CN103058429B - New process for comprehensively utilizing brown alga chemical calcium wastewater - Google Patents
New process for comprehensively utilizing brown alga chemical calcium wastewater Download PDFInfo
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- CN103058429B CN103058429B CN201310042437.7A CN201310042437A CN103058429B CN 103058429 B CN103058429 B CN 103058429B CN 201310042437 A CN201310042437 A CN 201310042437A CN 103058429 B CN103058429 B CN 103058429B
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- water
- waste
- electrodialysis
- brown alga
- calcium
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- 239000011575 calcium Substances 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 54
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 34
- 239000000126 substance Substances 0.000 title claims abstract description 29
- 239000002351 wastewater Substances 0.000 title claims abstract description 17
- 238000000909 electrodialysis Methods 0.000 claims abstract description 39
- 230000002308 calcification Effects 0.000 claims abstract description 26
- 238000010612 desalination reaction Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 89
- 239000002699 waste material Substances 0.000 claims description 59
- 208000004434 Calcinosis Diseases 0.000 claims description 25
- 239000013505 freshwater Substances 0.000 claims description 19
- 238000005189 flocculation Methods 0.000 claims description 17
- 230000016615 flocculation Effects 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910001424 calcium ion Inorganic materials 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 13
- 238000005187 foaming Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 210000002249 digestive system Anatomy 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000008399 tap water Substances 0.000 claims description 5
- 235000020679 tap water Nutrition 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 19
- 238000004064 recycling Methods 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 4
- 235000010413 sodium alginate Nutrition 0.000 description 4
- 239000000661 sodium alginate Substances 0.000 description 4
- 229940005550 sodium alginate Drugs 0.000 description 4
- 238000013517 stratification Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 235000010410 calcium alginate Nutrition 0.000 description 2
- 239000000648 calcium alginate Substances 0.000 description 2
- 229960002681 calcium alginate Drugs 0.000 description 2
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000003311 flocculating effect Effects 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000009287 sand filtration Methods 0.000 description 2
- -1 4.8L altogether Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention provides a new process for comprehensively utilizing brown alga chemical calcium wastewater. The process is the comprehensive utilization process established based on brown alga chemical calcium wastewater recycling which uses an electrodialysis desalination technology as a core. Two new comprehensive utilization technologies of the calcium wastewater, namely a two-time calcification pretreatment technology and a calcium wastewater electrodialysis concentration utilization technology, are provided to realize economically comprehensive utilization of the brown alga chemical calcium wastewater. By adopting the process provided by the invention, two new comprehensive utilization technologies of the calcium wastewater are further developed based on the calcium wastewater electrodialysis desalination technology, the utilization value of the calcium wastewater is improved, the treatment cost of the calcium wastewater is reduced, and the economical recycling of the calcium wastewater is really achieved.
Description
Technical field
The invention belongs to environmental protection, chemical technology field, be specifically related to a kind of brown alga chemical industry waste Ca water Novel integrated and utilize technique.
Background technology
The huge water loss of brown alga chemical industry has become the bottleneck of its development, existing wastewater treatment mode high cost, cannot realize the economic reuse of factory effluent, the power that makes enterprise lose reform is that the sector cannot realize the immediate cause that reduces water consumption, therefore, waste Ca water reuse technology is the unique channel that realizes brown alga chemical industry water-saving and emission-reducing cheaply.The approach that reduces waste Ca water reuse cost reduces its processing cost except adopting new technology, need the further utility value of exploitation waste Ca water, realize the comprehensive utilization of waste Ca water, the reuse cost of waste Ca water is further reduced, really realize the economic reuse of waste Ca water.
