CN1025114C - Method for purifying kelp immersion water - Google Patents

Method for purifying kelp immersion water Download PDF

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Publication number
CN1025114C
CN1025114C CN 90100214 CN90100214A CN1025114C CN 1025114 C CN1025114 C CN 1025114C CN 90100214 CN90100214 CN 90100214 CN 90100214 A CN90100214 A CN 90100214A CN 1025114 C CN1025114 C CN 1025114C
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China
Prior art keywords
kelp
soaking liquid
earth metal
soaking
purifying method
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Expired - Fee Related
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CN 90100214
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Chinese (zh)
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CN1045959A (en
Inventor
薛德明
马建红
裴振清
王学良
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Yellow Sea Qingdao Seaweed Industry Co
Hangzhou Desalination Of Sea Water And Water Treatmant Technique Development Cen
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Yellow Sea Qingdao Seaweed Industry Co
Hangzhou Desalination Of Sea Water And Water Treatmant Technique Development Cen
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Priority to CN 90100214 priority Critical patent/CN1025114C/en
Publication of CN1045959A publication Critical patent/CN1045959A/en
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Publication of CN1025114C publication Critical patent/CN1025114C/en
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Abstract

The present invention relates to a purification method of sea chemical industry kelp soak for removing turbidity, ' carbohydrate gum' and decolourization, which comprises flocculation, sterilization, mildew prevention, filtration and decolourization. Kelp soak water solution with high purity prepared by the method has the advantages that water quality is clean and transparent, a pollution index value is FI</=4, a cycle for unpicking and washing an electrodialyzer is prolonged by more than 5 times, a mannite yield is improved by 30%, more than 1/3 energy sources and productive expenses are saved, etc. The purification method is also suitable for the separation course of similar other chemical industry.

