CN103264995A - Sulfuric acid recovery technique in process of producing cystine by adopting sulfuric acid method - Google Patents
Sulfuric acid recovery technique in process of producing cystine by adopting sulfuric acid method Download PDFInfo
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- CN103264995A CN103264995A CN2013102088262A CN201310208826A CN103264995A CN 103264995 A CN103264995 A CN 103264995A CN 2013102088262 A CN2013102088262 A CN 2013102088262A CN 201310208826 A CN201310208826 A CN 201310208826A CN 103264995 A CN103264995 A CN 103264995A
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Abstract
The invention discloses a sulfuric acid recovery technique in the process of producing cystine by adopting a sulfuric acid method. The sulfuric acid recovery technique comprises the steps of: (1) simultaneously flowing hydrolysate and water through an anion-exchange membrane diffusion dialyzer, controlling the flow velocity of the hydrolysate and water so that the pH value of the hydrolysate flowing out is 1-1.5 and the water flowing out becomes acid liquor; and (2) flowing the hydrolysate and water out to simultaneously flow through an electrodialyzer, so that the pH value of the hydrolysate flowing out from a desalting chamber of the electrodialyzer is 3-4 through controlling the electrified voltage and the flow rate of the hydrolysate and water, wherein the hydrolystae flows in cystine production procedure, and the water flowing out from a concentration chamber of the electrodialyzer becomes diluted acid liquor which is used for replacing the water in the step (1), thus realizing the recovery cycle of sulfuric acid. The technique is simple and easy for steps, the consumption of alkali and liquid ammonia in cystine production can be reduced, the raw materials can be saved, the production cost can be lowered, the content of salt in waste water can be decreased, and the treating difficulty and treatment cost of waste water can be lowered.
Description
Technical field
The present invention relates to sulfuric acid recovery technology in a kind of Production By Sulfuric Acid Process Gelucystine process.
Background technology
The technology that the sulphuric acid hydrolysis hair is produced Gelucystine generally comprises following operation: hydrolysis, once neutralization, once decolouring, secondary neutralization, secondary decolourization, neutralize for three times and operation such as make with extra care.The hydrolyzed solution that can produce after hydrolysis is finished, in hydrolyzed solution, add alkali general sulfuric acid neutralization wherein, neutralization back Gelucystine is separated out, filtration obtains crude product of Gelucystine, filtrate continuation neutralizes with sodium bicarbonate, filtration obtains Gelucystine secondary crude product, filtrate continuation neutralizes with liquefied ammonia, filtration obtains three crude products of Gelucystine, and filtrate can further be extracted the chromium propylhomoserin, and final salt bearing liquid wastes enters sewage disposal device and handles, owing to need to consume a large amount of alkali and liquefied ammonia in the N-process, and can produce a large amount of salt, not only strengthened the difficulty of sewage disposal, and made the excess sulfuric acid in the hydrolyzed solution can not get effective utilization.Above-mentioned processing mode causes that raw material availability is low, wastage of material and energy consumption increase, and directly causes the rising of production cost.Therefore, invent a kind of method that reclaims sulfuric acid in the hydrolyzed solution, wherein excess sulfuric acid is separated, and is used for producing again, and consumption and reduction sewage disposal difficulty to reduce alkali, liquefied ammonia just seem very important.
Summary of the invention
The purpose of this invention is to provide sulfuric acid recovery technology in a kind of Production By Sulfuric Acid Process Gelucystine process.
In order to realize the foregoing invention purpose, sulfuric acid provided by the present invention reclaims technology and may further comprise the steps:
(1) allows hydrolyzed solution that hair in the Production By Sulfuric Acid Process Gelucystine process forms through sulphuric acid hydrolysis and the water anion-exchange membrane diffusion dialysis device inner chamber of flowing through simultaneously, part of sulfuric acid in the hydrolyzed solution enters in the water by anion-exchange membrane, the flow velocity of control hydrolyzed solution and water, make the pH value of the hydrolyzed solution that flows out in the anion-exchange membrane diffusion dialysis device be 1-1.5, the water that flows out in the anion-exchange membrane diffusion dialysis device then becomes acid solution;
(2) allow above-mentioned pH value be the hydrolyzed solution of 1-1.5 and the water electrodialyzer of flowing through simultaneously, flow by control energising voltage and hydrolyzed solution and water, make the pH value of the hydrolyzed solution that flows out in the electrodialyzer diluting compartment be 3-4, pH value is that the hydrolyzed solution of 3-4 enters the Gelucystine production process; The water that flows out in the electrodialyzer concentration compartments then becomes diluted acid, and diluted acid is used for the water of alternative steps (1), can realize that then the circulation that sulfuric acid reclaims carries out.
Described hydrolyzed solution also need filter to remove solids impurity wherein before flowing into anion-exchange membrane diffusion dialysis device, blocks anion-exchange membrane diffusion dialysis device to prevent solids impurity.
