CN103058429A - 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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- CN103058429A CN103058429A CN2013100424377A CN201310042437A CN103058429A CN 103058429 A CN103058429 A CN 103058429A CN 2013100424377 A CN2013100424377 A CN 2013100424377A CN 201310042437 A CN201310042437 A CN 201310042437A CN 103058429 A CN103058429 A CN 103058429A
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- water
- waste
- electrodialysis
- brown alga
- calcium
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 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
- 239000007788 liquid Substances 0.000 claims description 17
- 238000005189 flocculation Methods 0.000 claims description 16
- 230000016615 flocculation Effects 0.000 claims description 16
- 238000012545 processing Methods 0.000 claims description 15
- 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 9
- 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
- 238000005516 engineering process Methods 0.000 abstract description 19
- 238000004064 recycling Methods 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 description 7
- 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
- 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
Landscapes
- 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, can't realize the economic reuse of factory effluent, the power that makes enterprise lose reform is the immediate cause that the sector can't realize reducing the water consumption, therefore, the 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 the waste Ca water can reach 350-700ppm, and too high calcium amount can cause the fouling under the concentration polarization effect in the long playing process of electrodialysis, reduces electrodialytic desalting efficient, 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 the waste Ca water with the effective method of utilizing of calcium ion simultaneously, utilizes technique then to become the new problem that the present invention faces so 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 provides 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 have been proposed: the dense water conservancy technology of secondary calcification pretreatment technology and waste Ca water electrodialysis, further improved 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 kind of brown alga chemical industry waste Ca water comprehensive utilization process is characterised in that: comprise the steps:
A, with waste Ca water with rush rare clear glue solution and mix a calcification by 1:1-3:1 by volume, it is floating to flocculate;
B, separate subnatant and enter follow-up electrodialysis process, flocculation floating layer in upper strata adds an amount of calcium water makes wherein that calcium contents is higher than 400ppm, finishes the secondary calcification;
C, the subnatant after the above-mentioned processing is carried out the electrodialysis desalination decalcification;
Fresh water after processing in D, the C step is mixed in proportion into specific conductivity with tap water and 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 the calcification and enter new round circulation; Dense water after processing in the C step and brown alga chemical industry floating dreg liquid by volume 2:1-3:1 mix, make its calcification flocculation, and clear liquid is drained as waste water after the flocculation, and upper strata slag liquid further adds calcium water, makes flocculation complete, reaches simple helix and pushes requirement.
Further, in the described A step, waste Ca water with rush rare clear glue solution and need foam so that floating.
Further, in the described C step after the electrodialysis process fresh water specific conductivity be controlled at 2-4ms/cm
2, further process calcium ion in the electrodialysis fresh water when the calcium ion concn in the electrodialysis fresh water uses strong cation-exchanging resin during greater than 40ppm, if the calcium ion concn in the electrodialysis fresh water less than 40ppm, then directly enters step D.
Further, molten gas foaming or mechanical foaming are adopted in described foaming, and molten gas foaming needs before mixing waste Ca water to be carried out molten gas foaming, 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 the secondary calcification, take full advantage of the remaining calcium in the waste Ca water, under the prerequisite that guarantees algin production yield, further improved the utility value of waste Ca water, reduce simultaneously the consumption of follow-up calcium water, 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, calcium ion concn can reach more than the 1000ppm in the dense water after electrodialysis is concentrated, the present invention is with the calcification flocculation agent of dense water as floating dreg liquid, take full advantage of the calcium ion of enrichment in the dense water, turn waste into wealth, reduce simultaneously the use of calcium water raw material, 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 have been developed, formed 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 present invention further is utilized effectively it as flocculation agent by technique of the present invention the calcium ion that waste Ca water gathers.