Description

Method for purifying kelp immersion water
The invention belongs to chemical separating, particularly marine chemical industry seaweed industry method of purifying kelp-soaking liquid.
In seaweed industry, from the kelp soaking aqueous solution, can extract iodine, N.F,USP MANNITOL, Chemicals such as muriate.Kelp soaking water constituent complexity still has organism and colloids such as a large amount of fucoidins, algin, laminarin, amino acid, pigment, tannin except containing the higher inorganic electrolyte of concentration, also have impurity such as sea-tangle disintegrating slag, silt, suspended substance.Extract in the N.F,USP MANNITOL technological process in the sea-tangle comprehensive utilization, this class impurity system is referred to as " carbohydrate gum ".A large amount of existence of " carbohydrate gum " are given and to be carried iodine and purification N.F,USP MANNITOL technology is brought very burden and difficulty, have a strong impact on product yield and production cost.For example, in the ion-exchange technique of extracting iodine, meeting contaminated ion exchange resin, plug ion exchange column.In traditional water recrystallization ion exchange process purification N.F,USP MANNITOL technology, must centrifugally repeatedly get rid of " carbohydrate gum ", could guarantee quality product, serious waste water.Adopting the ion product to change in the EDBM desalination process, " carbohydrate gum " can stop up electrodialyzer membrane stack and contaminated ion exchange membrane, makes the electrodialyzer can not long-time running and cause that current efficiency is low, and current consumption increases, the frequent cleaning labour intensity that disintegrates is big, consequences such as equipment damage is serious, therefore, people wished before carrying iodine or separating purification N.F,USP MANNITOL always, with someway kelp-soaking liquid being carried out purifying treatment, remove this class " carbohydrate gum ",, increase economic efficiency so that improve processing condition.For this reason, also carried out some explorations, but all do not have successfully.For example, once carried out earlier kelp soaking water being added NaOH and transferred about PH to 12, the sedimentation some hrs, the siphon clear liquid passes through sand filtration again, the filtering method of charcoal absorption hay tank (" sea-tangle industry data " 2 phases in 1977).The carrying out that also has kelp soaking water added alkali transfer PH=11~12, by foaming or add calcium chloride again and stir and precipitate, add the acid neutralization then, enter softening (" sea water desaltination " 1975 2 phases of Na-ion exchanger again; " a collection of selected materials of electrodialytic technique data " 1976).Produce in the N.F,USP MANNITOL current technology in sea-tangle comprehensive utilization industry, adopt aforesaid method that kelp soaking water is purified basically.But there is following drawback in these methods: 1) processing efficiency is low, needs 1~2 hour with alkali retrogradation clarification; 2) equipment is huge; 3) poor processing effect, its pollution index of kelp-soaking liquid FI value of handling through this method is very big, to such an extent as to can't measure out, serious contaminated ion exchange resin, therefore the plug ion exchange column, is removed because of the bad and residual impurity wherein of feed liquid purification in the existing way that can only lean on repeatedly centrifugal washing to get rid of " carbohydrate gum " in the N.F,USP MANNITOL technology of producing, therefore consume the great lot of water resources and the energy, influence yield and production cost.
Task of the present invention provides a kind of efficient height, effective kelp-soaking liquid turbidity removal, the purifying method of removing " carbohydrate gum " and decolouring.
The purifying method of kelp-soaking liquid provided by the invention comprises: a kind of kelp-soaking liquid that makes flocculates, and suspended substance, organism and colloid is separated from kelp-soaking liquid condense out, forms solid-liquid biphase method clearly; A kind of use has the porous high surface area, and the filtrate that can adsorb and hold back " carbohydrate gum " aggregate is the filter method of feature; A kind of sterilization presses down mould and a kind of decoloring method of decolorizing resin activating and regenerating.
Detailed description of the invention.
Method of the present invention is:
1, adds basic metal, the oxide compound of alkaline-earth metal or the inorganic anion flocculation agent of their oxyhydroxide, strong base-weak acid salt or soluble phosphate by the dosing injector in flocculation, the kelp-soaking liquid, make PH=13~14 of the sea-tangle aqueous solution.Circulation is stirred, the most coacervation of colloid in the kelp-soaking liquid, and float on the feed liquid with formation bulk scum silica frost such as suspended substance, residues, emit clear liquor.
2, secondary flocculation.Add oxide compound, alkaline earth metal hydroxides or the alkaline-earth metal soluble salt coagulant aids of alkaline-earth metal in the kelp soaking clear liquor successively and contain-COOH or-CONH 2The sodium polyacrylate of functional group, polyacrylamide organic polymer coargulator, the consumption of above-mentioned inorganic coagulant aids are 5~15g/L, and the consumption of above-mentioned organic polymer coargulator is 0.5~5g/L.The oxide compound of above-mentioned alkaline-earth metal, the oxyhydroxide of alkaline-earth metal or alkaline-earth metal soluble salt coagulant aids are calcium oxide, magnesium oxide, magnesium hydroxide, calcium hydroxide, calcium chloride, magnesium chloride, nitrocalcite, magnesium nitrate, magnesiumcarbonate, trimagnesium phosphate etc.Stirred 5~10 minutes.40~80 rev/mins of rotating speeds.Clarified 10~15 minutes." carbohydrate gum " of composition complexity forms the different aggregate of proportion, and adsorbs other impurity together by come-up and sedimentation respectively by in electrically and the bridging effect, take off surely in the kelp-soaking liquid after flocculating, and two partly separates up and down from kelp-soaking liquid.