Acid content is low excessively in the hydrolyzed solution, Gelucystine will be separated out, for acid in the recovery hydrolyzed solution as much as possible with prevent from the acid recovery process, separating out Gelucystine and the obstruction that causes electrodialyzer, acid content in the hydrolyzed solution be maintained below the iso-electric point of Gelucystine and level that Gelucystine can not be separated out.By a large amount of experiments, find that the pH value of hydrolyzed solution just can reach the state that Gelucystine can not be separated out for 3-4.The present invention just is being based on above-mentioned theory and is making, the major part that reclaims in the hydrolyzed solution with anion-exchange membrane diffusion dialysis device is sour earlier, reclaim remaining small amount of acid with electrodialysis again, make the pH value of hydrolyzed solution reach 3-4, entering regeneration after the acid recovery produces, hydrolyzed solution can enter next procedure and neutralize, only need after most of acid recovery to extract Gelucystine with small amount of alkali and liquefied ammonia neutralizing hydrolysis liquid, because the amount of the salt that generates is less, therefore can better reclaim chromium propylhomoserin and effective difficulty that reduces sewage disposal.
The invention has the advantages that: 1, processing step is simple; 2, can be with most of acid recovery in the hydrolyzed solution, effectively reduce the consumption of alkali and liquefied ammonia in the Production By Sulfuric Acid Process Gelucystine process, saved raw material, reduced production cost; 3, reduce the content that the Production By Sulfuric Acid Process Gelucystine produces salt in the waste water, reduced intractability and the processing cost of waste water.
Embodiment
Anion-exchange membrane diffusion dialysis device is currently available products, and the diffusion liquid outlet that it has the diffusion liquid import of diffusion liquid inflow and supplies diffusion liquid to flow out supplies the stoste import of stoste inflow and the stoste outlet of flowing out for stoste; Its inside arranges at interval by some anionresin diaphragms and dividing plate and is divided into a plurality of stoste chambers and a plurality of diffusion sap cavities chamber, and namely the both sides of each diaphragm are respectively stoste chamber and diffusion sap cavity chamber; One end of stoste chamber is communicated with the stoste outlet, and its other end is communicated with the stoste import; One end of diffusion sap cavity chamber is communicated with the import of diffusion liquid, and the other end of crossing the sap cavity chamber is communicated with the outlet of diffusion liquid.
Electrodialyzer is similarly currently available products, and it has for the water outlet of the water-in of tap water or softening water inflow and the outflow of supplying water, for the fluid inlet of stoste inflow and the liquid outlet that flows out for stoste; Its inside is divided into a plurality of diluting compartments and concentration compartments by some yin, yang ion-exchange membranees to arranging at interval with dividing plate; One end of diluting compartment is communicated with fluid inlet, and the other end of diluting compartment is communicated with liquid outlet; One end of concentration compartments is communicated with water-in, and the other end of concentration compartments is communicated with water outlet.
The concrete steps that reclaim sulfuric acid in the hydrolyzed solution are as described below.
(1) during Gelucystine is produced, hair is behind the first solids impurity of removing after filtration wherein of the hydrolyzed solution that sulphuric acid hydrolysis produces, hydrolyzed solution is sent into anion-exchange membrane diffusion dialysis device by the stoste import, hydrolyzed solution is flowed through and is flowed out from the stoste outlet behind the stoste chamber, simultaneously tap water or softening water are sent into anion-exchange membrane diffusion dialysis device by the import of diffusion liquid, current flow out from the outlet of diffusion liquid behind diffusion sap cavity chamber; SO in the hydrolyzed solution under the effect of anion-exchange membrane in the stoste chamber
4 2-Ion enters into the indoor water of diffusion sap cavity, along with SO in the hydrolyzed solution preferentially by anion-exchange membrane
4 2-Passing through of ion, the H that volume is less
+It is indoor that ion also enters into the diffusion sap cavity by anion-exchange membrane, to keep the charge balance of anion-exchange membrane both sides.Because the concentration of the total soluble matters of solution will be higher than diffusion sap cavity chamber far away in the stoste chamber, so the SO in the hydrolyzed solution
4 2-Ion and H
+Ion can be in a large number enter into diffusion sap cavity chamber by anion-exchange membrane, reaches balance up to the osmotic pressure of anion-exchange membrane both sides solution, and diffusion just can stop.The take-off rate that flows to that flows to take-off rate and control water by the control hydrolyzed solution just can make from the pH value control 1-1.5 of the hydrolyzed solution of stoste outlet outflow, and the water that flows out from the outlet of diffusion liquid then becomes acid solution, and this acid solution is restored acid, the about 160g/l of its concentration.That is to say hydrolyzed solution after above-mentioned processing, most of acid wherein is recovered, and restored acid can be used for producing again.
