2）Per-meate side, for by NF membrane（2）In obtained penetrating fluid It is removed cation impurity；

Chelating resin column（4）, it is connected to except cation impurity device（3）, for removing cation impurity device（3）Obtained production Water removes salt treatment using resin；

Ion-exchange membrane electrolyzer（5）, it is connected to chelating resin column（4）, for chelating resin column（4）Production water carry out at electrolysis Reason, obtains caustic soda and chlorine.

2. the purification devices of abraum salt according to claim 1, which is characterized in that NF membrane（2）Molecular cut off 100~ 500Da。

3. the purification devices of abraum salt according to claim 1, which is characterized in that NF membrane（2）Material is selected from acetate fiber One kind in plain Type of Collective object, polyamide, polyester, polyimides or polyvinyl.

4. the purification devices of abraum salt according to claim 1, which is characterized in that remove cation impurity device（3）Include Reaction tank（32）Tank is added with precipitating reagent（31）, precipitating reagent adds tank（31）For to reaction tank（32）Middle addition precipitating reagent, instead Ying Chi（32）It is connected to NF membrane（2）Per-meate side, for by NF membrane（2）Penetrating fluid and precipitating reagent carry out precipitation reaction； Equipment for separating liquid from solid（33）, it is connected to reaction tank（32）, for being separated by solid-liquid separation to the feed liquid after precipitation reaction；It is separated by solid-liquid separation Device（33）Per-meate side and chelating resin column（4）Connection.

5. the purification devices of abraum salt according to claim 1, which is characterized in that precipitating reagent adds tank（31）In be equipped with NaOH Or Na₂CO₃。

6. the purification devices of abraum salt according to claim 1, which is characterized in that equipment for separating liquid from solid（33）It refer to ceramic filtering Film；Ceramic filtration membrane is that average pore size is 0.005 μm~0.5 μm or molecular cut off is 5000~1000000Da.

7. the purification devices of abraum salt according to claim 1, which is characterized in that chelating resin model refer to S-930 or D463。