CN105836976B - The integrated conduct method of long-chain alkanedioic crystalline mother solution - Google Patents
The integrated conduct method of long-chain alkanedioic crystalline mother solution Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a kind of integrated conduct method of long-chain alkanedioic crystalline mother solution, reclaim the long-chain alkanedioic in waste water and obtain byproduct glauber salt using hyperfiltration technique, macroporous adsorbent technology, nanofiltration, freezing denitration technology, crystallization and evaporation technology, realization is turned waste into wealth, comprehensive utilization of resources, it is final obtain hyposaline waste water can after biochemical treatment qualified discharge.
Description
Technical field
The invention belongs to biological chemical field, more particularly to a kind of integrated treatment side of long-chain alkanedioic crystalline mother solution
Method.
Background technology
Long-chain alkanedioic is obtained for raw material is produced by microorganism conversion with the long chain alkane (paraffin) of ten two-ten six carbon
.Into alkanoic acid, the pH of zymotic fluid is reduced alkane transformations, in order to maintain constant thalline most suitable in the fermentation process of alkanoic acid long
PH, needed in fermentation process add NaOH, in addition filtering fermentation liquor clarification carry out thalline separate when, in order to allow binary acid into
Salt dissolves, and still needs to add a large amount of NaOH (total addition level of NaOH is and binary acid equivalent).During Crystallization Separation
Binary acid is crystallized with molecular state in order to reduce binary acid degree of ionization, the sulfuric acid with NaOH equivalent must be added again.
Contain sodium sulphate 45-55g/L in final crystalline mother solution waste water, fine long-chain alkanedioic crystal 0.5-1.5g/L, impurity is organic
Sour 8-12g/L, protein 0.7-1.3g/L, COD total amount 10000-12000mg/L, pH4.0, and have different smell, in fawn
Color.
Due to, a large amount of sodium sulphate are contained in mother liquor waste water, because osmotic pressure is too high, microorganism is difficult to survive, it is impossible to carry out
Biochemical treatment, conventional processes are as follows：
From friendship desalination+biochemical treatment：Because sodium sulphate content is too high in mother liquor waste water, waste water per ton needs to expend regeneration tree
The hydrochloric acid 100kg of fat, only NaOH 25kg, acid and alkali consumption more than 100 yuan of RMB/ tons of waste water, the long-chain two in waste water in addition
First alkanoic acid treats as pollutant process, resource serious waste.In addition, the alkanoic acid micro crystal long in waste water can block resin, make
Into from handing over system washing amount big, it is impossible to continuous operation；
Evaporating and concentrating process：The direct multiple-effect evaporation of waste water, on the one hand expends huge steam cost, on the other hand due to evaporation
Contain albumen, pigment, alkanoic acid long, foul smell in the sodium sulphate being concentrated to give, it is impossible to as by-product sale, can only be used as danger
Strategically secure body offal treatment, waste water ton cost of water treatment is more than 300 yuan of RMB.
In view of as above reason, it is necessary to study a kind of integrated conduct method of long-chain alkanedioic crystalline mother solution, to solve
Problems of the prior art.
The content of the invention
The present invention is completed in view of at least one above mentioned problem, and it is an object of the present invention to provide one kind
The integrated conduct method of long-chain alkanedioic crystalline mother solution, it is characterised in that comprise the following steps：
Long-chain alkanedioic crystalline mother solution carries out filtering and concentrating using milipore filter, obtains the first trapped fluid and the first filtrate；
First trapped fluid set uses reuse in the alkaline filtrate of filtering fermentation liquor unit；
First filtrate carries out adsorption-edulcoration using macroporous adsorbent, obtains colourless, odorless removing impurities filtrate and saturation macropore
Adsorbent；
Saturation macroporous adsorbent is parsed using NaOH solution, obtain high chroma, stench, the organic wastewater of high concentration and
Recover the macroporous adsorbent of adsorption capacity；
The no color or smell removal of impurities filtrate is filtered using NF membrane, obtains the second filtrate and the second trapped fluid；
Second trapped fluid crystallisation by cooling simultaneously separates crystal using centrifuge, obtains sal glauberi crystal and hyposaline crystallization
Mother liquor；
After sal glauberi crystal heating for dissolving use forced-circulation evaporator crystallization and evaporation, obtain byproduct glauber salt and
A small amount of steam condensate, steam condensate set is used filtering fermentation liquor unit and is used as water-dialyzing；
The high chroma, stench, the organic wastewater of high concentration, the second filtrate and hyposaline crystalline mother solution merge, using life
Change is processed, and realizes qualified discharge.
