CN104844487A - Method for decoloring methionine crystallization mother liquor by adopting membrane integration technology - Google Patents
Method for decoloring methionine crystallization mother liquor by adopting membrane integration technology Download PDFInfo
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- CN104844487A CN104844487A CN201510157062.8A CN201510157062A CN104844487A CN 104844487 A CN104844487 A CN 104844487A CN 201510157062 A CN201510157062 A CN 201510157062A CN 104844487 A CN104844487 A CN 104844487A
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Abstract
The invention provides a method for decoloring a methionine crystallization mother liquor by adopting a membrane integration technology. The method comprises the following steps: 1, carrying out ultrafiltration (UF) system treatment on methionine; and 2, carrying out nanofiltration (NF) membrane decoloring purification system treatment, adding pure water to the obtained nanofiltration concentrate, carrying out filter washing, directly conveying the obtained substance to a burning device, burning, and allowing an NF permeation liquid to directly enter a subsequent process. The clean production membrane integration decoloring technology is adopted to substitute active carbon decoloring in order to remove colloids and other pigments in the methionine crystallization mother liquor, so the generation of solid wastes of an enterprise is reduced, and the working environment of a decoloring workshop is improved; and high concentration multiple of the membrane technology is used, so the emission amount of wastewater is reduced, and the running pressure of the wastewater treatment station of the enterprise is reduced.
Description
Technical field
The present invention relates to the technique of a kind of membrane integrating technique process methionine(Met) crystalline mother solution decolouring.
Background technology
Methionine(Met), also known as methionine(Met), is one of indispensable amino acid forming human body, participates in protein synthesis.Because it can not self generate, so must be obtained by outside in vivo.If methionine(Met) lacks will cause body internal protein biosynthesis block, cause body damage.The membrane lipid over oxidation that in body, oxyradical causes is the reason causing the multiple infringement of body.Lipid peroxide can damage primary and secondary lysosome membrane, and the acid phosphatase as hydrolysis contained in lysosome is discharged, and the organoid important to cell and mitochondrial membrane etc. causes damage, and methionine(Met) resists these infringements by number of ways.In recent years, domestic and international market is to the strong growth year by year of the demand of methionine(Met).Particularly domestic market, domestic feed methionine(Met) can not be met the need of market far away for many years, every year all will from external a large amount of import, and now become the bulk product of China's medicinal chemicals import, import volume is up to tens thousand of ton for several years running, and import volume crosses hundred million dollars.Estimate that domestic and international market also increases with larger ratio the demand of methionine(Met) from now on, domestic market imbalance between supply and demand in a short time still cannot solve, and also needs a large amount of import.Therefore, the market outlook developing methionine(Met) are very good.
At present, methionine(Met) produces the main method adopting chemosynthesis, and the methionine(Met) feed liquid decrease temperature crystalline be synthesized obtains methionine(Met), but leaves a large amount of methionine(Met) crystalline mother solutions.The treating method of existing methionine(Met) crystalline mother solution mainly adopts the technology such as multiple-effect evaporation, MVR, reverse osmosis membrane to be concentrated into higher concentration, then through the decolouring of gac, continues to return front end crystallization.But this processing disadvantages is as follows: 1, in methionine(Met) crystalline mother solution containing a large amount of pigment, greatly reduce the efficiency that multiple-effect evaporation, MVR, reverse osmosis membrane are concentrated; Decolour if gac is mentioned concentrated front end by 2, required amounts of activated carbon is too large; 3, activated carbon decolorizing causes production environment severe, and dust pollution is serious, and the gac after decolouring becomes the outer process of useless solid needs committee.
Summary of the invention
Technical problem to be solved by this invention is to provide the method for a kind of membrane integrating technique process methionine(Met) crystalline mother solution decolouring, adopt the integrated decolouring technology of cleaner production film, remove the pigments such as the colloid in methionine solution, substitute activated carbon decolorizing, thus reduce the generation of the solid waste of enterprise, also improve the Working environment in decolouring workshop, utilize the high concentration multiple of embrane method simultaneously, reduce wastewater discharge, reduce the operating pressure at scale wastewater treatment station.For this reason, the present invention is by the following technical solutions:
Adopt the technique of membrane integrating technique process methionine(Met) crystalline mother solution, it is characterized in that it carries out following steps process successively to methionine(Met) crystalline mother solution:
1), ultrafiltration system process (UF);
2), nanofiltration membrane decolorization and purification system process (NF); Nanofiltration concentrated solution is delivered directly to incinerator after adding pure water filter wash and burns, and the permeate of nanofiltration directly enters subsequent technique.
