CN105481136B - The integrated conduct method of waste Ca water and spent acid water circulation use in a kind of algin production - Google Patents
The integrated conduct method of waste Ca water and spent acid water circulation use in a kind of algin production Download PDFInfo
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- CN105481136B CN105481136B CN201510840391.2A CN201510840391A CN105481136B CN 105481136 B CN105481136 B CN 105481136B CN 201510840391 A CN201510840391 A CN 201510840391A CN 105481136 B CN105481136 B CN 105481136B
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Abstract
The invention belongs to the technical field of seaweed chemical production, is specifically related to the integrated conduct method of waste Ca water and spent acid water circulation use in a kind of algin production.This kind of integrated conduct method, comprises the following steps：（1）Suspension in waste Ca water is removed；（2）Decalcifying agent is added in waste Ca water and carries out decalcification processing, is then settled；（3）Recycle-water is directly used as after the removal of impurities of gained supernatant is handled；Calcium carbonate is added into waste acid water, reaction obtains calcium chloride solution, and hydrochloric acid is then added in calcium chloride solution causes calcium chloride mass concentration to be at least up to 12%；（4）After calcium chloride solution is filtered, glue calcification process in algin production is directly used in.The technique, which overcomes, settles the shortcomings of difficult, cost is high, generation a large amount of calcium salt discarded objects in wastewater treatment, realize the comprehensive cyclic utilization of algin processing waste water.
Description
Technical field
The invention belongs to the technical field of seaweed chemical production, is specifically related to waste Ca water in a kind of algin production and gives up
The integrated conduct method that sour water recycles.
Background technology
In seaweed chemical industry, with the algin of brown alga production（Also known as sodium alginate, sodium alginate）, its production technology
Existing more than 40 years history, has been widely used for the multiple fields such as food, weaving, printing and dyeing, chemical industry, medicine, agricultural, demand at present
Measure increasing.The production of present China algin, it is largely to use calcification, acidization, often produces one ton of product water consumption and exist
600-800 tons, except produce more than 100 tons immersion edible seaweed high-concentration waste water, more than 20 ton pH value outside 1.5 or so waste acid water, its
Remaining is waste Ca water of the hardness in German degree 50-90, and these waste water directly discharge after COD drops in sewage disposal at present, cause
Can a large amount of wastes of water resource, especially current freshwater resources be increasingly reduced, reduce water consume and accomplish that cleanly production turns into brown
The key of phycocolloid industry future survival and development.
Caused waste Ca water and waste acid water in algin production, calcium ion content is high and contains a small amount of low molecule algin,
Waste acid water pH value 1.5 or so, it is relatively difficult into environment friendly system processing, but it is not other in addition to containing above-mentioned substance in waste water
Impurity.
It is existing at present to there is chemical precipitation method, hyperfiltration, electroosmose process, resin ion to hand over for waste Ca water handling process
Method etc. is changed, wherein " wastewater recycling method in a kind of seaweed chemical production " open one kind uses chemical precipitation method by waste water
Again by the method for the further reuse of technique waste water after middle calcium ion removal；" the double alkali of calcic waste water sink in processing brown alga chemical industry
Shallow lake method " is disclosed the method for the further reuse of technique waste water after a kind of double alkaline precipitations of use remove calcium ion in waste water；It is " brown
The open one kind of the process of processing and the circulating and recovering zero-emission of phycocolloid production waste water " is given up using reverse osmosis technology handling process
Water and then the further method of reuse；The patent of invention of " a kind of New process for comprehensively utilizing brown alga chemical calcium wastewater " discloses one
Kind electrodialysis and resin cation handling process method.
Following defect be present in existing waste Ca water processing method：（1）The recycle-water for being used as flocculant process with aluminum oxide can not
Produced in foodstuff glue；（2）The pure chemistry precipitation method, 4-5 hours or overnight need to be stood during processing, time oversize unsuitable industrialization
Commercial cultivation；（3）Counter-infiltration, electrodialysis, resin method processing cost are too high, add product cost, it is competing to reduce enterprise product
Strive power.