According to a further aspect of the invention, in long-chain alkanedioic crystalline mother solution, sodium sulphate 45-55g/L, long-chain alkanedioic
0.5-1.5g/L, impurity organic acid 8-12g/L, protein 0.7-1.3g/L, COD total amount 10000-12000mg/L, pH4.0, have
Different smell, it is khaki, contain a small amount of fine long-chain alkanedioic crystal.
According to a further aspect of the invention, long-chain alkanedioic crystalline mother solution concentrates 25-30 after being filtered using milipore filter
Times.
According to a further aspect of the invention, long-chain alkanedioic content 15-45g/L in the first trapped fluid.
According to a further aspect of the invention, the turbidity≤0.2NTU of the first filtrate.
According to a further aspect of the invention, saturation macroporous adsorbent is parsed using 4%NaOH solution.
According to a further aspect of the invention, crystallized after the second trapped fluid is cooled to-5-5 DEG C.
According to a further aspect of the invention, the material of milipore filter includes Al2O3、TiO2, polysulfones, polyether sulfone, modified poly (ether-sulfone),
Kynoar or polytetrafluoroethylene (PTFE)；The filtering accuracy of milipore filter is 20-200nm, and hyperfiltration membrane assembly mode is doughnut, volume
Formula, board-like or tubular type；The filter pressure of milipore filter is less than 10bar.
According to a further aspect of the invention, macroporous adsorbent includes low pole or nonpolar macroporous adsorbent.
According to a further aspect of the invention, NF membrane is the polymeric membrane of wound module mode, and its molecular cut off is 200-
300D, its rejection to magnesium sulfate is 90-98%, and operating pressure is 0-42bar, and operation temperature is 0-45 DEG C；Forced circulation
Evaporator includes the forced-circulation evaporator of multi-effect forced circulation evaporation device or carrying vapour compressor.
Compared with prior art, the beneficial effects of the present invention are：The present invention is using long-chain two in milipore filter recovery mother liquor
First alkanoic acid product, using pigment, stink, dissolubility long-chain alkanedioic, dissolving in macroporous adsorbent removal milipore filter filtrate
Property low pole and non polar impurities, using the further concentrated vitriol sodium of NF membrane, and by freezing denitration, obtained after evaporative crystallization
The byproduct glauber salt of high-purity.Long-chain alkanedioic is reclaimed by the present invention and glauber salt byproduct realizes resource comprehensive profit
With, the cost for wastewater treatment that overbalances of product is reclaimed, realize 25 yuan of RMB/ tons of waste water of profit.
Brief description of the drawings
Fig. 1 is the integrated conduct method flow chart of long-chain alkanedioic crystalline mother solution according to the preferred embodiment of the invention.
Specific embodiment
Below in conjunction with the accompanying drawings, preferred forms of the invention are described by preferred embodiment, specific implementation here
Mode is to explain the present invention, and be should not be construed as limiting the invention, of the invention spiritual and real not departing from
In the case of matter scope, various changes and modifications can be made, these should be all included within protection scope of the present invention.
Referring to Fig. 1, the preferred embodiment of the present invention provides a kind of integrated conduct method of long-chain alkanedioic crystalline mother solution.
