CN106565050A - Folic acid wastewater treatment process - Google Patents

Folic acid wastewater treatment process Download PDF

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Publication number
CN106565050A
CN106565050A CN201510643455.XA CN201510643455A CN106565050A CN 106565050 A CN106565050 A CN 106565050A CN 201510643455 A CN201510643455 A CN 201510643455A CN 106565050 A CN106565050 A CN 106565050A
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CN
China
Prior art keywords
acid
waste water
folic acid
filter
ammonia nitrogen
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Pending
Application number
CN201510643455.XA
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Chinese (zh)
Inventor
熊澍维
鄢舒意
张龑
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HUANGGANG HUAYANG PHARMACEUTICAL CO Ltd
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HUANGGANG HUAYANG PHARMACEUTICAL CO Ltd
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Priority to CN201510643455.XA priority Critical patent/CN106565050A/en
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Abstract

The invention belongs to an industrial wastewater treatment process, and specifically relates to a folic acid wastewater treatment process. The folic acid wastewater treatment process comprises the following steps: precise filtration of folic acid wastewater: the precise filtration is precoating filtration or direct filtration; acid separation, purification and recycling: a step of adsorbing hydrochloric acid and sulfuric acid in precisely-filtered wastewater by adopting macroporous resin, after adsorption saturation of the macroporous resin, carrying out backwashing with purified water, and carrying out desorption so as to obtain a mixed acid solution of hydrochloric acid and sulfuric acid, wherein the residual is ammonia-nitrogen wastewater; ammonia-nitrogen separation, purification and recycling: a step of subjecting the ammonia-nitrogen wastewater to deamination through a gas membrane method at normal temperature so as to remove ammonia-nitrogen substances from the ammonia-nitrogen wastewater; and neutralization: a step of mixing the above-mentioned obtained mixed acid of hydrochloric acid and sulfuric acid with the ammonia-nitrogen substances, adjusting the amount of the mixed acid and the ammonia-nitrogen substances until the pH of a mixed solution to be neutral, and subjecting the neutralized solution to filtering with a filter membrane so as to obtain an ammonium chloride/ammonium sulfate mixed nitrogen fertilizer and a residual solution. Thus, the folic acid wastewater treatment process provided by the invention realizes wastewater treatment up-to-standard discharge and waste recycling, reduces cost and increases benefits for enterprises, and facilitates energy conservation and emission reduction at the same time.