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 that is based upon take the electrodialytic desalting technology as core, two kinds of novel waste Ca water comprehensive utilization techniques have been proposed: the dense water conservancy technology of secondary calcification pretreatment technology and waste Ca water electrodialysis, realized the economy comprehensive utilization of brown alga chemical industry waste Ca water, its step comprises: with waste Ca water with rush rare clear glue solution and be mixed in proportion a calcification, it is floating to flocculate; Separate subnatant and enter follow-up electrodialysis process, flocculation floating layer in upper strata adds the calcification of an amount of calcium water secondary; Subnatant after the above-mentioned processing is carried out the electrodialysis desalination decalcification, and strong cation-exchanging resin is further removed calcium ion remaining in the electrodialysis fresh water; Product water after the above-mentioned processing 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 the calcification and enter new round circulation; Dense water after the above-mentioned processing is mixed in proportion as calcification agent and brown alga chemical industry floating dreg liquid, makes its calcification flocculation.The present invention has further developed two kinds of waste Ca water comprehensive utilization new technologies on the basis of waste Ca water electrodialysis process technology, improved the utility value of waste Ca water, has reduced the waste Ca water processing cost, has really realized the economic reuse of waste Ca water.
Specifically be described in detail technical scheme of the present invention below in conjunction with embodiment.
Embodiment one: present embodiment proposes a kind of brown alga chemical industry waste Ca water Novel integrated and utilizes technique, may further comprise the steps:
(1), production plant gets waste Ca water 5L, calcium content 550ppm wherein, specific conductivity 11.4ms/cm2, production plant get and rush rare clear glue solution 5L, specific conductivity 2.3 ms/cm
2To rush rare clear glue solution and under churned mechanically effect, add in the waste Ca water, and it be mixed, standing demix;
(2), behind the standing demix, the emulsion tube sucking-off of bottom clear liquid, 4.8L altogether, calcium content 270ppm, specific conductivity 5.8ms/cm
2, enter follow-up electrodialysis cell after the filtration and process; The top glue continues to add CaCl
2100g is made into the quality volume fraction and is 10% CaCl
2Solution adds under churned mechanically effect, and it is mixed, and with getting cotton-shaped calcium alginate behind the filter-cloth filtering, adopts the lime acetate method to detect to such an extent that sodium alginate is 7.5g, and through control experiment, the sodium alginate amount that produces after direct calcification with alginic glue is identical;
(3), subnatant adopts first sand filtration to carry out pre-treatment, with visible Impurity removal, the electrodialysis desalination decalcification, waste Ca water is all adopted in dense water and fresh water water inlet, deep or light volume ratio is 1:2, fresh water specific conductivity 2.0ms/cm after the electrodialysis process
2, calcium content 45ppm, the use strong cation-exchanging resin is further processed the calcium ion in the electrodialysis fresh water, the waste water calcic 35ppm after above-mentioned processing; Dense water conductivity 11.8 ms/cm after the electrodialysis process
2, calcium content 730ppm;
(4), the fresh water after the electrodialysis process and tap water be mixed in proportion and rush rare Digestive system as process water and carry out reuse afterwards, filter to produce waste Ca water after the calcification and enter new round circulation;
(5), the dense water after the electrodialysis process replaces part calcium water as the calcification agent, with brown alga chemical industry floating dreg liquid by volume 3:1 mix, make its calcification flocculation, feed liquid layering after the flocculation, subnatant enters the 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 the workshop product;
Embodiment two: present embodiment proposes a kind of brown alga chemical industry waste Ca water Novel integrated and utilizes technique, may further comprise the steps:
(1), production plant gets waste Ca water 60L, calcium content 450ppm wherein, specific conductivity 7.0ms/cm
2, production plant is got and is rushed rare clear glue solution 20L, specific conductivity 2.1 ms/cm
2Waste Ca water is placed dissolving, pressure 0.4MPa, after molten gas is complete according to volume ratio 3:1 with rush rare clear glue solution and in line mixer, mix standing demix;
(2), behind the standing demix, the bottom clear liquid is discharged, 58L altogether, calcium content 380ppm, specific conductivity 5.5ms/cm
2, enter follow-up electrodialysis cell and process; The top glue continues to add CaCl
2420g is made into the quality volume fraction and is 10% CaCl
2Solution adds under churned mechanically effect, and it is mixed, and with getting the flocculence calcium alginate behind the filter-cloth filtering, adopts the lime acetate method to detect to such an extent that sodium alginate is 32g, and through control experiment, the sodium alginate amount that produces after direct calcification with alginic glue is identical;
