CN105836976A - Comprehensive treatment method of long-chain dialkyl acid crystallization mother liquor - Google Patents
Comprehensive treatment method of long-chain dialkyl acid crystallization mother liquor Download PDFInfo
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Abstract
The invention discloses a comprehensive treatment method of long-chain dialkyl acid crystallization mother liquor. By adopting an ultrafiltration technology, a macroporous sorbent technology, a nanofiltration technology, a refrigeration denitration technology, and a crystallizing evaporation technology, long-chain dialkyl acid in wastewater is recovered and a sodium sulphate by-product is obtained, so that the waste is turned into treasure, the resources are comprehensively utilized, and the ultimately obtained low-salinity wastewater is emitted up to standard after being biochemically treated.
Description
Technical field
The invention belongs to biological chemical field, particularly to the General Office of a kind of long-chain alkanedioic crystalline mother solution
Reason method.
Background technology
Long-chain alkanedioic is to be that raw material is converted by microorganism with the long chain alkane (paraffin) of ten two-ten six carbon
Produce and obtain.In the sweat of long alkanoic acid, alkane transformations becomes alkanoic acid, and the pH of fermentation liquid reduces, in order to
Maintain constant thalline optimum pH, sweat needs to add sodium hydroxide, additionally clarifies at filtering fermentation liquor
When carrying out thalline separation, in order to allow binary acid become salt to dissolve, still need to add a large amount of sodium hydroxide (sodium hydroxide
Total addition level and binary acid equivalent).Binary acid is made in order to reduce binary acid ionization degree during Crystallization Separation
Crystallize with molecularity, must add again and the sulphuric acid of sodium hydroxide equivalent.In final crystalline mother solution waste water
Containing sodium sulfate 45-55g/L, fine long-chain alkanedioic crystal 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, and have foreign odor taste, in fawn
Color.
Due to, containing a large amount of sodium sulfate in mother liquor waste water, owing to osmotic pressure is too high, microorganism is difficult to survive,
Cannot be carried out biochemical treatment, conventional processes is as follows:
From handing over desalination+biochemical treatment: owing in mother liquor waste water, sodium sulphate content is too high, waste water per ton needs to expend
The hydrochloric acid 100kg of regenerating resin, sodium hydroxide 25kg, only acid and alkali consumption more than 100 yuan of RMB/ ton waste water,
Additionally the long-chain alkanedioic in waste water treats as Pollutant Treatment, resource serious waste.It addition, in waste water
Long alkanoic acid micro crystal can block resin, causes from friendship system washing amount big, it is impossible to run continuously；
Evaporating and concentrating process: the direct multiple-effect evaporation of waste water, on the one hand expends huge steam cost, on the other hand
Owing to the sodium sulfate that evaporation and concentration obtains containing albumen, pigment, long alkanoic acid, foul smell, it is impossible to as
By-product sale, processes only as dangerous solid waste, and 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 the integrated conduct method of a kind of long-chain alkanedioic crystalline mother solution,
To solve problems of the prior art.
Summary of the invention
Complete the present invention in view of at least one the problems referred to above, and it is an object of the present invention to carry
Integrated conduct method for a kind of long-chain alkanedioic crystalline mother solution, it is characterised in that comprise the following steps:
Long-chain alkanedioic crystalline mother solution uses ultrafilter membrane to carry out filtering and concentrating, it is thus achieved that the first trapped fluid and first
Filtrate；
Reuse in the alkaline filtrate of filtering fermentation liquor unit used by first trapped fluid set；
First filtrate uses macroporous adsorbent to carry out adsorption-edulcoration, it is thus achieved that colourless, the removing impurities filtrate of odorless and full
And macroporous adsorbent；
Saturated macroporous adsorbent uses NaOH solution to resolve, it is thus achieved that high chroma, stench, the having of high concentration
Machine waste water and the macroporous adsorbent of recovery absorbability；
Described no color or smell remove impurity filtrate uses NF membrane to filter, it is thus achieved that the second filtrate and the second trapped fluid；
Second trapped fluid crystallisation by cooling also uses centrifuge separation crystal, it is thus achieved that sal glauberi crystal and low contain
Salt-pepper noise mother solution；
Forced-circulation evaporator crystallization and evaporation is used, it is thus achieved that side-product unit after sal glauberi crystal heating for dissolving
Bright powder and a small amount of steam condensate, steam condensate set is used filtering fermentation liquor unit and is used as water-dialyzing；
Described high chroma, stench, the organic wastewater of high concentration, the second filtrate and hyposaline crystalline mother solution merge,
Use biochemical treatment, it is achieved qualified discharge.