On the basis adopting technique scheme, the present invention also can adopt following further technical scheme:
The pH of methionine(Met) crystalline mother solution is between 3-5, the methionine(Met) containing 2-5% in methionine(Met) crystalline mother solution.
The rate of recovery of ultrafiltration system to methionine(Met) controls more than 99%, and the concentration of concentrated solution side methionine(Met) controls below 0.2%, its to the clearance of total suspended substance more than 99%.
The membrane module that ultrafiltration system adopts is hollow-fibre membrane, and mould material is selected from polypropylene, polyvinylidene difluoride (PVDF), polyvinyl chloride, polyethersulfone.
First the permeate of ultrafiltration enters the first step nanofiltration system of nanofiltration membrane decolorization and purification system, and first step nanofiltration system adopts continuous stripping, arranges 3 cover nanofiltration system altogether, 3 cover nanofiltration system series operations, and finally a set of nanofiltration system adopts filter wash mode; The permeate through nanofiltration decolouring of first step nanofiltration system enters the second stage nanofiltration system of nanofiltration membrane decolorization and purification system, and the concentrated solution of first step nanofiltration system goes to burn or the process of decontaminated water treatment plant; Second stage nanofiltration system arranges 3 cover systems altogether, 3 cover nanofiltration system series operations; The permeate through nanofiltration decolouring of second stage nanofiltration system enters follow-up workshop section, and the concentrated solution of second stage nanofiltration system returns first step nanofiltration system and again carries out nanofiltration process.
The rate of recovery of nanofiltration membrane decolorization and purification system process to methionine(Met) controls more than 99%, and the concentration of concentrated solution side methionine(Met) controls below 0.2%, its to the clearance of the pigments such as colloid more than 75%.
The membrane module that nanofiltration adopts is rolling diaphragm, and mould material is selected from cellulose acetate (CA), SPSF (SPS), sulfonated polyether sulfone (SPES) and polyvinyl alcohol (PVA).
Owing to adopting technique scheme, present invention process proposes methionine(Met) crystalline mother solution film decoloring method, and it has following technique effect:
(1), innovatively by " ultrafiltration+nanofiltration " technology be applied to the decolouring of methionine(Met) crystalline mother solution, utilize ultrafiltration to remove the impurity such as suspended substance and oily matter, feed liquid turbidity is declined, the nanofiltration system that energy available protecting is follow-up.Methionine(Met) crystalline mother solution enters nanofiltration membrane decolorization and purification system after filtering, and albumen, pigment and some macromole organic impuritys are trapped in concentrated solution side by nanofiltration membrane, and methionine(Met) etc. enter permeate side with water and are separated, and realize the purification of desorbed solution.
(2), improve the yield of methionine(Met), reduce the generation of solid waste, reduce environmental protection pressure, reduce energy consumption and production cost;
(3) decolouring of nanofiltration membrane decolorization and purification system, is adopted (to have very high rejection to albumen, pigment and some macromole organic impuritys, and to the low rejection of effective constituent), the material concentration produced in water side is remained unchanged substantially, and material also can not enrichment in dense water side, thus pure water needed for minimizing filter wash, also significantly can not dilute feed liquid simultaneously.
(5), realize under the prerequisite reaching higher methionine(Met) yield, the suitability for industrialized production that realizes of final less expensive is run, and is enterprise's create beneficial result, reduces production run cost, improve the market competitiveness of enterprise.
Accompanying drawing explanation
Fig. 1 is the schema that the present invention adopts membrane integrating technique process methionine(Met) technique.
Embodiment
With reference to accompanying drawing, the technique of employing membrane integrating technique process methionine(Met) crystalline mother solution provided by the present invention, the pH of methionine(Met) crystalline mother solution is between 3-5, the methionine(Met) containing 2-5% in feed liquid, and described technique carries out following steps process successively to methionine(Met) crystalline mother solution:
1), ultrafiltration system process (UF);
2), nanofiltration membrane decolorization and purification system process (NF); Nanofiltration concentrated solution is delivered directly to incinerator after adding pure water filter wash and burns, and the permeate of nanofiltration directly enters the subsequent techniques such as follow-up multiple-effect evaporation, MVR, reverse osmosis membrane be concentrated, and concentrated solution returns crystallization again.