Description

A kind of folic acid waste water treatment process
Technical field
The invention belongs to technique for treating industrial wastewater, and in particular to a kind of folic acid waste water treatment process.
Background technology
Folic acid(folic acid)Also FA is, is a kind of water soluble vitamin, be necessary material of human body when using sugar and amino acid, be body cell growth and the necessary material of breeding.Folic acid is widely used in the fields such as feed, food and medicine.In terms of feed, adding folic acid can improve the immunity of animal, promote the growth of animal.In terms of medicine food, folic acid with health care, anti-anemia action, promotes the too high effect of children's intelligence development and anti-uric acid concentration as nutrient.Thus, folic acid suffers from being widely applied in world wide.
From in terms of world wide, folic acid is produced all in China, and domestic folic acid industry waste water there is no the handling process technology of economy, and a large amount of highly acids can be produced during the manufacturing of folic acid(The acid content of 1-10%), high ammonia nitrogen(1500mg/L), it is high in salt(1-3% is mainly sodium chloride, sodium sulphate), high COD(1500mg/L)Etc. the sewage for being difficult to process qualified discharge.These waste water treatmentntrol difficults, relatively costly, the enterprise for much preparing folic acid is arranged steathily, and the environment that thereby results in, ecological and social concern are projected.At present the country also has for folic acid waste water treatment process technology, and such as ammonia-nitrogen desorption, energy consumption is high with operating cost, solves the problems, such as ammonia nitrogen in waste water, but causes air pollution;Problem high in salt, is diluted using a large amount of water, and cost of sewage disposal is on the one hand significantly increased, and another aspect factory water amount of blowdown increases, and is not reduced the salinity total amount to the discharge of earth's surface natural water;Using UF membrane sodium chloride desalination, film concentrated water needs for biochemical treatment again after a large amount of running water dilutions;For highly acid, lime or NaOH are neutralized, and substantial increase solid waste is also significantly increased with salt content in waste water, operation energy consumption with expense;Also technical staff processes folic acid waste water using " neutralization-coagulating sedimentation pretreatment-hydrolysis acidification and PACT techniques ", or the process route combined using " chemistry neutralization+and oxygen/aerobic PACT biochemical treatments " carries out administering folic acid waste water, but it is neutralized acid using additional neutralization reagent, then desalination and ammonia nitrogen substances are carried out, its high cost and effect is unsatisfactory.
The content of the invention
It is an object of the invention to:The a large amount of waste water produced in folic acid production process are solved the problems, such as, the treatment of wastes with processes of wastes against one another, refuse reclamation reduces the operation energy consumption and correlative charges in folic acid production process.
The present invention is to realize that the technical scheme that above-mentioned technical purpose is taken is:A kind of folic acid waste water treatment process, comprises the steps:
(1)Secondary filter is carried out to folic acid waste water, the secondary filter is precoat filtration or directly filters;The precoat filtration is taken and is filtered in screen surface precoated diatomite filter aid, expanded perlite or powdered ion-exchange resin;The direct filtration is filtered using Porous cartridge filter or filter membrane;
(2)Acid isolates and purifies recovery, using hydrochloric acid and sulfuric acid in waste water after macroporous resin adsorption secondary filter, is backwashed with pure water after macroporous resin adsorption saturation, and desorption obtains hydrochloric acid and sulfuric acid mixed acid solution, remaining for ammonia nitrogen waste water;
(3)Ammonia nitrogen isolates and purifies recovery, to ammonia nitrogen waste water using gaseous state embrane method deamination or dewatering microporous film is carried out under normal temperature, deviates from the ammonia nitrogen substances in ammonia nitrogen waste water;
(4)Neutralization, blend step(2)The hydrochloric acid sulfuric acid mixed acid and step of gained(3)The ammonia nitrogen substances of gained are mixed, adjust the amount of the two and cause mixed solution in neutrality, carry out membrane filtration to solution after neutralization again and obtain oronain/sulphur ammonium mixing nitrogenous fertilizer and residual solution, it is that 7-8, COD are less than 300mg/L, solution of the salt concentration less than 200mg/L less than 50mg, PH that the residual solution is ammonia nitrogen concentration;
(5)Carry out activated sludge process, Halophiles or Aerobic-anaerobic group technology to residual solution to process.
Used as the preferred technical scheme of the present invention, the handling process to folic acid waste water is carried out at normal temperatures.
Used as the preferred technical scheme of the present invention, the Porous cartridge filter is porous web cartridge filter or porous plate cartridge filter.