Remaining calcium contents in waste Ca water can reach 350-700ppm, and calcium amount too high in the long playing process of electrodialysis can cause the fouling under concentration polarization effect, reduces electrodialytic desalting efficiency, even causes pole plate to cancel.Therefore, developing a kind of calcium ion concn that reduces can be to solve the remaining too high optimal path of calcium amount in waste Ca water by effective calcium ion method of utilizing simultaneously, utilizes technique to become the new problem that the present invention faces therefore propose a kind of brown alga chemical industry waste Ca water Novel integrated.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of brown alga chemical industry waste Ca water Novel integrated and utilizes technique; On the basis of the brown alga chemical industry waste Ca water utilization process take electrodialytic technique as core, two kinds of novel waste Ca water comprehensive utilization techniques are proposed: the dense water conservancy technology of secondary calcification pretreatment technology and waste Ca water electrodialysis, further improve the utility value of waste Ca water, turn waste into wealth, really realized the economy comprehensive utilization of brown alga chemical industry waste Ca water.The present invention realizes according to following technical scheme:
1, a brown alga chemical industry waste Ca water comprehensive utilization process, is characterised in that: comprise the steps:
A, by waste Ca water with rush rare clear glue solution and mix a calcification by 1:1-3:1 by volume, flocculate floating;
B, separation subnatant enter follow-up electrodialysis process, and flocculation floating layer in upper strata adds appropriate calcium water to make wherein calcium contents higher than 400ppm, complete secondary calcification;
C, above-mentioned subnatant after treatment is carried out to electrodialysis desalination decalcification;
In D, C step fresh water after treatment be mixed in proportion into specific conductivity with tap water need be lower than 3ms/cm
2rare water that rushes rush rare Digestive system and carry out reuse, filter and produce waste Ca water after calcification and enter new round circulation; In C step dense water after treatment and brown alga chemical industry floating dreg liquid by volume 2:1-3:1 mix, make its calcification flocculation, after flocculation, clear liquid is drained as waste water, upper strata slag liquid further adds calcium water, makes flocculation completely, reaches simple helix extruding requirement.
Further, in described A step, waste Ca water with rush rare clear glue solution and need foam so that floating.
Further, in described C step, after electrodialysis process, fresh water specific conductivity is controlled at 2-4ms/cm
2, in the time that being greater than 40ppm, the calcium ion concn in electrodialysis fresh water use strong cation-exchanging resin further to process the calcium ion in electrodialysis fresh water, if the calcium ion concn in electrodialysis fresh water is less than 40ppm, directly enter step D.
Further, described foaming adopts molten gas foaming or mechanical foaming, and molten gas foaming need be carried out molten gas foaming to waste Ca water before mixing, and mechanical foaming can stir foaming after mixing.
Compared with prior art, advantage of the present invention and positively effect are as follows:
1, the present invention proposes secondary calcification, take full advantage of the remaining calcium in waste Ca water, guaranteeing under the prerequisite of algin production yield, further improve the utility value of waste Ca water, reduce the consumption of follow-up calcium water simultaneously, saved cost, reduced the introducing of inorganic salt, also alleviate the processing load of electrodialysis process unit, reduced processing cost;
2, the scheme of utilizing of the dense water of electrodialysis has been proposed, more than in dense water after electrodialysis is concentrated, calcium ion concn can reach 1000ppm, the calcification flocculation agent of the present invention using dense water as floating dreg liquid, take full advantage of the calcium ion of enrichment in dense water, turn waste into wealth, reduce the use of calcium water raw material simultaneously, reduced production cost;
3, the present invention is on the basis of the waste Ca water circulation reusing technology take electrodialytic technique as core, two kinds of practicable comprehensive utilization techniques are developed, form a kind of novel brown alga chemical industry waste Ca water comprehensive utilization process, this technique has improved resource utilization, further reduce production cost, really realized the economic circulation utilization of waste Ca water;
4, the calcium ion that the present invention gathers waste Ca water is further utilized effectively it as flocculation agent by technique of the present invention.
Embodiment
The present invention proposes a kind of brown alga chemical industry waste Ca water Novel integrated and utilizes technique, this technique is the comprehensive utilization process on the brown alga chemical industry waste Ca water recycle basis being based upon take electrodialytic desalting technology as core, two kinds of novel waste Ca water comprehensive utilization techniques are proposed: the dense water conservancy technology of secondary calcification pretreatment technology and waste Ca water electrodialysis, realize the economy comprehensive utilization of brown alga chemical industry waste Ca water, its step comprises: by waste Ca water with rush rare clear glue solution and be mixed in proportion a calcification, flocculate floating; Separate subnatant and enter follow-up electrodialysis process, flocculation floating layer in upper strata adds the calcification of appropriate calcium water secondary; Above-mentioned subnatant after treatment is carried out to electrodialysis desalination decalcification, and strong cation-exchanging resin is further removed calcium ion remaining in electrodialysis fresh water; Above-mentioned product water after treatment and tap water are mixed in proportion and rush rare Digestive system as process water and carry out reuse afterwards, filter to produce waste Ca water after calcification and enter new round circulation; Above-mentioned dense water after treatment is mixed in proportion as calcification agent and brown alga chemical industry floating dreg liquid, makes its calcification flocculation.The present invention, on the basis of waste Ca water electrodialysis process technology, has further developed two kinds of waste Ca water comprehensive utilization new technologies, has improved the utility value of waste Ca water, has reduced waste Ca water processing cost, has really realized the economic reuse of waste Ca water.