According to a further aspect of the invention, in long-chain alkanedioic crystalline mother solution, sodium sulfate 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 foreign odor taste, khaki, containing a small amount of fine long-chain alkanedioic
Crystal.
According to a further aspect of the invention, long-chain alkanedioic crystalline mother solution uses ultrafilter membrane to concentrate after filtering
25-30 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, saturated macroporous adsorbent uses 4%NaOH solution to resolve.
According to a further aspect of the invention, crystallize after the second trapped fluid is cooled to-5 5 DEG C.
According to a further aspect of the invention, the material of ultrafilter membrane includes Al2O3、TiO2, polysulfones, polyether sulfone, modification
Polyether sulfone, Kynoar or politef；The filtering accuracy of ultrafilter membrane is 20-200nm, ultrafilter membrane group
Part mode is doughnut, rolling, board-like or tubular type；The filter pressure of ultrafilter membrane 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, its molecular cut off
For 200-300D, it is 90-98% to the rejection of magnesium sulfate, and operation pressure is 0-42bar, and operation temperature is
0-45℃；Forced-circulation evaporator includes multi-effect forced circulation evaporation device or the forced circulation of carrying vapour compressor
Vaporizer.
Compared with prior art, the beneficial effects of the present invention is: the present invention uses ultrafilter membrane to reclaim in mother solution
Long-chain alkanedioic product, uses macroporous adsorbent to remove the pigment in ultrafilter membrane filtrate, stink, dissolubility
Long-chain alkanedioic, dissolubility low pole and non polar impurities, use NF membrane further concentrated vitriol sodium,
And through freezing denitration, after evaporative crystallization, obtain highly purified side-product Matrii Sulfas Exsiccatus.Length is reclaimed by the present invention
Chain alkanedioic and Matrii Sulfas Exsiccatus side-product realize comprehensive utilization of resources, and the waste water that overbalances reclaiming product processes
Cost, it is achieved 25 yuan of RMB/ ton waste water of getting a profit.
Accompanying drawing explanation
Fig. 1 is the integrated conduct method stream of long-chain alkanedioic crystalline mother solution according to the preferred embodiment of the invention
Cheng Tu.
Detailed description of the invention
Below in conjunction with the accompanying drawings, the preferred forms of the present invention, tool here are described by preferred embodiment
Body embodiment is to explain the present invention, and should not be construed as limitation of the present invention, without departing from
In the case of spirit and substance of the present invention scope, can make various changes and modifications, these all should comprise
Within protection scope of the present invention.