(2) allow the pH value that flows out from the outlet of the stoste of anion-exchange membrane diffusion dialysis device be the hydrolyzed solution of 1-1.5, send in the electrodialyzer by fluid inlet, flow through and flow out from liquid outlet behind the diluting compartment, allow tap water or softening water enter in the electrodialyzer by water-in simultaneously, flow through and flow out from water outlet behind the concentration compartments, flow out water and become diluted acid.Electrodialyzer is alternately to be arranged and dividing plate arranges at interval and is divided into a plurality of diluting compartments and concentration compartments by some yin, yang ion-exchange membranees, under the effect of applying direct current electric field, after hydrolyzed solution enters diluting compartment, negatively charged ion in the solution and positively charged ion just begin to do orientation movement, negatively charged ion anode direction moves, and positively charged ion moves to cathode direction.Because ion-exchange membrane has the selective permeation performance, the fixedly cation exchange groups of cationic exchange membrane is electronegative, therefore allows water middle-jiao yang, function of the spleen and stomach IONS OF H
+By stopping negatively charged ion SO
4 2-By; The fixedly cation exchange groups of anion-exchange membrane is positively charged, therefore allows the negatively charged ion SO in the water
4 2-By stopping positively charged ion H
+By, cause zwitterion in the diluting compartment to be moved in the concentration compartments and go, finally the hydrolyzed solution acid content that flows out from diluting compartment constantly descends.By the flow of control energising voltage and hydrolyzed solution and water, the pH value of the hydrolyzed solution that can flow out from liquid outlet is controlled at 3-4, and the Gelucystine production that this hydrolyzed solution is used for then becomes diluted acid from the water of water outlet outflow.
When the diluted acid that produces in the above-mentioned steps (2) reach a certain amount of after, tap water or softening water in the available diluted acid alternative steps (1), thus can realize that the circulation that sulfuric acid reclaims carries out, and arrive the purpose of reduce water consumption.
Claims (2)
1. sulfuric acid reclaims technology in the Production By Sulfuric Acid Process Gelucystine process, it is characterized in that may further comprise the steps:
(1) allows hydrolyzed solution that hair in the Production By Sulfuric Acid Process Gelucystine process forms through sulphuric acid hydrolysis and the water anion-exchange membrane diffusion dialysis device inner chamber of flowing through simultaneously, part of sulfuric acid in the hydrolyzed solution enters in the water by anion-exchange membrane, the flow velocity of control hydrolyzed solution and water, making the pH value of the hydrolyzed solution that flows out in the anion-exchange membrane diffusion dialysis device is 1-1.5, and the water that flows out in the anion-exchange membrane diffusion dialysis device then becomes acid solution;
(2) allow the above-mentioned pH value be the hydrolyzed solution of 1-1.5 and the water electrodialyzer of flowing through simultaneously, flow by control energising voltage and hydrolyzed solution and water, making the pH value of the hydrolyzed solution that flows out in the electrodialyzer diluting compartment is 3-4, and pH value is that the hydrolyzed solution of 3-4 enters the Gelucystine production process; The water that flows out in the electrodialyzer concentration compartments then becomes diluted acid, and diluted acid is used for the water of alternative steps (1), can realize that then the circulation that sulfuric acid reclaims carries out.
2. sulfuric acid reclaims technology in the Production By Sulfuric Acid Process Gelucystine process as claimed in claim 1, it is characterized in that described hydrolyzed solution flows into anion-exchange membrane diffusion dialysis device before, also need filter to remove solids impurity wherein.
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| CN2013102088262A CN103264995A (en) | 2013-05-30 | 2013-05-30 | Sulfuric acid recovery technique in process of producing cystine by adopting sulfuric acid method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105084600A (en) * | 2015-08-28 | 2015-11-25 | 浙江奇彩环境科技有限公司 | Method for efficiently treating salt-containing organic wastewater and application of method |
| CN109534561A (en) * | 2018-12-27 | 2019-03-29 | 山东天维膜技术有限公司 | A kind of processing method and its device of aluminium foil nitric acid chemical conversion technique waste water |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5859964A (en) * | 1981-10-07 | 1983-04-09 | Ajinomoto Co Inc | Novel type crystal of l-cystine |
| CN101348452A (en) * | 2007-07-20 | 2009-01-21 | 湖州金电化学技术有限公司 | Preparation of homocystine |
-
2013
- 2013-05-30 CN CN2013102088262A patent/CN103264995A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5859964A (en) * | 1981-10-07 | 1983-04-09 | Ajinomoto Co Inc | Novel type crystal of l-cystine |
| CN101348452A (en) * | 2007-07-20 | 2009-01-21 | 湖州金电化学技术有限公司 | Preparation of homocystine |
Non-Patent Citations (2)
| Title |
|---|
| 刘勋等: "提取法生产氨基酸的最新技术进展", 《氨基酸和生物资源》 * |
| 赵敏等: "电渗析技术用于猪毛水解液脱酸的研究", 《氨基酸和生物资源》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105084600A (en) * | 2015-08-28 | 2015-11-25 | 浙江奇彩环境科技有限公司 | Method for efficiently treating salt-containing organic wastewater and application of method |
| CN105084600B (en) * | 2015-08-28 | 2017-11-24 | 浙江奇彩环境科技股份有限公司 | A kind of method and its application of efficient process salt-containing organic wastewater |
| CN109534561A (en) * | 2018-12-27 | 2019-03-29 | 山东天维膜技术有限公司 | A kind of processing method and its device of aluminium foil nitric acid chemical conversion technique waste water |
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Application publication date: 20130828 |