3, sterilization presses down mould.Press down mould promotor through the sterilization that adds as isothiazolones, formaldehyde, hydrogen peroxide, hypochlorous acid or hypochlorite in the kelp soaking clear liquor after the flocculation, consumption is that 5~10mg/L stirs.Static 5 minutes, so that kill bacterium, the mould that is present in the kelp soaking feed liquid or suppress it and multiply breeding.
4, filter.The kelp-soaking liquid that sterilization presses down after mould filters by filter method provided by the present invention, makes solid-liquid separation.Here said filtration is meant that by carclazyte, wilkinite, diatomite or the perlite of Powdered or granular filtrate as having the porous high surface area making filtrate form thickness on the porous supporter is the filtering layer of 10~50mm, control filtering velocity V≤2500L/m 2H.Can adopt mechanism filter-pressing or vacuum filtration.Through the filtering kelp-soaking liquid of aforesaid method, its pollution index value FI≤7.
5, decolouring.Kelp-soaking liquid after the filtration decolours by ion exchange column.Here the ion exchange resin in the said ion exchange column can be regenerated and be used repeatedly, and does not adsorb only adsorpting pigment of N.F,USP MANNITOL, as the D-280 decolorizing resin.Pollution index value FI≤4 of the kelp soaking feed liquid after the decolouring.
Use method of purifying kelp-soaking liquid provided by the present invention, can be prepared into the kelp soaking aqueous solution of high purification efficiently, economically.Compare with existing purification techniques, clean method provided by the invention has following outstanding advantage:
Though 1, existing method of purifying kelp-soaking liquid purifies the kelp soaking feed liquid, the pollution index value that purifies back kelp soaking feed liquid is very big, so that can't record.If carry out ion-exchange or electrodialysis process with this feed liquid, meeting severe contamination ion exchange resin and plug ion exchange membrane cause equipment normally not move.Adopt pollution index value FI≤4 of the kelp soaking feed liquid of the inventive method purification, water quality is transparent, bright and clean colourless, the phenomenon that meets ion exchange resin column, ion exchange column, electrodialysis membrane stack fully, the safe long-term reliably operation continuously of assurance equipment, make electrodialyzer unpick and wash cycle stretch-out more than 5 times, prolong at least 1 times of work-ing life of ion exchange resin, ion-exchange membrane or semi-permeable membranes simultaneously, and improve the desalination rate more than 50%.
2, in the subsequent technique of N.F,USP MANNITOL products production, thereby because the operation that the high purification of kelp soaking feed liquid has been got rid of repeatedly centrifugal washing in the existing production technique, got rid of " carbohydrate gum ", avoided refining consume, make the N.F,USP MANNITOL yield improve 30%, save energy consumption and productive expense simultaneously more than 1/3rd.
3, facility compact, production efficiency height.
4, reduce labor intensity, improved production environment.
The purifying method of the kelp soaking aqueous solution provided by the present invention also is applicable to similarly other chemical separation process.
Embodiment 1:
Get kelp soaking aqueous solution 500mL, drip NaoH solution to kelp soaking solution ph=14.Drip Na3PO4 solution then, make its P2O5 concentration 〉=200mg/L, drip polyacrylamide solution again, concentration 1mg/L.Stirred 50 rev/mins of rotating speeds 5 minutes.Static 30 minutes.Kelp-soaking liquid top is floating the bulk scum silica frost, and the retrogradation of feed liquid bottom has the cotton-shaped aggregate of bulk, and middle feed liquid is transparent.
Kelp-soaking liquid adding Nacio sterilization after the flocculation presses down mould, consumption 5mg/L, 5 minutes time.
Choose the non-woven fabrics or the filter cloth of suitable dimension and put into B, will be put on the filter cloth after powder shape perlite and the diatomite balanced mix, form the thin layer of thickness 20mm.Filter control filtering velocity 3~4mL/min-cm with the kelp soaking feed liquid that the suction filtration mode will be flocculated after the sterilization 2Feed liquid is filtered after stain index value FI=6.5, then, adds hydrochloric acid in the kelp soaking filtrate and is neutralized to PH=6~7, with the decolouring of D-280 decolorizing resin.The kelp soaking feed liquid cleaning of decolouring back is colourless, pollution index value FI=4.
Embodiment 2:
Get kelp soaking aqueous solution 500mL, drip Ca(OH) 2 solution are to kelp soaking solution ph=14, feed Co 2Gas stirring was reacted 10 minutes, added sodium polyacrylate, and concentration 2mg/L stirred 50 rev/mins of rotating speeds 5 minutes.The very fast layering of kelp soaking feed liquid, the bulk suspensoid is formed at feed liquid top, feed liquid bottom deposition bulk flocculation aggressiveness, middle feed liquid is transparent.
Kelp soaking feed liquid after the flocculation adds isothiazolones, and consumption is 1 of a kelp soaking amount, 5 minutes time.
Choose the non-woven fabrics or the filter cloth of suitable dimension and put into B, will be placed on the filter cloth after powder perlite and the diatomite balanced mix, form the filtering layer of thickness 20mm.Filter control filtering velocity to 3~4mL/min-cm with the suction filtration mode kelp-soaking liquid that sterilization presses down after mould that will flocculate 2Pollution index value FI=6.5 after feed liquid is filtered.
Then, add hydrochloric acid in the kelp soaking filtrate and be neutralized to PH=6~7 again with the decolouring of D-280 decolorizing resin.The kelp soaking feed liquid cleaning of decolouring back is colourless, pollution index value FI=4.