The integrated conduct method of the long-chain alkanedioic crystalline mother solution is comprised the following steps：
Long-chain alkanedioic crystalline mother solution carries out filtering and concentrating using milipore filter, obtains the first trapped fluid and the first filtrate；
First trapped fluid set uses reuse in the alkaline filtrate of filtering fermentation liquor unit；
First filtrate carries out adsorption-edulcoration using macroporous adsorbent, obtains colourless, odorless removing impurities filtrate and saturation macropore
Adsorbent；
Saturation macroporous adsorbent is parsed using NaOH solution, obtain high chroma, stench, the organic wastewater of high concentration and
Recover the macroporous adsorbent of adsorption capacity；
The no color or smell removal of impurities filtrate is filtered using NF membrane, obtains the second filtrate and the second trapped fluid；
Second trapped fluid crystallisation by cooling simultaneously separates crystal using centrifuge, obtains sal glauberi crystal and hyposaline crystallization
Mother liquor；
After sal glauberi crystal heating for dissolving use forced-circulation evaporator crystallization and evaporation, obtain byproduct glauber salt and
A small amount of steam condensate, steam condensate set is used filtering fermentation liquor unit and is used as water-dialyzing；
The high chroma, stench, the organic wastewater of high concentration, the second filtrate and hyposaline crystalline mother solution merge, using life
Change is processed, and realizes qualified discharge.
Preferably, in long-chain alkanedioic crystalline mother solution, sodium sulphate 45-55g/L, long-chain alkanedioic 0.5-1.5g/L,
Impurity organic acid 8-12g/L, protein 0.7-1.3g/L, COD total amount 10000-12000mg/L, pH4.0, there is different smell, yellowish
Brown, contains a small amount of fine long-chain alkanedioic crystal.
Preferably, 25-30 times is concentrated after long-chain alkanedioic crystalline mother solution is filtered using milipore filter.
Preferably, long-chain alkanedioic content 15-45g/L in the first trapped fluid.
Preferably, the turbidity≤0.2NTU of the first filtrate.
Preferably, saturation macroporous adsorbent is parsed using 4%NaOH solution.
Preferably, crystallized after the second trapped fluid is cooled to-5-5 DEG C.
Preferably, the material of milipore filter includes Al2O3、TiO2, polysulfones, polyether sulfone, modified poly (ether-sulfone), Kynoar or
Polytetrafluoroethylene (PTFE)；The filtering accuracy of milipore filter is 20-200nm, and hyperfiltration membrane assembly mode is doughnut, rolling, board-like or pipe
Formula；The filter pressure of milipore filter is less than 10bar.
Preferably, macroporous adsorbent includes low pole or nonpolar macroporous adsorbent.
Preferably, NF membrane is the polymeric membrane of wound module mode, and its molecular cut off is 200-300D, and it is to sulfuric acid
The rejection of magnesium is 90-98%, and operating pressure is 0-42bar, and operation temperature is 0-45 DEG C；Forced-circulation evaporator includes multiple-effect
The forced-circulation evaporator of forced-circulation evaporator or carrying vapour compressor.
Preferably, the long-chain alkanedioic crystalline mother solution waste water that the present invention cannot be processed for traditional handicraft, there is provided a kind of
Turn waste into wealth, the wastewater treatment scheme of comprehensive utilization of resources.Specifically, crystallized present invention also offers a kind of long-chain alkanedioic
The integrated conduct method of mother liquor, comprises the following steps：
A, wherein long-chain alkanedioic crystalline mother solution, sodium sulphate 45-55g/L, long-chain alkanedioic 0.5-1.5g/L, impurity
Organic acid 8-12g/L, protein 0.7-1.3g/L, COD total amount 10000-12000mg/L, pH4.0, there is different smell, fawn
Color, containing a small amount of fine long-chain alkanedioic crystal, is filtered using milipore filter, concentrates 25-30 times, obtains the He of trapped fluid 1