Specifically describe technical scheme of the present invention in detail below in conjunction with embodiment.
Embodiment mono-: the present embodiment proposes a kind of brown alga chemical industry waste Ca water Novel integrated and utilizes technique, comprises the following steps:
(1), production plant gets waste Ca water 5L, wherein calcium content 550ppm, specific conductivity 11.4ms/cm2, production plant is got and is rushed rare clear glue solution 5L, specific conductivity 2.3 ms/cm
2.Add in waste Ca water under churned mechanically effect rushing rare clear glue solution, it is mixed, stratification;
(2), after stratification, the emulsion tube sucking-off of bottom clear liquid, 4.8L altogether, calcium content 270ppm, specific conductivity 5.8ms/cm
2, after filtration, enter follow-up electrodialysis cell processing; Top glue continues to add CaCl
2100g, is made into quality volume fraction and is 10% CaCl
2solution adds under churned mechanically effect, and it is mixed, and with obtaining cotton-shaped calcium alginate after filter-cloth filtering, adopts lime acetate method to detect to such an extent that sodium alginate is 7.5g, and through control experiment, the sodium alginate amount producing after direct calcification with alginic glue is identical;
(3), subnatant first adopts sand filtration to carry out pre-treatment, by visible Impurity removal, electrodialysis desalination decalcification, dense water and fresh water water inlet all adopt waste Ca water, deep or light volume ratio is 1:2, fresh water specific conductivity 2.0ms/cm after electrodialysis process
2, calcium content 45ppm, uses strong cation-exchanging resin further to process the calcium ion in electrodialysis fresh water, through above-mentioned waste water calcic 35ppm after treatment; Dense water conductivity 11.8 ms/cm after electrodialysis process
2, calcium content 730ppm;
(4) fresh water, after electrodialysis process and tap water are mixed in proportion and rush rare Digestive system as process water and carry out reuse afterwards, filter to produce waste Ca water after calcification and enter new round circulation;
(5), the dense water after electrodialysis process replaces part calcium water as calcification agent, with brown alga chemical industry floating dreg liquid by volume 3:1 mix, make its calcification flocculation, feed liquid layering after flocculation, subnatant enters environmental protection treatment workshop as waste water, and upper strata slag liquid adds 5gCaCl
2, be mixed with 10%CaCl
2solution evenly adds, further flocculation, and relatively flocculating effect is good with workshop product;
Embodiment bis-: the present embodiment proposes a kind of brown alga chemical industry waste Ca water Novel integrated and utilizes technique, comprises the following steps:
(1), production plant is got waste Ca water 60L, wherein calcium content 450ppm, specific conductivity 7.0ms/cm
2, production plant is got and is rushed rare clear glue solution 20L, specific conductivity 2.1 ms/cm
2.Waste Ca water is placed in to dissolving, and pressure 0.4MPa mixes stratification in line mixer with rushing rare clear glue solution according to volume ratio 3:1 after molten gas;
(2), after stratification, bottom clear liquid is discharged, 58L altogether, calcium content 380ppm, specific conductivity 5.5ms/cm
2, enter follow-up electrodialysis cell processing; Top glue continues to add CaCl
2420g, is made into quality volume fraction and is 10% CaCl
2solution adds under churned mechanically effect, and it is mixed, and with obtaining flocculence calcium alginate after filter-cloth filtering, adopts lime acetate method to detect to such an extent that sodium alginate is 32g, and through control experiment, the sodium alginate amount producing after direct calcification with alginic glue is identical;
(3), subnatant first adopts sand filtration to carry out pre-treatment, by visible Impurity removal, electrodialysis desalination decalcification, dense water and fresh water water inlet all adopt waste Ca water, deep or light volume ratio is 1:2, fresh water specific conductivity 2.0ms/cm after electrodialysis process
2, calcium content 60ppm, uses strong cation-exchanging resin further to process the calcium ion in electrodialysis fresh water, through above-mentioned waste water calcic 30ppm after treatment; Dense water conductivity 10.5 ms/cm after electrodialysis process
2, calcium content 1040ppm;
(4) fresh water, after electrodialysis process and tap water are mixed in proportion and rush rare Digestive system as process water and carry out reuse afterwards, filter to produce waste Ca water after calcification and enter new round circulation;
(5), the dense water after electrodialysis process replaces part calcium water as calcification agent, with brown alga chemical industry floating dreg liquid by volume 2:1 mix, make its calcification flocculation, feed liquid layering after flocculation, subnatant enters environmental protection treatment workshop as waste water, and upper strata slag liquid adds 60gCaCl
2, be mixed with 10%CaCl
2solution evenly adds, further flocculation, and relatively flocculating effect is good with workshop product.