Seeing Fig. 1, the preferred embodiment of the present invention provides the integrated treatment of a kind of long-chain alkanedioic crystalline mother solution
Method.The integrated conduct method of this long-chain alkanedioic crystalline mother solution comprises the following steps:
Long-chain alkanedioic crystalline mother solution uses ultrafilter membrane to carry out filtering and concentrating, it is thus achieved that the first trapped fluid and first
Filtrate；
Reuse in the alkaline filtrate of filtering fermentation liquor unit used by first trapped fluid set；
First filtrate uses macroporous adsorbent to carry out adsorption-edulcoration, it is thus achieved that colourless, the removing impurities filtrate of odorless and full
And macroporous adsorbent；
Saturated macroporous adsorbent uses NaOH solution to resolve, it is thus achieved that high chroma, stench, the having of high concentration
Machine waste water and the macroporous adsorbent of recovery absorbability；
Described no color or smell remove impurity filtrate uses NF membrane to filter, it is thus achieved that the second filtrate and the second trapped fluid；
Second trapped fluid crystallisation by cooling also uses centrifuge separation crystal, it is thus achieved that sal glauberi crystal and low contain
Salt-pepper noise mother solution；
Forced-circulation evaporator crystallization and evaporation is used, it is thus achieved that side-product unit after sal glauberi crystal heating for dissolving
Bright powder and a small amount of steam condensate, steam condensate set is used filtering fermentation liquor unit and is used as water-dialyzing；
Described high chroma, stench, the organic wastewater of high concentration, the second filtrate and hyposaline crystalline mother solution merge,
Use biochemical treatment, it is achieved qualified discharge.
Preferably, in long-chain alkanedioic crystalline mother solution, sodium sulfate 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 foreign odor taste, khaki, containing a small amount of fine long-chain alkanedioic
Crystal.
Preferably, long-chain alkanedioic crystalline mother solution uses ultrafilter membrane to concentrate 25-30 times after filtering.
Preferably, long-chain alkanedioic content 15-45g/L in the first trapped fluid.
Preferably, the turbidity≤0.2NTU of the first filtrate.
Preferably, saturated macroporous adsorbent uses 4%NaOH solution to resolve.
Preferably, crystallize after the second trapped fluid is cooled to-5 5 DEG C.
Preferably, the material of ultrafilter membrane includes Al2O3、TiO2, polysulfones, polyether sulfone, modified poly (ether-sulfone), poly-partially
Fluorothene or politef；The filtering accuracy of ultrafilter membrane is 20-200nm, and hyperfiltration membrane assembly mode is hollow
Fiber, rolling, board-like or tubular type；The filter pressure of ultrafilter membrane 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,
It is 90-98% to the rejection of magnesium sulfate, and operation pressure is 0-42bar, and operation temperature is 0-45 DEG C；Force
Circulating evaporator includes multi-effect forced circulation evaporation device or the forced-circulation evaporator of carrying vapour compressor.
Preferably, the present invention is directed to the long-chain alkanedioic crystalline mother solution waste water that traditional handicraft cannot process, carry
Turn waste into wealth for one, the waste water processing scheme of comprehensive utilization of resources.Specifically, present invention also offers one
Plant the integrated conduct method of long-chain alkanedioic crystalline mother solution, comprise the following steps:
A, long-chain alkanedioic crystalline mother solution, wherein sodium sulfate 45-55g/L, long-chain alkanedioic 0.5-1.5
G/L, impurity organic acid 8-12g/L, protein 0.7-1.3g/L, COD total amount 10000-12000mg/L,
PH4.0, has foreign odor taste, khaki, containing a small amount of fine long-chain alkanedioic crystal, uses ultrafilter membrane to enter
Row filters, and concentrates 25-30 times, it is thus achieved that trapped fluid 1 and filtrate 1；
B, the trapped fluid 1 of step a gained, wherein long-chain alkanedioic content 15-45g/L, can overlap and use fermentation
Reuse in the alkaline filtrate of liquid filter element；
C, the filtrate 1 of step b gained, turbidity≤0.2NTU, use macroporous adsorbent to carry out adsorption-edulcoration, obtain
Colourless, the removing impurities filtrate of odorless and saturated macroporous adsorbent, absorption flow is 3-10 times of bed volume/little
Time, adsorption temp is 10-30 DEG C；
D, the saturated macroporous adsorbent of step c gained, use 4%NaOH solution to resolve, it is thus achieved that high chroma,
Stench, the organic wastewater of high concentration and the macroporous adsorbent of recovery absorbability；Resolution temperature is 20-50 DEG C,
Resolve agent flux be 1-3 times of bed volume/hour, macroporous adsorbent exchange capacity is 150-400 times of bed body
Long-pending；
E, the no color or smell remove impurity filtrate of step c gained, use NF membrane to filter, it is thus achieved that filtrate 2 and cutting
Staying liquid 2, the cycles of concentration of NF membrane is 2 times, and in trapped fluid, sodium sulfate concentration is 90-110g/L；
F, the trapped fluid 2 of step e gained, be cooled to-5 5 DEG C, crystallizes and use centrifuge separation crystal,
Obtaining sal glauberi crystal and hyposaline crystalline mother solution, in crystalline mother solution, the content of sodium sulfate is 8-12g/L；
Forced-circulation evaporator crystallization and evaporation is used after the sal glauberi crystal heating for dissolving that g, step f obtain,
Obtaining side-product Matrii Sulfas Exsiccatus and a small amount of steam condensate, filtering fermentation liquor unit conduct used by steam condensate set
Water-dialyzing uses；
Filtrate 2 that high chroma that h, step d obtain, stench, the organic wastewater of high concentration and step e obtain and
The hyposaline crystalline mother solution that step f obtains merges, and the COD merging waste water is 9000-11000mg/L, sodium sulfate
Content≤5g/L, uses biochemical treatment, it is achieved qualified discharge.