As the preferred technical scheme of the present invention, step(4)The filter membrane is milipore filter, miillpore filter, NF membrane, microfiltration membranes, hollow fiber ultrafiltration membrane or Sai Er filter membranes.
Used as the preferred technical scheme of the present invention, the activated sludge process adopts anaerobic grain activated sludge.
Beneficial effects of the present invention:
1. the core of the folic acid waste water treatment process of the present invention is for the characteristics of folic acid waste water highly acid, high ammonia nitrogen, difficult biochemical treatment high in salt and direct, taking first separating acid, separating the technology for isolating and purifying of ammonia nitrogen again;Isolated hydrochloric acid sulfuric acid mixed acid can mix nitrogenous fertilizer with the ammonia nitrogen substances reaction generation that ammonia nitrogen obtains is separated as agricultural oronain/sulphur ammonium during isolating and purifying;And the chlorion after being isolated and purified contained by remaining sewage, sulfate ion, ammonia nitrogen and salt decline to a great extent, qualified discharge can be processed by conventional, simple biochemical process;
2. carry out at normal temperatures in whole sewage treatment process, do not increase the extra cost of sewage disposal, and obtain the product with certain export value, using only 4.5 yuan of this folic acid waste water treatment process folic acid waste water treatment and integral cost per ton.
Therefore, folic acid waste water treatment process of the invention realizes sewage disposal qualified discharge and waste cycling and reutilization, and energy-saving and emission-reduction are beneficial to while being enterprise's cost efficiency.
Specific embodiment
Detailed explanation is done to the folic acid waste water treatment process and its preferred technical scheme of the present invention with reference to embodiment.
Embodiment 1
A kind of folic acid waste water treatment process in the present embodiment, comprises the steps:First secondary filter is carried out to folic acid waste water, be used to remove the material of the ultrahigh molecular weight in folic acid waste water at normal temperatures using secondary filter, the pretreating process as separating acid and separation ammonia nitrogen substances;The means of the secondary filter for adopting here are mainly precoat filtration.Wherein, precoat filtration is preferably to take and is filtered in screen surface precoated diatomite filter aid, expanded perlite or powdered ion-exchange resin, and one is to ensure that the velocity ratio that filtrate body has had, it is ensured that the rate of filtration;Two is can to adsorb more particulate matter or macromolecular substances.
Next to that carrying out isolating and purifying recovery to acid, at normal temperatures using the hydrochloric acid and sulfuric acid in waste water after macroporous resin adsorption secondary filter, backwashed with pure water after macroporous resin adsorption saturation, desorption obtains hydrochloric acid and sulfuric acid mixed acid solution, remaining for ammonia nitrogen waste water;Retain hydrochloric acid sulfuric acid mixed acid solution, and remaining ammonia nitrogen waste water is carried out to isolate and purify recovery;
Isolating and purifying recovery to ammonia nitrogen, mainly using gaseous state embrane method deamination is carried out under normal temperature, adopt hydrochloric acid obtained above and sulfuric acid mixed acid solution for the adsorptive gaseous strip-up acquisition of absorbing liquid ammonia, obtain the ammonia nitrogen substances in ammonia nitrogen waste water.
Then, acid is carried out isolating and purifying the hydrochloric acid sulfuric acid mixed acid solution obtained by reclaiming and ammonia nitrogen isolates and purifies the ammonia nitrogen substances obtained by reclaiming and mixed, the consumption of both adjustment causes mixed solution in neutral or alkalescent;Membrane filtration is carried out to the product after neutralization and obtains oronain/sulphur ammonium mixing nitrogenous fertilizer and residual solution, it is that 7-8, COD are less than 300mg/L, solution of the salt concentration less than 200mg/L less than 50mg, PH that the residual solution is ammonia nitrogen concentration;Resulting oronain/sulphur ammonium mixing nitrogenous fertilizer can be sold nearby for agricultural.The filter membrane is milipore filter, miillpore filter, NF membrane, microfiltration membranes, hollow fiber ultrafiltration membrane or Sai Er filter membranes.
In order to reduce destruction of the residual solution to environment, need further to carry out residual solution conventional sewage handling process process, such as activated sludge process, Halophiles or Aerobic-anaerobic group technology is processed.
Embodiment 2