Filtrate 1；
Trapped fluid 1 obtained by b, step a, wherein long-chain alkanedioic content 15-45g/L, can cover and use filtering fermentation liquor
Reuse in the alkaline filtrate of unit；
Filtrate 1 obtained by c, step b, turbidity≤0.2NTU carries out adsorption-edulcoration using macroporous adsorbent, obtain it is colourless,
The removing impurities filtrate of odorless and saturation macroporous adsorbent, absorption flow are 3-10 times/hour of bed volume, and adsorption temp is 10-
30℃；
Saturation macroporous adsorbent obtained by d, step c, is parsed using 4%NaOH solution, obtain high chroma, stench,
The organic wastewater of high concentration and the macroporous adsorbent of recovery adsorption capacity；Resolution temperature is 20-50 DEG C, and parsing agent flux is 1-3
Times bed volume/hour, macroporous adsorbent exchange capacity is 150-400 times of bed volume；
No color or smell removal of impurities filtrate obtained by e, step c, is filtered using NF membrane, obtains filtrate 2 and trapped fluid 2,
The cycles of concentration of NF membrane is 2 times, and sodium sulfate concentration is 90-110g/L in trapped fluid；
Trapped fluid 2 obtained by f, step e, is cooled to-5-5 DEG C, crystallizes and separates crystal using centrifuge, obtains ten water
Sodium sulfate crystal and hyposaline crystalline mother solution, the content of sodium sulphate is 8-12g/L in crystalline mother solution；
Forced-circulation evaporator crystallization and evaporation is used after the sal glauberi crystal heating for dissolving that g, step f are obtained, is obtained
Byproduct glauber salt and a small amount of steam condensate, steam condensate set are used filtering fermentation liquor unit and are used as water-dialyzing；
The filtrate 2 and step f that high chroma, stench, the organic wastewater of high concentration and the step e that h, step d are obtained are obtained are obtained
The hyposaline crystalline mother solution for obtaining merges, and the COD for merging waste water is 9000-11000mg/L, sodium sulphate content≤5g/L, using life
Change is processed, and realizes qualified discharge.
Preferably, its material of the milipore filter described in step a includes but is not limited to Al2O3、TiO2, it is polysulfones, polyether sulfone, modified
Polyether sulfone, Kynoar, polytetrafluoroethylene (PTFE) etc., the preferred Al of milipore filter of the present invention2O3、TiO2Material；The filtering accuracy of milipore filter
It is 20-200nm, the present invention preferably 20-100nm, hyperfiltration membrane assembly mode is doughnut, rolling, board-like, tubular type etc., this hair
Bright preferred tubular module mode；The filter pressure position 0-10bar of milipore filter, the filter type of milipore filter is cross-flow or dead end mistake
Filter, the present invention preferably cross-flow filtration, particularly preferred film layer is TiO2Supporting layer is the stainless steel tubular membrane of 316L stainless steels.
Preferably, the macroporous adsorbent described in step c includes but is not limited to low pole or nonpolar macroporous adsorbent, preferably
Low pole macroporous adsorbent.
Preferably, the NF membrane described in step e is the polymeric membrane of wound module mode, and its molecular cut off is 200-
300D, its rejection to magnesium sulfate is 90-98%, and operating pressure is 0-42bar, and operation temperature is 0-45 DEG C.
Preferably, the forced-circulation evaporator described in step g includes but is not limited to multi-effect forced circulation evaporation device or band steams
The forced-circulation evaporator of vapour compressor, sodium sulphate reaches supersaturation in evaporator, and in-vitro separation crystal Mother liquor is returned steams
Hair device continues to evaporate.
Preferably, using a kind of long-chain alkanedioic crystalline mother solution comprehensive processing technique of the invention, mother liquor waste water per ton
In can reclaim long-chain alkanedioic 0.5-1.5kg, obtain byproduct glauber salt 40-50kg.