Preferably, its material of the ultrafilter membrane described in step a includes but not limited to Al2O3、TiO2, polysulfones, polyethers
Sulfone, modified poly (ether-sulfone), Kynoar, politef etc., the preferred Al of ultrafilter membrane of the present invention2O3、TiO2
Material；The filtering accuracy of ultrafilter membrane is 20-200nm, the preferred 20-100nm of the present invention, hyperfiltration membrane assembly mode
For doughnut, rolling, board-like, tubular type etc., the present invention preferred tubular module mode；The filtration of ultrafilter membrane
Pressure position 0-10bar, the filter type of ultrafilter membrane is cross-flow or dead-end filtration, the preferred cross flow filter of the present invention,
Particularly preferably film layer is TiO2Supporting layer is 316L stainless rustless steel tubular membrane.
Preferably, the macroporous adsorbent described in step c includes but not limited to low pole or nonpolar macroporous absorption
Agent, 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, it is 90-98% to the rejection of magnesium sulfate, and operation pressure is 0-42bar, and operation temperature is
0-45℃。
Preferably, the forced-circulation evaporator described in step g include but not limited to multi-effect forced circulation evaporation device or
The forced-circulation evaporator of carrying vapour compressor, sodium sulfate reaches supersaturation in vaporizer, and in-vitro separation is brilliant
After body, mother solution Returning evaporimeter continues evaporation.
Preferably, a kind of long-chain alkanedioic crystalline mother solution comprehensive processing technique of the present invention, mother per ton are used
Liquid waste water can reclaim long-chain alkanedioic 0.5-1.5kg, it is thus achieved that side-product Matrii Sulfas Exsiccatus 40-50kg.