A kind of folic acid waste water treatment process in the present embodiment, comprises the steps:First secondary filter is carried out to folic acid waste water, be used to remove the material of the ultrahigh molecular weight in folic acid waste water at normal temperatures using secondary filter, as separating acid and the pretreating process of separation ammonia nitrogen substances;The means of the secondary filter for adopting here are predominantly directly filtered.The direct filtration is filtered using Porous cartridge filter or filter membrane, and preferably Porous cartridge filter is porous web cartridge filter or porous plate cartridge filter.Whether the precoat filtration in embodiment 1, or directly filtration can be reused in the present embodiment, avoid the waste of filtering material, reduce the expense of folic acid wastewater treatment.
Next to that carrying out isolating and purifying recovery to acid, at normal temperatures using the hydrochloric acid and sulfuric acid in waste water after macroporous resin adsorption secondary filter, backwashed with pure water after macroporous resin adsorption saturation, desorption obtains hydrochloric acid and sulfuric acid mixed acid solution, remaining for ammonia nitrogen waste water;Retain hydrochloric acid sulfuric acid mixed acid solution, and remaining ammonia nitrogen waste water is carried out to isolate and purify recovery;Dewatering microporous film ammonia nitrogen removal is carried out in the case where recovery is isolated and purified to ammonia nitrogen using normal temperature, both the concentration difference with ammonia nitrogen waste water drives ammonia nitrogen waste water by hydrophobic microporous membrane filtration as driving force, obtains the ammonia nitrogen substances in ammonia nitrogen waste water.
Then, acid is carried out isolating and purifying the hydrochloric acid sulfuric acid mixed acid solution obtained by reclaiming and ammonia nitrogen isolates and purifies the ammonia nitrogen substances obtained by reclaiming and mixed, the consumption of both adjustment causes mixed solution in neutral or alkalescent;Membrane filtration is carried out to the product after neutralization and obtains oronain/sulphur ammonium mixing nitrogenous fertilizer and residual solution, it is that 7-8, COD are less than 300mg/L, solution of the salt concentration less than 200mg/L less than 50mg, PH that the residual solution is ammonia nitrogen concentration;Resulting oronain/sulphur ammonium mixing nitrogenous fertilizer can be sold nearby for agricultural.The filter membrane is any one in milipore filter, miillpore filter, NF membrane, microfiltration membranes, hollow fiber ultrafiltration membrane or Sai Er filter membranes.
In order to reduce destruction of the residual solution to environment, need further to carry out residual solution conventional sewage handling process process, the present embodiment adopts anaerobic grain Wastewater Treated by Activated Sludge Process residual solution.
When acid is isolated and purified using macroporous resin adsorption in embodiment 1 and embodiment 2, using " acid is sluggish " effect of resin adsorption, when folic acid waste water is filtered, HCl, H2SO4 it is adsorbed with resin on, then pure water backwash desorption obtains HCl, H2SO4 mixed acid after adsorption saturation, and here difference with the prior art is:The H+ not absorbed merely for HCl, H2SO4 in HCl, H2SO4 mixed acid of resin adsorption, reduces separating the concentration of the salt after example purifying acid in solution, also does basis for follow-up neutralization procedure.
Depickling, ammonia nitrogen removal and desalination are being carried out in embodiment 1 and embodiment 2(Oronain/sulphur ammonium mixing nitrogenous fertilizer)Process up to standard by inexpensive biochemical process of the waste water for remaining afterwards using routine, fully reduce the processing cost of folic acid waste water, in production application, the processing cost of the folic acid waste water that averagely gets off is only 4.5 yuan/ton;Originally it is simultaneously that the acid of the pending degraded component of sewage, ammonia nitrogen, salt become the mixing nitrogenous fertilizer for having sales value, directly can sells nearby.
Simultaneously, isolating and purifying for acid is that the resins exchange adsorbing separation power of normal temperature is mainly concentration difference --- the natural power that high concentration spreads to low concentration, remain membrane filtration processes in form, acid isolate and purify macroreticular resin used can be repeatedly utilized so that with film, reduced investment, stable, management it is simple.
The membrane filtration that isolates and purifies of ammonia nitrogen is physical filtering process, and ammonia can spread and other compositions in whole process(Including water)Can not spread so that the ammonia nitrogen substances that purification is obtained more are purified, it is ensured that the oronain that neutralization is obtained/sulphur ammonium mixes the quality of nitrogenous fertilizer so as to may be directly applied to agricultural.
It should be appreciated that the above-mentioned specific embodiment of the present invention is used only for exemplary illustration or explains the principle of the present invention, and it is not construed as limiting the invention.Therefore, any modification, equivalent substitution and improvements done in the case of without departing from the spirit and scope of the present invention etc., should be included within the scope of the present invention.Additionally, the whole that claims of the present invention are intended to fall in the equivalents on scope and border or this scope and border changes and modifications example.