Preferably, it is present invention also offers a kind of integrated conduct method of long-chain alkanedioic crystalline mother solution including following
Step：
Long-chain alkanedioic crystalline mother solution is taken, wherein containing sodium sulphate 45g/L, fine long-chain alkanedioic crystal 0.7g/
L, impurity organic acid 9g/L, protein 1g/L, COD total amount 10700mg/L, pH4.0, and have different smell, in khaki, treatment
Method is as follows：
A, long-chain alkanedioic crystalline mother solution, it is TiO to use film layer2, supporting layer is that the stainless steel membrane of 316L stainless steels enters
Row filtering, filtering accuracy is 100nm, filter pressure position 5bar, concentrates 30 times, obtains trapped fluid 1 and filtrate 1,
Trapped fluid 1 obtained by b, step a, wherein long-chain alkanedioic content 21g/L, set use filtering fermentation liquor unit
Reuse in alkaline filtrate；
Filtrate 1 obtained by c, step b, turbidity 0.2NTU carries out adsorption-edulcoration using macroporous adsorbent, obtains colourless, nothing
Smelly removing impurities filtrate and saturation macroporous adsorbent, absorption flow are 3 times/hour of bed volume, and adsorption temp is 10 DEG C；
Saturation macroporous adsorbent obtained by d, step c, is parsed using 4%NaOH solution, obtain high chroma, stench,
The organic wastewater of high concentration and the macroporous adsorbent of recovery adsorption capacity；Resolution temperature is 45 DEG C, and parsing agent flux is 2 times of beds
Volume/hour, macroporous adsorbent exchange capacity is 280 times of bed volumes；
No color or smell removal of impurities filtrate obtained by e, step c, is filtered, NF membrane using rolling macromolecule material NF membrane
Molecular cut off be 200D, filtration temperature be 30 DEG C, filter pressure position 39bar, obtain filtrate 2 and trapped fluid 2, NF membrane
Cycles of concentration is 2 times, and sodium sulfate concentration is 90g/L in trapped fluid；
Trapped fluid 2 obtained by f, step e, is cooled to-5-5 DEG C, crystallizes and separates crystal using centrifuge, obtains ten water
Sodium sulfate crystal and hyposaline crystalline mother solution, the content of sodium sulphate is 8g/L in crystalline mother solution；
Using the forced-circulation evaporator of carrying vapour compressor after the sal glauberi crystal heating for dissolving that g, step f are obtained
Crystallization and evaporation, sodium sulphate reaches supersaturation in evaporator, and in-vitro separation crystal Mother liquor Returning evaporimeter continues to evaporate.Obtain
Byproduct glauber salt and a small amount of steam condensate, steam condensate set are used filtering fermentation liquor unit and are used as water-dialyzing；
The filtrate 2 and step f that high chroma, stench, the organic wastewater of high concentration and the step e that h, step d are obtained are obtained are obtained
The hyposaline crystalline mother solution for obtaining merges, and the COD for merging waste water is 9300mg/L, sodium sulphate content 4g/L, real using biochemical treatment
Existing qualified discharge；
Long-chain alkanedioic 0.7kg is reclaimed in i, mother liquor waste water per ton, byproduct glauber salt 40kg is obtained.
Preferably, it is present invention also offers a kind of integrated conduct method of long-chain alkanedioic crystalline mother solution including following
Step：
Long-chain alkanedioic crystalline mother solution is taken, wherein containing sodium sulphate 55g/L, fine long-chain alkanedioic crystal 1.3g/
L, impurity organic acid 11g/L, protein 0.9g/L, COD total amount 11000mg/L, pH4.0, and have different smell, in khaki,
Processing method is as follows：
A, long-chain alkanedioic crystalline mother solution, it is TiO2 to use film layer, and supporting layer enters for the stainless steel membrane of 316L stainless steels
Row filtering, filtering accuracy is 100nm, filter pressure position 9bar, concentrates 29 times, obtains trapped fluid 1 and filtrate 1；
Trapped fluid 1 obtained by b, step a, wherein long-chain alkanedioic content 37.7g/L, set use filtering fermentation liquor unit
Alkaline filtrate in reuse；
Filtrate 1 obtained by c, step b, turbidity 0.15NTU carries out adsorption-edulcoration using macroporous adsorbent, obtains colourless, nothing
Smelly removing impurities filtrate and saturation macroporous adsorbent, absorption flow are 5 times/hour of bed volume, and adsorption temp is 20 DEG C；
Saturation macroporous adsorbent obtained by d, step c, is parsed using 4%NaOH solution, obtain high chroma, stench,
The organic wastewater of high concentration and the macroporous adsorbent of recovery adsorption capacity；Resolution temperature is 45 DEG C, and parsing agent flux is 1.5 times of beds
Layer volume/hour, macroporous adsorbent exchange capacity is 300 times of bed volumes；