The rate of recovery of ultrafiltration system to methionine(Met) controls more than 99%, and the concentration of concentrated solution side methionine(Met) controls below 0.2%, its to the clearance of total suspended substance more than 99%.The membrane module that ultrafiltration system adopts is hollow-fibre membrane, and mould material is selected from polypropylene, polyvinylidene difluoride (PVDF), polyvinyl chloride, polyethersulfone, and their resistance to crockings are strong, adopts matting flux recovery good; Have, to suspended substance, there is high rejection; Easy and simple to handle, the features such as floor space is little.
First the permeate of ultrafiltration enters the first step nanofiltration system of nanofiltration membrane decolorization and purification system, and first step nanofiltration system adopts continuous stripping, arranges 3 cover nanofiltration system altogether, 3 cover nanofiltration system series operations, and finally a set of nanofiltration system adopts filter wash mode; The permeate through nanofiltration decolouring of first step nanofiltration system enters the second stage nanofiltration system of nanofiltration membrane decolorization and purification system, and the concentrated solution of first step nanofiltration system goes to burn or the process of decontaminated water treatment plant; Second stage nanofiltration system arranges 3 cover systems altogether, 3 cover nanofiltration system series operations; The permeate through nanofiltration decolouring of second stage nanofiltration system enters follow-up workshop section, and the concentrated solution of second stage nanofiltration system returns first step nanofiltration system and again carries out nanofiltration process.
The rate of recovery of nanofiltration membrane decolorization and purification system process to methionine(Met) controls more than 99%, and the concentration of concentrated solution side methionine(Met) controls below 0.2%, its to the clearance of the pigments such as colloid more than 75%.The membrane module that nanofiltration adopts is rolling diaphragm, and mould material is selected from cellulose acetate (CA), SPSF (SPS), sulfonated polyether sulfone (SPES) and polyvinyl alcohol (PVA).The same resistance to crocking of these films is strong, adopts matting flux recovery good; Have, to larger molecular organicses such as pigments, there is high rejection; Easy and simple to handle, the features such as floor space is little.
Above percentage is mass percent.
The function description of ultrafiltration system, nanofiltration membrane decolorization and purification system is as follows:
1, ultrafiltration system
Ultrafiltration system in step 1) comprises the equipment such as transferpump, ultra-filtration equipment.Ultra filtration membrane technology has that floor space is little, feed liquid good purification, level of automation high.Native system adopts the tubular fibre of special macromolecule material; its surface active layer is fine and close; there is withstand voltage, the feature such as anti-pollution, easy cleaning, long service life; and the clarity of clear liquid can be ensured for a long time; to colloid, suspended particle, turbidity, bacterium, larger molecular organics, there is good separating power, nanofiltration system is below played a good protection.Ultra-filtration equipment adopts the automatic operation scheme of cross flow filter.Flux recovery adopts backwash mode, simultaneously in conjunction with the mode of regular matting, recovers membrane flux to greatest extent.
Principal feature:
1) tubular fibre outside surface active layer porosity is high, therefore fiber unit plane accumulated amount is large;
2) molecular weight cut off is accurate, and separation efficiency is high;
3) tubular fibre intensity is high, inner pressed separatory membrane technology, adopts matting, recovers membrane flux part to greatest extent;
4) energy consumption is low;
5) operation and maintenance is simple.
Main technical details
1) operation scheme: operation every day two classes, run 20h, film maintains 4 hours;
2) service temperature: 5 ~ 40 DEG C;
3) design pressure :≤0.20Mpa;
4) rate of recovery: >=99%;
5) methionine concentration in debris :≤0.2%;
2, nanofiltration membrane decolorization and purification system
Step 2) in nanofiltration membrane decolorization and purification System Take methionine(Met) except the task of larger molecular organics, decolouring etc.Methionine(Met) enters nanofiltration membrane decolorization and purification system after filtering, and albumen, pigment and some macromole organic impuritys are trapped in concentrated solution side by nanofiltration membrane, and methionine(Met) etc. enter permeate side with water and are separated, and realize the purification of desorbed solution.