The content of the invention
It is an object of the invention to not thorough, the increasing for caused waste Ca water and spent acid water process in the production of current algin
The problem of cannot effectively being utilized after the stress problems of big follow-up environmental protection treatment, and processing and provide in a kind of algin production
The integrated conduct method of waste Ca water and spent acid water circulation use.Integrated conduct method of the present invention is in treatment for reuse waste Ca water
And while waste acid water, can reach the output object comprehensive utilization in processing procedure, technique overcome settled in wastewater treatment it is difficult, into
This height, the shortcomings of a large amount of calcium salt discarded objects is produced, realize the comprehensive cyclic utilization of algin processing waste water.
The technical scheme is that：The integrated treatment side of waste Ca water and spent acid water circulation use in a kind of algin production
Method, comprise the following steps：（1）Suspension containing low molecule calcium alginate in waste Ca water is removed；（2）By step（1）
Decalcifying agent is added in waste Ca water after processing and carries out decalcification processing, is then settled, obtains supernatant and sediment calcium carbonate；
（3）Gained supernatant is first passed through to the recycle-water for being directly used as that latting drown process is digested in algin production after removal of impurities is handled；By institute
Obtain sediment calcium carbonate to add into waste acid water after collection, reaction obtains calcium chloride solution, then molten in the calcium chloride of gained
Hydrochloric acid is added in liquid causes calcium chloride mass concentration to be at least up to 12%；（4）Gained mass concentration is at least to 12% calcium chloride
After solution is filtered, glue calcification process in algin production is directly used in.
The step（1）The suspension containing low molecule calcium alginate in waste Ca water is gone using air floatation machine or centrifuge
Remove.
The step（2）Middle decalcifying agent is sodium carbonate.
The step（2）The addition of middle decalcifying agent is 1~1.2 times of calcium ion mole in waste Ca water.
The step（2）Middle sedimentation uses standing sedimentation 0.5~1 hour.
The step（2）Middle sedimentation carries out continuous sedimentation using inclined plate sedimentation pond.
The step（3）Middle supernatant carries out removal of impurities processing by 300 mesh net filtrations or centrifuge.
The step（3）The salt content of middle recycle-water is less than or equal to 3%.
The step（4）The calcium chloride solution that middle mass concentration is at least 12% is filtered by 300 mesh nets.
Beneficial effects of the present invention are：The synthesis of waste Ca water and spent acid water circulation use in algin production of the present invention
Waste Ca water Treatment for Reuse removes the suspensions such as a small amount of calcium alginate in waste Ca water using Bubble-floating Method or centrifugal process in processing method,
The factor for calcium carbonate sinking speed of eliminating the effects of the act, using chemical reagent sedimentation, by 1-1.2 times of mol ratio of calcium ion to waste Ca water
Middle addition decalcifying agent, waste Ca water hardness is handled to German degree below 5, supernatant is filtered or centrifugation direct reuse is in algin
Production digestion latting drown process.Waste Ca water reprocessing is no more than 3% using to salt content；The Treatment for Reuse of waste acid water, above-mentioned processing
Sediment afterwards, reacts with waste acid water to obtain calcium chloride solution after collection, and concentrated hydrochloric acid is added in above-mentioned processing makes gained chlorine
Change calcium concentration and reach more than 12%, the calcification process of algin production is directly used in after filtering.Treatment for reuse waste Ca water of the present invention and
While waste acid water, the output object comprehensive utilization in processing procedure is can reach, technique, which overcomes, settles difficult, cost in wastewater treatment
Height, the shortcomings of a large amount of calcium salt discarded objects is produced, realize the comprehensive cyclic utilization of algin processing waste water.
The integrated conduct method of waste Ca water and spent acid water circulation use causes in waste Ca water not only in the algin production
Do not contain calcium ion while be free of low molecule algin, waste acid water has been fully processed, and environment friendly system processing is tired in the absence of entering
The problem of difficult.The integrated conduct method makes the Ca in algin production2+And H+Reach complete recycling, greatly reduce brown alga
Glue workshop cost.The recycle-water salt content after as long as lot of experiments finds processing, completely can be by after its decalcification below 3%
Reuse does not influence into technique on production technology and product quality, can greatly reduce the industrial water amount of algin；And locate
Calcium carbonate caused by waste Ca water and waste acid water reaction generation calcium chloride are managed, calcification process can be back to use, not only make use of processing
Calcium carbonate solid waste caused by water, the problem of also solving spent acid water process difficulty, add recycling for various raw material
Rate, the comprehensive utilization of waste is realized, reduce production cost while having saved with water, reduce environmental pollution.