Preferably, present invention also offers the integrated conduct method of a kind of long-chain alkanedioic crystalline mother solution, bag
Include following steps:
Take long-chain alkanedioic crystalline mother solution, wherein contain sodium sulfate 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 foreign odor
Taste, in khaki, processing method is as follows:
A, long-chain alkanedioic crystalline mother solution, using film layer is TiO2, supporting layer is that 316L is stainless stainless
Steel membrane filters, and filtering accuracy is 100nm, filter pressure position 5bar, concentrates 30 times, it is thus achieved that trapped fluid 1
With filtrate 1,
B, the trapped fluid 1 of step a gained, wherein long-chain alkanedioic content 21g/L, fermentation liquid mistake used by set
Reuse in the alkaline filtrate of filter unit；
C, the filtrate 1 of step b gained, turbidity 0.2NTU, use macroporous adsorbent to carry out adsorption-edulcoration, it is thus achieved that
Colourless, the removing impurities filtrate of odorless and saturated macroporous adsorbent, absorption flow is 3 times/hour of bed volume,
Adsorption temp is 10 DEG C；
D, the saturated macroporous adsorbent of step c gained, use 4%NaOH solution to resolve, it is thus achieved that high chroma,
Stench, the organic wastewater of high concentration and the macroporous adsorbent of recovery absorbability；Resolution temperature is 45 DEG C, solves
Analysis agent flux be 2 times of bed volume/hour, macroporous adsorbent exchange capacity is 280 times of bed volume；
E, the no color or smell remove impurity filtrate of step c gained, use rolling macromolecule material NF membrane to filter,
The molecular cut off of NF membrane is 200D, and filtration temperature is 30 DEG C, filter pressure position 39bar, it is thus achieved that filtrate 2
With trapped fluid 2, the cycles of concentration of NF membrane is 2 times, and in trapped fluid, sodium sulfate concentration is 90g/L；
F, the trapped fluid 2 of step e gained, be cooled to-5 5 DEG C, crystallizes and use centrifuge separation crystal,
Obtaining sal glauberi crystal and hyposaline crystalline mother solution, in crystalline mother solution, the content of sodium sulfate is 8g/L；
The forced circulation of carrying vapour compressor is used after the sal glauberi crystal heating for dissolving that g, step f obtain
Vaporizer crystallization and evaporation, sodium sulfate reaches supersaturation in vaporizer, and after in-vitro separation crystal, mother solution returns and steams
Send out device and continue evaporation.Obtaining side-product Matrii Sulfas Exsiccatus and a small amount of steam condensate, fermentation used by steam condensate set
Liquid filter element uses as water-dialyzing；
Filtrate 2 that high chroma that h, step d obtain, stench, the organic wastewater of high concentration and step e obtain and
The hyposaline crystalline mother solution that step f obtains merges, and the COD merging waste water is 9300mg/L, sodium sulphate content
4g/L, uses biochemical treatment, it is achieved qualified discharge；
I, mother liquor waste water per ton reclaim long-chain alkanedioic 0.7kg, it is thus achieved that side-product Matrii Sulfas Exsiccatus 40kg.
Preferably, present invention also offers the integrated conduct method of a kind of long-chain alkanedioic crystalline mother solution, bag
Include following steps:
Take long-chain alkanedioic crystalline mother solution, wherein contain sodium sulfate 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
Foreign odor taste, in khaki, processing method is as follows:
A, long-chain alkanedioic crystalline mother solution, using film layer is TiO2, and supporting layer is that 316L is stainless stainless
Steel membrane filters, and filtering accuracy is 100nm, filter pressure position 9bar, concentrates 29 times, it is thus achieved that trapped fluid 1
With filtrate 1；
B, the trapped fluid 1 of step a gained, wherein long-chain alkanedioic content 37.7g/L, fermentation liquid used by set
Reuse in the alkaline filtrate of filter element；
C, the filtrate 1 of step b gained, turbidity 0.15NTU, use macroporous adsorbent to carry out adsorption-edulcoration, obtain
Obtaining colourless, the removing impurities filtrate of odorless and saturated macroporous adsorbent, absorption flow is 5 times/hour of bed volume,
Adsorption temp is 20 DEG C；
D, the saturated macroporous adsorbent of step c gained, use 4%NaOH solution to resolve, it is thus achieved that high chroma,
Stench, the organic wastewater of high concentration and the macroporous adsorbent of recovery absorbability；Resolution temperature is 45 DEG C, solves
Analysis agent flux be 1.5 times of bed volume/hour, macroporous adsorbent exchange capacity is 300 times of bed volume；
E, the no color or smell remove impurity filtrate of step c gained, use rolling macromolecule material NF membrane to filter,
The molecular cut off of NF membrane is 250D, and filtration temperature is 33 DEG C, filter pressure position 40bar, it is thus achieved that filtrate 2
With trapped fluid 2, the cycles of concentration of NF membrane is 2 times, and in trapped fluid, sodium sulfate concentration is 110g/L；
F, the trapped fluid 2 of step e gained, be cooled to-5 5 DEG C, crystallizes and use centrifuge separation crystal,
Obtaining sal glauberi crystal and hyposaline crystalline mother solution, in crystalline mother solution, the content of sodium sulfate is 10g/L；
The forced circulation of carrying vapour compressor is used after the sal glauberi crystal heating for dissolving that g, step f obtain
Vaporizer crystallization and evaporation, sodium sulfate reaches supersaturation in vaporizer, and after in-vitro separation crystal, mother solution returns and steams
Send out device and continue evaporation.Obtaining side-product Matrii Sulfas Exsiccatus and a small amount of steam condensate, fermentation used by steam condensate set
Liquid filter element uses as water-dialyzing；
Filtrate 2 that high chroma that h, step d obtain, stench, the organic wastewater of high concentration and step e obtain and
The hyposaline crystalline mother solution that step f obtains merges, and the COD merging waste water is 9800mg/L, sodium sulphate content
4.9g/L, uses biochemical treatment, it is achieved qualified discharge；
I, mother liquor waste water per ton reclaim long-chain alkanedioic 1.3kg, it is thus achieved that side-product Matrii Sulfas Exsiccatus 50kg.