Claims (5)

1. a kind of folic acid waste water treatment process, it is characterised in that comprise the steps:
(1)Secondary filter is carried out to folic acid waste water, the secondary filter is precoat filtration or directly filters;The precoat filtration is taken and is filtered in screen surface precoated diatomite filter aid, expanded perlite or powdered ion-exchange resin;The direct filtration is filtered using Porous cartridge filter or filter membrane;
(2)Acid isolates and purifies recovery, using hydrochloric acid and sulfuric acid in waste water after macroporous resin adsorption secondary filter, is backwashed with pure water after macroporous resin adsorption saturation, and desorption obtains hydrochloric acid and sulfuric acid mixed acid solution, remaining for ammonia nitrogen waste water;
(3)Ammonia nitrogen isolates and purifies recovery, to ammonia nitrogen waste water using gaseous state embrane method deamination or dewatering microporous film is carried out under normal temperature, deviates from the ammonia nitrogen substances in ammonia nitrogen waste water;
(4)Neutralization, blend step(2)The hydrochloric acid sulfuric acid mixed acid and step of gained(3)The ammonia nitrogen substances of gained are mixed, adjust the amount of the two and cause mixed solution in neutrality, carry out membrane filtration to solution after neutralization again and obtain oronain/sulphur ammonium mixing nitrogenous fertilizer and residual solution, it is that 7-8, COD are less than 300mg/L, solution of the salt concentration less than 200mg/L less than 50mg, PH that the residual solution is ammonia nitrogen concentration;
(5)Carry out activated sludge process, Halophiles or Aerobic-anaerobic group technology to residual solution to process.
2. a kind of folic acid waste water treatment process according to claim 1, it is characterised in that the handling process to folic acid waste water is carried out at normal temperatures.
3. a kind of folic acid waste water treatment process according to claim 1, it is characterised in that the Porous cartridge filter is porous web cartridge filter or porous plate cartridge filter.
4. a kind of folic acid waste water treatment process according to claim 1, it is characterised in that step(4)The filter membrane is milipore filter, miillpore filter, NF membrane, microfiltration membranes, hollow fiber ultrafiltration membrane or Sai Er filter membranes.
5. a kind of folic acid waste water treatment process according to claim 1, it is characterised in that the activated sludge process adopts anaerobic grain activated sludge.
CN201510643455.XA 2015-10-08 2015-10-08 Folic acid wastewater treatment process Pending CN106565050A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108840497A (en) * 2018-06-04 2018-11-20 宿迁新亚科技有限公司 A method of sewage middle and high concentration ammonia nitrogen is removed with large aperture synthetic resin
CN112321023A (en) * 2020-11-04 2021-02-05 江苏瑞祥化工有限公司 Method for removing acid from chlorobenzene washing wastewater
CN112500415A (en) * 2020-11-13 2021-03-16 安徽泰格维生素实业有限公司 Method for recovering folic acid from wastewater in folic acid dissolution and elutriation stage

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CN102503016A (en) * 2011-12-19 2012-06-20 杭州浙大合力科技有限公司 Device and method for treating ammonia nitrogen wastewater, recycling ammonia and preparing ammonium sulfate
CN104609633A (en) * 2015-02-16 2015-05-13 阮氏化工(常熟)有限公司 Method and device for utilizing sewage containing ammonia and sodium

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CN102030438A (en) * 2010-11-16 2011-04-27 湖南康盟环保科技有限公司 Treatment method of ammonia nitrogen wastewater
CN102476880A (en) * 2010-11-26 2012-05-30 攀钢集团钢铁钒钛股份有限公司 Treatment method of wastewater with sedimentated vanadium
CN102503016A (en) * 2011-12-19 2012-06-20 杭州浙大合力科技有限公司 Device and method for treating ammonia nitrogen wastewater, recycling ammonia and preparing ammonium sulfate
CN104609633A (en) * 2015-02-16 2015-05-13 阮氏化工(常熟)有限公司 Method and device for utilizing sewage containing ammonia and sodium

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108840497A (en) * 2018-06-04 2018-11-20 宿迁新亚科技有限公司 A method of sewage middle and high concentration ammonia nitrogen is removed with large aperture synthetic resin
CN112321023A (en) * 2020-11-04 2021-02-05 江苏瑞祥化工有限公司 Method for removing acid from chlorobenzene washing wastewater
CN112500415A (en) * 2020-11-13 2021-03-16 安徽泰格维生素实业有限公司 Method for recovering folic acid from wastewater in folic acid dissolution and elutriation stage

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