No color or smell removal of impurities filtrate obtained by e, step c, is filtered, NF membrane using rolling macromolecule material NF membrane
Molecular cut off be 250D, filtration temperature be 33 DEG C, filter pressure position 40bar, obtain filtrate 2 and trapped fluid 2, NF membrane
Cycles of concentration is 2 times, and sodium sulfate concentration is 110g/L in trapped fluid；
Trapped fluid 2 obtained by f, step e, is cooled to-5-5 DEG C, crystallizes and separates crystal using centrifuge, obtains ten water
Sodium sulfate crystal and hyposaline crystalline mother solution, the content of sodium sulphate is 10g/L in crystalline mother solution；
Using the forced-circulation evaporator of carrying vapour compressor after the sal glauberi crystal heating for dissolving that g, step f are obtained
Crystallization and evaporation, sodium sulphate reaches supersaturation in evaporator, and in-vitro separation crystal Mother liquor Returning evaporimeter continues to evaporate.Obtain
Byproduct glauber salt and a small amount of steam condensate, steam condensate set are used filtering fermentation liquor unit and are used as water-dialyzing；
The filtrate 2 and step f that high chroma, stench, the organic wastewater of high concentration and the step e that h, step d are obtained are obtained are obtained
The hyposaline crystalline mother solution for obtaining merges, and the COD for merging waste water is 9800mg/L, sodium sulphate content 4.9g/L, using biochemical treatment,
Realize qualified discharge；
Long-chain alkanedioic 1.3kg is reclaimed in i, mother liquor waste water per ton, byproduct glauber salt 50kg is obtained.
Preferably, it is present invention also offers a kind of integrated conduct method of long-chain alkanedioic crystalline mother solution including following
Step：
Long-chain alkanedioic crystalline mother solution is taken, wherein containing sodium sulphate 53g/L, fine long-chain alkanedioic crystal 1.5g/
L, impurity organic acid 12g/L, protein 1.2g/L, COD total amount 10900mg/L, pH4.0, and have different smell, in khaki,
Processing method is as follows：
A, long-chain alkanedioic crystalline mother solution, it is TiO to use film layer2, supporting layer is that the stainless steel membrane of 316L stainless steels enters
Row filtering, filtering accuracy is 50nm, filter pressure position 7bar, concentrates 28 times, obtains trapped fluid 1 and filtrate 1,
Trapped fluid 1 obtained by b, step a, wherein long-chain alkanedioic content 42g/L, set use filtering fermentation liquor unit
Reuse in alkaline filtrate；
Filtrate 1 obtained by c, step b, turbidity 0.1NTU carries out adsorption-edulcoration using macroporous adsorbent, obtains colourless, nothing
Smelly removing impurities filtrate and saturation macroporous adsorbent, absorption flow are 9 times/hour of bed volume, and adsorption temp is 25 DEG C；
Saturation macroporous adsorbent obtained by d, step c, is parsed using 4%NaOH solution, obtain high chroma, stench,
The organic wastewater of high concentration and the macroporous adsorbent of recovery adsorption capacity；Resolution temperature is 45 DEG C, and parsing agent flux is 1.5 times of beds
Layer volume/hour, macroporous adsorbent exchange capacity is 150 times of bed volumes；
No color or smell removal of impurities filtrate obtained by e, step c, is filtered, NF membrane using rolling macromolecule material NF membrane
Molecular cut off be 300D, filtration temperature be 30 DEG C, filter pressure position 42bar, obtain filtrate 2 and trapped fluid 2, NF membrane
Cycles of concentration is 2 times, and sodium sulfate concentration is 106g/L in trapped fluid；
Trapped fluid 2 obtained by f, step e, is cooled to-5-5 DEG C, crystallizes and separates crystal using centrifuge, obtains ten water
Sodium sulfate crystal and hyposaline crystalline mother solution, the content of sodium sulphate is 9g/L in crystalline mother solution；
Using the forced-circulation evaporator of carrying vapour compressor after the sal glauberi crystal heating for dissolving that g, step f are obtained
Crystallization and evaporation, sodium sulphate reaches supersaturation in evaporator, and in-vitro separation crystal Mother liquor Returning evaporimeter continues to evaporate.Obtain
Byproduct glauber salt and a small amount of steam condensate, steam condensate set are used filtering fermentation liquor unit and are used as water-dialyzing；
The filtrate 2 and step f that high chroma, stench, the organic wastewater of high concentration and the step e that h, step d are obtained are obtained are obtained
The hyposaline crystalline mother solution for obtaining merges, and the COD for merging waste water is 9700mg/L, sodium sulphate content 4.5g/L, using biochemical treatment,
Realize qualified discharge；
Long-chain alkanedioic 1.5kg is reclaimed in i, mother liquor waste water per ton, byproduct glauber salt 48kg is obtained.