In summary, recycle-water is caused to can be used for foodstuff glue production using processing method of the present invention；Processing time
It is short, it is adapted to industrialized production to utilize；Processing cost is low, and then reduces the production cost of product.
Embodiment
Below by embodiment, the present invention will be described in detail.
Embodiment 1
The integrated conduct method of waste Ca water and spent acid water circulation use in a kind of algin production, comprises the following steps：（1）
Removed, obtained clear by the suspension containing low molecule calcium alginate is derived from the 10L waste Ca waters in algin workshop using centrifuge
Clear liquid body；Wherein the German degree of waste Ca water is 55, salt content 0.32%；（2）By step（1）In waste Ca water after processing
The sodium carbonate 10.41g for adding 1 times of calcium ion mole carries out decalcification processing.Then settled, it is small using standing sedimentation 1
When, obtain supernatant and sediment calcium carbonate；（3）Gained supernatant is first passed through into 300 mesh net filtrations or centrifuge is carried out
Removal of impurities is handled；It is directly used as digesting the recycle-water of latting drown process, wherein recycle-water after removal of impurities is handled in algin production
Salt content is 0.33%, and German degree is 4.6.Gained sediment calcium carbonate is added to the 40ml waste acid waters that pH is 1.6 after collection
In, 30% hydrochloric acid 30ml is added, calcium carbonate is stirred well to and reacts completely, it is 12.5% calcium chloride solution that reaction, which obtains concentration,
Then hydrochloric acid is added in the calcium chloride solution of gained causes calcium chloride mass concentration to be at least up to 12%；（4）Gained quality is dense
After the calcium chloride solution spent for 12.5% is filtered by 300 mesh nets, glue calcification process in algin production is directly used in.
Embodiment 2
The integrated conduct method of waste Ca water and spent acid water circulation use in a kind of algin production, comprises the following steps：（1）
Removed, obtained by the suspension containing low molecule calcium alginate is derived from the 500L waste Ca waters in algin workshop using air soluble method air supporting
To supernatant liquid；Wherein the German degree of waste Ca water is 68, salt content 0.45%；（2）By step（1）Useless calcium after processing
The sodium carbonate 708g that 1.1 times of calcium ion moles are added in water carries out decalcification processing.Then settled, using standing sedimentation
0.5 hour, obtain supernatant and sediment calcium carbonate；（3）Gained supernatant is first passed through into disk centrifugal separator centrifugation to be cleaned
Processing, wherein rotating speed are 4000 revs/min；It is directly used as digesting returning for latting drown process in algin production after removal of impurities is handled
With water, the wherein salt content of recycle-water is 0.43%, and German degree is 2.8.Gained sediment calcium carbonate is added to pH after collection
In 1.5 4700ml waste acid waters, to add 30% hydrochloric acid 800ml, being stirred well to calcium carbonate and react completely, reaction obtains dense
Spend for 12.2% calcium chloride solution, hydrochloric acid is then added in the calcium chloride solution of gained causes calcium chloride mass concentration to be at least up to
To 12%；（4）After the calcium chloride solution that gained mass concentration is 12.2% is filtered by 300 mesh nets, brown alga is directly used in
Glue calcification process in glue production.