Preferably, present invention also offers the integrated conduct method of a kind of long-chain alkanedioic crystalline mother solution, bag
Include following steps:
Take long-chain alkanedioic crystalline mother solution, wherein contain sodium sulfate 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
Foreign odor taste, in khaki, processing method is as follows:
A, long-chain alkanedioic crystalline mother solution, using film layer is TiO2, supporting layer is that 316L is stainless stainless
Steel membrane filters, and filtering accuracy is 50nm, filter pressure position 7bar, concentrates 28 times, it is thus achieved that trapped fluid 1 He
Filtrate 1,
B, the trapped fluid 1 of step a gained, wherein long-chain alkanedioic content 42g/L, fermentation liquid mistake used by set
Reuse in the alkaline filtrate of filter unit；
C, the filtrate 1 of step b gained, turbidity 0.1NTU, use macroporous adsorbent to carry out adsorption-edulcoration, it is thus achieved that
Colourless, the removing impurities filtrate of odorless and saturated macroporous adsorbent, absorption flow is 9 times/hour of bed volume,
Adsorption temp is 25 DEG C；
D, the saturated macroporous adsorbent of step c gained, use 4%NaOH solution to resolve, it is thus achieved that high chroma,
Stench, the organic wastewater of high concentration and the macroporous adsorbent of recovery absorbability；Resolution temperature is 45 DEG C, solves
Analysis agent flux be 1.5 times of bed volume/hour, macroporous adsorbent exchange capacity is 150 times of bed volume；
E, the no color or smell remove impurity filtrate of step c gained, use rolling macromolecule material NF membrane to filter,
The molecular cut off of NF membrane is 300D, and filtration temperature is 30 DEG C, filter pressure position 42bar, it is thus achieved that filtrate 2
With trapped fluid 2, the cycles of concentration of NF membrane is 2 times, and in trapped fluid, sodium sulfate concentration is 106g/L；
F, the trapped fluid 2 of step e gained, be cooled to-5 5 DEG C, crystallizes and use centrifuge separation crystal,
Obtaining sal glauberi crystal and hyposaline crystalline mother solution, in crystalline mother solution, the content of sodium sulfate is 9g/L；
The forced circulation of carrying vapour compressor is used after the sal glauberi crystal heating for dissolving that g, step f obtain
Vaporizer crystallization and evaporation, sodium sulfate reaches supersaturation in vaporizer, and after in-vitro separation crystal, mother solution returns and steams
Send out device and continue evaporation.Obtaining side-product Matrii Sulfas Exsiccatus and a small amount of steam condensate, fermentation used by steam condensate set
Liquid filter element uses as water-dialyzing；
Filtrate 2 that high chroma that h, step d obtain, stench, the organic wastewater of high concentration and step e obtain and
The hyposaline crystalline mother solution that step f obtains merges, and the COD merging waste water is 9700mg/L, sodium sulphate content
4.5g/L, uses biochemical treatment, it is achieved qualified discharge；
I, mother liquor waste water per ton reclaim long-chain alkanedioic 1.5kg, it is thus achieved that side-product Matrii Sulfas Exsiccatus 48kg.