This nanofiltration membrane decolorization and purification system adopts has excellent chemical physical stability, weather resistance, and the high yield water yield, to methionine(Met) and the low rejection of sodium carbonate and the membrane element to albumen, pigment height cutoff performance, by increasing the sheet number of film bag, shorten the length of inlet conduit, increase the width of water inlet filter, not only have higher water flux, and organism and the absorption of microorganism on film surface can be reduced, there is stronger anti-pollution ability.
After the decolouring of secondary nanofiltration system, methionine(Met) crystalline mother solution transmittance improves obviously, and the yield of methionine(Met) is more than 99%.
Principal feature:
Resistance to crocking is strong, adopts matting flux recovery good;
To larger molecular organicses such as pigments, there is high rejection;
Easy and simple to handle, floor space is little.
Claims (7)
1. adopt the technique of membrane integrating technique process methionine(Met) crystalline mother solution decolouring, it is characterized in that it carries out following steps process successively to methionine(Met) crystalline mother solution:
1), ultrafiltration system process (UF);
2), nanofiltration membrane decolorization and purification system process (NF); Nanofiltration concentrated solution is delivered directly to incinerator after adding pure water filter wash and burns, and the permeate of nanofiltration directly enters subsequent technique.
2. the technique adopting the decolouring of membrane integrating technique process methionine(Met) as claimed in claim 1, is characterized in that the pH of methionine(Met) crystalline mother solution is between 3-5, the methionine(Met) containing 2-5% in methionine(Met) crystalline mother solution.
3. the technique adopting the decolouring of membrane integrating technique process methionine(Met) crystalline mother solution as claimed in claim 1, it is characterized in that the rate of recovery of ultrafiltration system to methionine(Met) controls more than 99%, the concentration of concentrated solution side methionine(Met) controls below 0.2%, its to the clearance of total suspended substance more than 99%.
4. the technique adopting the decolouring of membrane integrating technique process methionine(Met) crystalline mother solution as claimed in claim 1, it is characterized in that the membrane module that ultrafiltration system adopts is hollow-fibre membrane, mould material is selected from polypropylene, polyvinylidene difluoride (PVDF), polyvinyl chloride, polyethersulfone.
5. the technique of acrylic acid waste water handling reclamation as claimed in claim 1, it is characterized in that in step (2), the nanofiltration permeate of former hydromining acrylic acid wastewater is water source, for the dense water side of electrodialysis system, partial continuous is run, and the dense water run continuously moves towards and moved towards contrary by the material of electrodialysis process.
6. the technique adopting the decolouring of membrane integrating technique process methionine(Met) crystalline mother solution as claimed in claim 1, it is characterized in that the rate of recovery of nanofiltration membrane decolorization and purification system process to methionine(Met) controls more than 99%, the concentration of concentrated solution side methionine(Met) controls below 0.2%, its to the clearance of the pigments such as colloid more than 75%.
7. the technique adopting the decolouring of membrane integrating technique process methionine(Met) crystalline mother solution as claimed in claim 1, it is characterized in that the membrane module that nanofiltration adopts is rolling diaphragm, mould material is selected from cellulose acetate (CA), SPSF (SPS), sulfonated polyether sulfone (SPES) and polyvinyl alcohol (PVA).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110372552A (en) * | 2019-07-31 | 2019-10-25 | 赵永春 | A kind of discoloration method improving Cystine Product quality and yield |
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| CN101831483A (en) * | 2010-04-20 | 2010-09-15 | 天津金耀集团有限公司 | Preparation method of L-methionine |
| CN104174181A (en) * | 2014-05-14 | 2014-12-03 | 重庆紫光化工股份有限公司 | Separation and purification system of organic synthesis feed liquid and separation and purification method thereof |
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2015
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Patent Citations (3)
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| CN1586502A (en) * | 2004-08-13 | 2005-03-02 | 北京奥路特生物医药研发有限公司 | Process for preparing compound coemzyme medicine and its compound coemzyme medicine and clinical use |
| CN101831483A (en) * | 2010-04-20 | 2010-09-15 | 天津金耀集团有限公司 | Preparation method of L-methionine |
| CN104174181A (en) * | 2014-05-14 | 2014-12-03 | 重庆紫光化工股份有限公司 | Separation and purification system of organic synthesis feed liquid and separation and purification method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110372552A (en) * | 2019-07-31 | 2019-10-25 | 赵永春 | A kind of discoloration method improving Cystine Product quality and yield |
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