The above; it is only preferred embodiment of the present invention; it is not the restriction of the present invention being made to other form; the equivalent embodiment that any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as equivalent variations is applied to other field the liquid of similar requirement, the control of gas; but every technical solution of the present invention content that do not depart from; any simple modification, equivalent variations and the remodeling above embodiment done according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (4)
1. a brown alga chemical industry waste Ca water comprehensive utilization process, is characterised in that: comprise the steps:
A, by waste Ca water with rush rare clear glue solution by volume 1:1-3:1 mix a calcification, flocculate floating;
B, separation subnatant enter follow-up electrodialysis process, and flocculation floating layer in upper strata adds appropriate calcium water to make wherein calcium contents higher than 400ppm, complete secondary calcification;
C, above-mentioned subnatant after treatment is carried out to electrodialysis desalination decalcification;
In D, C step fresh water after treatment be mixed in proportion into specific conductivity with tap water need be lower than 3ms/cm
2rare water that rushes rush rare Digestive system and carry out reuse, filter and produce waste Ca water after calcification and enter new round circulation; In C step dense water after treatment and brown alga chemical industry floating dreg liquid by volume 2:1-3:1 mix, make its calcification flocculation, after flocculation, clear liquid is drained as waste water, upper strata slag liquid further adds calcium water.
2. brown alga chemical industry waste Ca water comprehensive utilization process according to claim 1, is characterised in that: in described A step waste Ca water with rush rare clear glue solution mix before or mix after need to foam.
3. brown alga chemical industry waste Ca water comprehensive utilization process according to claim 2, is characterised in that: in described C step, after electrodialysis process, fresh water specific conductivity is controlled at 2-4ms/cm
2, in the time that being greater than 40ppm, the calcium ion concn in electrodialysis fresh water use strong cation-exchanging resin further to process the calcium ion in electrodialysis fresh water, if the calcium ion concn in electrodialysis fresh water is less than 40ppm, directly enter step D.
4. brown alga chemical industry waste Ca water comprehensive utilization process according to claim 3, is characterised in that: described foaming adopts molten gas foaming or mechanical foaming.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310042437.7A CN103058429B (en) | 2013-02-04 | 2013-02-04 | New process for comprehensively utilizing brown alga chemical calcium wastewater |
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| CN201310042437.7A CN103058429B (en) | 2013-02-04 | 2013-02-04 | New process for comprehensively utilizing brown alga chemical calcium wastewater |
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| CN103058429B true CN103058429B (en) | 2014-05-14 |
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| CN106145449B (en) * | 2016-08-17 | 2018-06-19 | 中国水产科学研究院黄海水产研究所 | A kind of seaweed chemical calcification waste water circulation reuse method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1359858A (en) * | 2000-12-19 | 2002-07-24 | 青岛海洋大学 | Process for purifying floated algin and waste Ca solution in algin factory |
| CN101870528A (en) * | 2010-05-27 | 2010-10-27 | 中国水产科学研究院黄海水产研究所 | Dibasic precipitation method for treating calcium-containing wastewater in phaeophyceae industry |
| CN102745841A (en) * | 2012-05-25 | 2012-10-24 | 中国水产科学研究院黄海水产研究所 | Novel brown algae chemical waste calcium water recycling process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2005121028A1 (en) * | 2004-06-10 | 2005-12-22 | Matsushita Electric Industrial Co., Ltd. | Apparatus for removing phosphorus |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1359858A (en) * | 2000-12-19 | 2002-07-24 | 青岛海洋大学 | Process for purifying floated algin and waste Ca solution in algin factory |
| CN101870528A (en) * | 2010-05-27 | 2010-10-27 | 中国水产科学研究院黄海水产研究所 | Dibasic precipitation method for treating calcium-containing wastewater in phaeophyceae industry |
| CN102745841A (en) * | 2012-05-25 | 2012-10-24 | 中国水产科学研究院黄海水产研究所 | Novel brown algae chemical waste calcium water recycling process |
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