Preferably, present invention also offers the integrated conduct method of a kind of long-chain alkanedioic crystalline mother solution, bag
Include following steps:
Long-chain alkanedioic crystalline mother solution, wherein sodium sulfate 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 foreign odor taste, khaki, containing a small amount of fine long-chain alkanedioic crystal, use ultrafilter membrane to filter,
Concentrate 25-30 times, it is thus achieved that trapped fluid 1 and filtrate 1；
The trapped fluid 1 of step a gained, wherein long-chain alkanedioic content 15-45g/L, can overlap and use fermentation liquid
Reuse in the alkaline filtrate of filter element；
The filtrate 1 of step b gained, turbidity≤0.2NTU, use macroporous adsorbent to carry out adsorption-edulcoration, it is thus achieved that
Colourless, the removing impurities filtrate of odorless and saturated macroporous adsorbent；
The saturated macroporous adsorbent of step c gained, uses 4%NaOH solution to resolve, it is thus achieved that high chroma, evil
Smelly, the organic wastewater of high concentration and recover the macroporous adsorbent of absorbability；
The no color or smell remove impurity filtrate of step c gained, uses NF membrane to filter, it is thus achieved that filtrate 2 and retaining
Liquid 2；
The trapped fluid 2 of step e gained, is cooled to-5 5 DEG C, crystallizes and use centrifuge separation crystal, it is thus achieved that
Sal glauberi crystal and hyposaline crystalline mother solution；
Use forced-circulation evaporator crystallization and evaporation after the sal glauberi crystal heating for dissolving that step f obtains, obtain
Obtaining side-product Matrii Sulfas Exsiccatus and a small amount of steam condensate, steam condensate set uses filtering fermentation liquor unit as thoroughly
Bleed uses；
The high chroma of step d acquisition, stench, the organic wastewater of high concentration and the filtrate 2 of step e acquisition and step
The hyposaline crystalline mother solution that f obtains merges, and uses biochemical treatment, it is achieved qualified discharge；
Preferably, its material of the ultrafilter membrane described in step a includes but not limited to Al2O3、TiO2, polysulfones, polyethers
Sulfone, modified poly (ether-sulfone), Kynoar, politef etc., the preferred Al of ultrafilter membrane of the present invention2O3、TiO2
Material；The filtering accuracy of ultrafilter membrane is 20-200nm, the preferred 20-100nm of the present invention, hyperfiltration membrane assembly mode
For doughnut, rolling, board-like, tubular type etc., the present invention preferred tubular module mode；The filtration of ultrafilter membrane
Pressure position 0-10bar, the filter type of ultrafilter membrane is cross-flow or dead-end filtration, the preferred cross flow filter of the present invention,
Particularly preferably film layer is TiO2Supporting layer is 316L stainless rustless steel tubular membrane；
Preferably, the macroporous adsorbent described in step c includes but not limited to low pole or nonpolar macroporous absorption
Agent, 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, it is 90-98% to the rejection of magnesium sulfate, and operation pressure is 0-42bar, and operation temperature is
0-45℃；
Preferably, the forced-circulation evaporator described in step g include but not limited to multi-effect forced circulation evaporation device or
The forced-circulation evaporator of carrying vapour compressor, sodium sulfate reaches supersaturation in vaporizer, and in-vitro separation is brilliant
After body, mother solution Returning evaporimeter continues evaporation.
In sum, the beneficial effects of the present invention is: the present invention uses hyperfiltration technique, macroporous adsorbent skill
Art, nanofiltration, freezing denitration technology, crystallization and evaporation technology reclaim the long-chain alkanedioic in waste water and obtain
Obtaining side-product Matrii Sulfas Exsiccatus, it is achieved turn waste into wealth, comprehensive utilization of resources, final acquisition hyposaline waste water can be through life
Qualified discharge after change process.