Claims (8)

1, a kind of purifying method of kelp-soaking liquid comprises flocculation, filters and decolouring, it is characterized in that:
(a), add oxide compound or its oxyhydroxide, strong base-weak acid salt or the soluble phosphate coagulant aids of basic metal, alkaline-earth metal in the kelp-soaking liquid, PH=13~14 of transferring kelp-soaking liquid, circulation is stirred;
(b), in the clear liquor that obtains by step (a) flocculation, add alkaline earth metal oxide, alkaline earth metal hydroxides or alkaline-earth metal soluble salt coagulant aids successively and contain-COOH or-CONH 2The sodium polyacrylate of functional group, polyacrylamide organic polymer coargulator stir and clarification;
(c), add isothiazolones, formaldehyde, hydrogen peroxide, hypochlorous acid or hypochlorite sterilization in the kelp-soaking liquid after the flocculation of footpath (a) and (b) secondary and press down mould promotor;
(d), sterilization presses down kelp-soaking liquid after mould with being equipped with Powdered and having the filtrate of porous high surface area, filter as carclazyte, wilkinite, diatomite, perlitic strainer;
(e), with the decolorizing resin post filtrate is decoloured.
2, the purifying method of kelp-soaking liquid according to claim 1 is characterized in that importing in the step (a) gas stirring.
3, the purifying method of kelp-soaking liquid according to claim 1, the consumption that it is characterized in that the alkaline earth metal oxide described in the step (b), alkaline earth metal hydroxides or alkaline-earth metal soluble salt coagulant aids is 5~15g/L, and the consumption of described organic polymer coargulator is 0.5~5g/L.
4, the purifying method of kelp-soaking liquid according to claim 1 is characterized in that the middle churning time of step (b) 5~10 minutes, 40~80 rev/mins of rotating speeds.
5, the purifying method of kelp-soaking liquid according to claim 1 is characterized in that the consumption that the sterilization described in the step (c) presses down mould promotor is 5~10mg/L.
6, the purifying method of kelp-soaking liquid according to claim 1 is characterized in that above-mentioned filtrate is granular.
7, the purifying method of kelp-soaking liquid according to claim 1, the thickness that it is characterized in that above-mentioned filtrate is 10~20mm.
8, the purifying method of kelp-soaking liquid according to claim 1 is characterized in that filtering velocity≤2500L/m in the step (d) 2.h.
CN 90100214 1990-01-10 1990-01-10 Method for purifying kelp immersion water Expired - Fee Related CN1025114C (en)

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Application Number Priority Date Filing Date Title
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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1045899C (en) * 1994-07-01 1999-10-27 国家海洋局杭州水处理技术开发中心 Improved method of purifying kelp-soaking liquid
CN100491314C (en) * 2006-04-18 2009-05-27 中国科学院海洋研究所 Method of purifying immersed liquid in extraction process of algin, iodine and mannitol
CN103072947B (en) * 2012-12-20 2014-12-17 青岛明月海藻集团有限公司 Method for extracting iodine from kelp
CN109832576A (en) * 2017-11-24 2019-06-04 道霖有限公司 Promote the wet treatment method of kelp freshness retentivity

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