Preferably, it is present invention also offers a kind of integrated conduct method of long-chain alkanedioic crystalline mother solution including following
Step：
Long-chain alkanedioic crystalline mother solution, wherein sodium sulphate 45-55g/L, long-chain alkanedioic 0.5-1.5g/L, impurity have
Machine acid 8-12g/L, protein 0.7-1.3g/L, COD total amount 10000-12000mg/L, pH4.0, there is different smell, khaki,
Containing a small amount of fine long-chain alkanedioic crystal, filtered using milipore filter, concentrated 25-30 times, obtained trapped fluid 1 and filtrate
1；
Trapped fluid 1 obtained by step a, wherein long-chain alkanedioic content 15-45g/L, can cover and use filtering fermentation liquor list
Reuse in the alkaline filtrate of unit；
Filtrate 1 obtained by step b, turbidity≤0.2NTU carries out adsorption-edulcoration using macroporous adsorbent, obtains colourless, nothing
Smelly removing impurities filtrate and saturation macroporous adsorbent；
Saturation macroporous adsorbent obtained by step c, is parsed using 4%NaOH solution, obtains high chroma, stench, height
The organic wastewater of concentration and the macroporous adsorbent of recovery adsorption capacity；
No color or smell removal of impurities filtrate obtained by step c, is filtered using NF membrane, obtains filtrate 2 and trapped fluid 2；
Trapped fluid 2 obtained by step e, is cooled to-5-5 DEG C, crystallizes and separates crystal using centrifuge, obtains ten water sulphur
Sour sodium crystal and hyposaline crystalline mother solution；
Forced-circulation evaporator crystallization and evaporation is used after the sal glauberi crystal heating for dissolving that step f is obtained, obtains secondary
Product glauber salt and a small amount of steam condensate, steam condensate set are used filtering fermentation liquor unit and are used as water-dialyzing；
The filtrate 2 and step f that high chroma, stench, the organic wastewater of high concentration and the step e that step d is obtained are obtained obtain
Hyposaline crystalline mother solution merge, using biochemical treatment, realize qualified discharge；
Preferably, its material of the milipore filter described in step a includes but is not limited to Al2O3、TiO2, it is polysulfones, polyether sulfone, modified
Polyether sulfone, Kynoar, polytetrafluoroethylene (PTFE) etc., the preferred Al of milipore filter of the present invention2O3、TiO2Material；The filtering accuracy of milipore filter
It is 20-200nm, the present invention preferably 20-100nm, hyperfiltration membrane assembly mode is doughnut, rolling, board-like, tubular type etc., this hair
Bright preferred tubular module mode；The filter pressure position 0-10bar of milipore filter, the filter type of milipore filter is cross-flow or dead end mistake
Filter, the present invention preferably cross-flow filtration, particularly preferred film layer is TiO2Supporting layer is the stainless steel tubular membrane of 316L stainless steels；
Preferably, the macroporous adsorbent described in step c includes but is not limited to low pole or nonpolar macroporous adsorbent, preferably
Low pole macroporous adsorbent；
Preferably, the NF membrane described in step e is the polymeric membrane of wound module mode, and its molecular cut off is 200-
300D, its rejection to magnesium sulfate is 90-98%, and operating pressure is 0-42bar, and operation temperature is 0-45 DEG C；
Preferably, the forced-circulation evaporator described in step g includes but is not limited to multi-effect forced circulation evaporation device or band steams
The forced-circulation evaporator of vapour compressor, sodium sulphate reaches supersaturation in evaporator, and in-vitro separation crystal Mother liquor is returned steams
Hair device continues to evaporate.