The invention is not restricted to above-mentioned specific embodiment.It is understood that without departing from the present invention spirit and
In the case of essential scope, can make various changes and modifications, these all should be included in the protection of the present invention
Within the scope of.
Claims (10)
1. the integrated conduct method of a long-chain alkanedioic crystalline mother solution, it is characterised in that include following step
Rapid:
Long-chain alkanedioic crystalline mother solution uses ultrafilter membrane to carry out filtering and concentrating, it is thus achieved that the first trapped fluid and first
Filtrate；
Reuse in the alkaline filtrate of filtering fermentation liquor unit used by first trapped fluid set；
First filtrate uses macroporous adsorbent to carry out adsorption-edulcoration, it is thus achieved that colourless, the removing impurities filtrate of odorless and full
And macroporous adsorbent；
Saturated macroporous adsorbent uses NaOH solution to resolve, it is thus achieved that high chroma, stench, the having of high concentration
Machine waste water and the macroporous adsorbent of recovery absorbability；
Described no color or smell remove impurity filtrate uses NF membrane to filter, it is thus achieved that the second filtrate and the second trapped fluid；
Second trapped fluid crystallisation by cooling also uses centrifuge separation crystal, it is thus achieved that sal glauberi crystal and low contain
Salt-pepper noise mother solution；
Forced-circulation evaporator crystallization and evaporation is used, it is thus achieved that side-product unit after sal glauberi crystal heating for dissolving
Bright powder and a small amount of steam condensate, steam condensate set is used filtering fermentation liquor unit and is used as water-dialyzing；
Described high chroma, stench, the organic wastewater of high concentration, the second filtrate and hyposaline crystalline mother solution merge,
Use biochemical treatment, it is achieved qualified discharge.
Technique the most according to claim 1, it is characterised in that in long-chain alkanedioic crystalline mother solution, sulphuric acid
Sodium 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 foreign odor taste, khaki, containing few
Measure fine long-chain alkanedioic crystal.
Technique the most according to claim 2, it is characterised in that long-chain alkanedioic crystalline mother solution uses ultrafiltration
Film concentrates 25-30 times after filtering.
4. according to the technique described in any one of claim 1-3, it is characterised in that long-chain binary in the first trapped fluid
Alkanoic acid content 15-45g/L.
Technique the most according to claim 4, it is characterised in that the turbidity≤0.2NTU of the first filtrate.
Technique the most according to claim 4, it is characterised in that saturated macroporous adsorbent uses 4%NaOH solution
Resolve.
Technique the most according to claim 5, it is characterised in that the second trapped fluid is tied after being cooled to-5 5 DEG C
Brilliant.
Technique the most according to claim 5, it is characterised in that the material of ultrafilter membrane includes Al2O3、TiO2、
Polysulfones, polyether sulfone, modified poly (ether-sulfone), Kynoar or politef；The filtering accuracy of ultrafilter membrane is
20-200nm, hyperfiltration membrane assembly mode is doughnut, rolling, board-like or tubular type；The filtration pressure of ultrafilter membrane
Power is less than 10bar.
Technique the most according to claim 5, it is characterised in that macroporous adsorbent includes low pole or nonpolar
Macroporous adsorbent.
Technique the most according to claim 5, it is characterised in that NF membrane is the high score of wound module mode
Sub-film, its molecular cut off is 200-300D, and it is 90-98% to the rejection of magnesium sulfate, and operation pressure is
0-42bar, operation temperature is 0-45 DEG C；Forced-circulation evaporator includes that multi-effect forced circulation evaporation device or band steam
The forced-circulation evaporator of vapour compressor.
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| CN110002653A (en) * | 2019-05-09 | 2019-07-12 | 麦王环境技术股份有限公司 | High-salt wastewater stable state recycling unit and technique |
| CN114426479A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Method and device for refining long-chain dicarboxylic acid |
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