(3), subnatant adopts first sand filtration to carry out pre-treatment, with visible Impurity removal, the electrodialysis desalination decalcification, waste Ca water is all adopted in dense water and fresh water water inlet, deep or light volume ratio is 1:2, fresh water specific conductivity 2.0ms/cm after the electrodialysis process
2, calcium content 60ppm, the use strong cation-exchanging resin is further processed the calcium ion in the electrodialysis fresh water, the waste water calcic 30ppm after above-mentioned processing; Dense water conductivity 10.5 ms/cm after the electrodialysis process
2, calcium content 1040ppm;
(4), the fresh water after the electrodialysis process and tap water be mixed in proportion and rush rare Digestive system as process water and carry out reuse afterwards, filter to produce waste Ca water after the calcification and enter new round circulation;
(5), the dense water after the electrodialysis process replaces part calcium water as the calcification agent, with brown alga chemical industry floating dreg liquid by volume 2:1 mix, make its calcification flocculation, feed liquid layering after the flocculation, subnatant enters the 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 the workshop product.
The above; it only is preferred embodiment of the present invention; be not to be the restriction of the present invention being made 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 break away from; to any simple modification, equivalent variations and remodeling that above embodiment does, still belong to the protection domain of technical solution of the present invention according to technical spirit 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, with waste Ca water with rush rare clear glue solution by volume 1:1-3:1 mix a calcification, it is floating to flocculate;
B, separate subnatant and enter follow-up electrodialysis process, flocculation floating layer in upper strata adds an amount of calcium water makes wherein that calcium contents is higher than 400ppm, finishes the secondary calcification;
C, the subnatant after the above-mentioned processing is carried out the electrodialysis desalination decalcification;
Fresh water after processing in D, the C step is mixed in proportion into specific conductivity with tap water and 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 the calcification and enter new round circulation; Dense water after processing in the C step and brown alga chemical industry floating dreg liquid by volume 2:1-3:1 mix, make its calcification flocculation, and the clear liquid that flocculates is afterwards drained as waste water, and 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 the described A step waste Ca water with rush rare clear glue solution and mix before or mix after need foam.
3. brown alga chemical industry waste Ca water comprehensive utilization process according to claim 2 is characterised in that: in the described C step after the electrodialysis process fresh water specific conductivity be controlled at 2-4ms/cm
2, further process calcium ion in the electrodialysis fresh water when the calcium ion concn in the electrodialysis fresh water uses strong cation-exchanging resin during greater than 40ppm, if the calcium ion concn in the electrodialysis fresh water less than 40ppm, then directly enters step D.
4. brown alga chemical industry waste Ca water comprehensive utilization process according to claim 3 is characterised in that: molten gas foaming or mechanical foaming are adopted in described 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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| 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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| Publication Number | Publication Date |
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| CN103058429A true CN103058429A (en) | 2013-04-24 |
| CN103058429B CN103058429B (en) | 2014-05-14 |
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| CN201310042437.7A Expired - Fee Related CN103058429B (en) | 2013-02-04 | 2013-02-04 | New process for comprehensively utilizing brown alga chemical calcium wastewater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106145449A (en) * | 2016-08-17 | 2016-11-23 | 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 (4)
| 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 |
| WO2005121028A1 (en) * | 2004-06-10 | 2005-12-22 | Matsushita Electric Industrial Co., Ltd. | Apparatus for removing phosphorus |
| 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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2013
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Patent Citations (4)
| 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 |
| WO2005121028A1 (en) * | 2004-06-10 | 2005-12-22 | Matsushita Electric Industrial Co., Ltd. | Apparatus for removing phosphorus |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106145449A (en) * | 2016-08-17 | 2016-11-23 | 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 |
| 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 |
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