In sum, the beneficial effects of the present invention are：The present invention is using hyperfiltration technique, macroporous adsorbent technology, nanofiltration
Technology, freezing denitration technology, crystallization and evaporation technology reclaim the long-chain alkanedioic in waste water and obtain byproduct glauber salt, realize
Turn waste into wealth, comprehensive utilization of resources, it is final obtain hyposaline waste water can after biochemical treatment qualified discharge.
The invention is not restricted to above-mentioned specific embodiment.It is understood that not departing from spirit and substance of the present invention model
In the case of enclosing, various changes and modifications can be made, these should be all included within protection scope of the present invention.
Claims (10)
1. a kind of integrated conduct method of long-chain alkanedioic crystalline mother solution, it is characterised in that comprise the following steps：
Long-chain alkanedioic crystalline mother solution carries out filtering and concentrating using milipore filter, obtains the first trapped fluid and the first filtrate；
First trapped fluid set uses reuse in the alkaline filtrate of long-chain alkanedioic filtering fermentation liquor unit；
First filtrate carries out adsorption-edulcoration using macroporous adsorbent, obtains no color or smell removal of impurities filtrate and saturation macroporous adsorbent；
Saturation macroporous adsorbent is parsed using NaOH solution, obtains high chroma, stench, the organic wastewater of high concentration and recovery
The macroporous adsorbent of adsorption capacity；
The no color or smell removal of impurities filtrate is filtered using NF membrane, obtains the second filtrate and the second trapped fluid；
Second trapped fluid crystallisation by cooling simultaneously separates crystal using centrifuge, obtains sal glauberi crystal and hyposaline crystallization is female
Liquid；
Forced-circulation evaporator crystallization and evaporation is used after sal glauberi crystal heating for dissolving, byproduct glauber salt and a small amount of is obtained
Steam condensate, steam condensate set is used long-chain alkanedioic filtering fermentation liquor unit and is used as water-dialyzing；
The high chroma, stench, the organic wastewater of high concentration, the second filtrate and hyposaline crystalline mother solution merge, at biochemistry
Reason, realizes qualified discharge.
2. integrated conduct method according to claim 1, it is characterised in that in long-chain alkanedioic crystalline mother solution, sodium sulphate
45-55g/L, long-chain alkanedioic 0.5-1.5g/L, impurity organic acid 8-12g/L, protein 0.7-1.3g/L, COD total amount
10000-12000mg/L, pH4.0, there is different smell, khaki, contain a small amount of fine long-chain alkanedioic crystal.
3. integrated conduct method according to claim 2, it is characterised in that long-chain alkanedioic crystalline mother solution uses ultrafiltration
Film concentrates 25-30 times after being filtered.
4. the integrated conduct method according to claim any one of 1-3, it is characterised in that long-chain binary in the first trapped fluid
Alkanoic acid content 15-45g/L.
5. integrated conduct method according to claim 4, it is characterised in that the turbidity≤0.2NTU of the first filtrate.
6. integrated conduct method according to claim 4, it is characterised in that saturation macroporous adsorbent uses 4%NaOH solution
Parsed.
7. integrated conduct method according to claim 5, it is characterised in that the second trapped fluid is tied after being cooled to-5-5 DEG C
It is brilliant.
8. integrated conduct method according to claim 5, it is characterised in that the material of milipore filter includes Al2O3、TiO2, it is poly-
Sulfone, polyether sulfone, modified poly (ether-sulfone), Kynoar or polytetrafluoroethylene (PTFE)；The filtering accuracy of milipore filter is 20-200nm, milipore filter
Modularity is doughnut, rolling, board-like or tubular type；The filter pressure of milipore filter is less than 10bar.
9. integrated conduct method according to claim 5, it is characterised in that macroporous adsorbent includes low pole or nonpolar
Macroporous adsorbent.
10. integrated conduct method according to claim 5, it is characterised in that NF membrane is the macromolecule of wound module mode
Film, its molecular cut off is 200-300D, and its rejection to magnesium sulfate is 90-98%, and operating pressure is 0-42bar, operation
Temperature is 0-45 DEG C；Forced-circulation evaporator includes the forced-circulation evaporation of multi-effect forced circulation evaporation device or carrying vapour compressor
Device.
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