Embodiment 3
The integrated conduct method of waste Ca water and spent acid water circulation use in a kind of algin production, comprises the following steps：（1）
Removed, obtained by the suspension containing low molecule calcium alginate is derived from the 500L waste Ca waters in algin workshop using air soluble method air supporting
To supernatant liquid；Wherein the German degree of waste Ca water is 85, salt content 0.82%；（2）By step（1）Useless calcium after processing
The sodium carbonate 965g that 1.2 times of calcium ion moles are added in water carries out decalcification processing.Then settled, using standing sedimentation
0.5 hour, obtain supernatant and sediment calcium carbonate；（3）Gained supernatant is first passed through into disk centrifugal separator centrifugation to be cleaned
Processing, wherein rotating speed are 4000 revs/min；It is directly used as digesting returning for latting drown process in algin production after removal of impurities is handled
With water, the wherein salt content of recycle-water is 0.80%, and German degree is 1.7.Gained sediment calcium carbonate is added to pH after collection
In 1.4 6400ml waste acid waters, to add 31% hydrochloric acid 1100ml, being stirred well to calcium carbonate and react completely, reaction obtains dense
Spend for 12.1% calcium chloride solution, hydrochloric acid is then added in the calcium chloride solution of gained causes calcium chloride mass concentration to be at least up to
To 12%；（4）After the calcium chloride solution that gained mass concentration is 12.2% is filtered by 300 mesh nets, brown alga is directly used in
Glue calcification process in glue production.
Claims (8)
1. the integrated conduct method of waste Ca water and spent acid water circulation use in a kind of algin production, comprises the following steps：
（1）Suspension containing low molecule calcium alginate in waste Ca water is removed；
（2）By step（1）Decalcifying agent is added in waste Ca water after processing and carries out decalcification processing, is then settled, obtained
Supernatant and sediment calcium carbonate；
（3）Gained supernatant is first passed through to the recycle-water for being directly used as that latting drown process is digested in algin production after removal of impurities is handled；
Gained sediment calcium carbonate is added into waste acid water after collection, reaction obtains calcium chloride solution, then in the chlorination of gained
Hydrochloric acid is added in calcium solution causes calcium chloride mass concentration to be at least up to 12%；Wherein the salt content of recycle-water is less than or equal to 3%；
（4）By gained mass concentration be at least 12% calcium chloride solution filtered after, be directly used in algin production in glue
Calcification process.
2. the integrated conduct method of waste Ca water and spent acid water circulation use in algin production according to claim 1, it is special
Sign is, the step（1）The suspension containing low molecule calcium alginate in waste Ca water is removed using air floatation machine or centrifuge.
3. the integrated conduct method of waste Ca water and spent acid water circulation use in algin production according to claim 1, it is special
Sign is, the step（2）Middle decalcifying agent is sodium carbonate.
4. the integrated conduct method of waste Ca water and spent acid water circulation use in algin production according to claim 1, it is special
Sign is, the step（2）The addition of middle decalcifying agent is 1~1.2 times of calcium ion mole in waste Ca water.
5. the integrated conduct method of waste Ca water and spent acid water circulation use in algin production according to claim 1, it is special
Sign is, the step（2）Middle sedimentation uses standing sedimentation 0.5~1 hour.
6. the integrated conduct method of waste Ca water and spent acid water circulation use in algin production according to claim 1, it is special
Sign is, the step（2）Middle sedimentation carries out continuous sedimentation using inclined plate sedimentation pond.
7. the integrated conduct method of waste Ca water and spent acid water circulation use in algin production according to claim 1, it is special
Sign is, the step（3）Middle supernatant carries out removal of impurities processing by 300 mesh net filtrations or centrifuge.
8. the integrated conduct method of waste Ca water and spent acid water circulation use in algin production according to claim 1, it is special
Sign is, the step（4）The calcium chloride solution that middle mass concentration is at least 12% is filtered by 300 mesh nets.
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| CN109368897A (en) * | 2018-10-31 | 2019-02-22 | 华北电力大学（保定） | A kind of milk of lime process recycles the system and application method of calcium ions and magnesium ions in desulfurization wastewater |
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| CN101870528B (en) * | 2010-05-27 | 2011-11-02 | 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 |
| CN103665184B (en) * | 2013-12-23 | 2015-08-19 | 山东洁晶集团股份有限公司 | A kind of method reducing hydrochloric acid calcium chloride consumption in sodium alginate production |
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Denomination of invention: A Comprehensive Treatment Method for Recycling of Waste Calcium Water and Waste Acid Water in the Production of Alginate Effective date of registration: 20230428 Granted publication date: 20171110 Pledgee: Rizhao Bank Co.,Ltd. Donggang sub branch Pledgor: SHANDONG JIEJING Group Corp. Registration number: Y2023980039602 |