The method of all-film extraction of valineTechnical field the invention belongs to the Xie Ansuan production technical field, is specifically related to a kind of method of all-film extraction of valine, promptly a kind of novel process that adopts full membrane technique to come the separation and purification valine fermentation liquid.
Background technology L-Xie Ansuan is one of eight big indispensable amino acids that people and animal self can not be synthesized and necessary dependence external source is supplied with as one of branched-chain amino acid, has different physiological roles.The L-Xie Ansuan is the material of synthetic protein, also can be used as the energy of organism and as the precursor of biological component, mainly in order to the transfusion of preparation aminoacids complex, synthetic polypeptide medicaments and food antioxidant etc., especially medical research and the treatment in effect and come into one's own day by day, along with deepening continuously that Xie Ansuan is studied, its range of application in food and fodder industry also will further enlarge.Therefore, the L-Xie Ansuan has enormous and latent market in medicine, food and fodder industry.
According to reports, world's amino acid gross annual output amount is about 2,000,000 tons, about 6000 tons of medicinal transfusion amino acid year demand, and wherein the L-Xie Ansuan is 400 tons.The production of L-Xie Ansuan at present is mainly based on Japan, and domestic does not still have a production in enormous quantities producer.The annual output total amount of China L-Xie Ansuan is less than 2000 tons, and the pharmaceutical grade L-Xie Ansuan overwhelming majority relies on import, a large amount of foreign exchanges of annual consumption.
At present, the production method of L-Xie Ansuan has extraction method, synthesis method, fermentation method.
1) extraction method: mainly be with protein for example soybean protein etc. be hydrolyzed, hydrochloric acid is added in the aqueous solution that contains Xie Ansuan then to generate and to be settled out Xie Ansuan-hydrochloride crystal, repeat this operation, this method separation efficiency is higher, extract simple to operate, with short production cycle, but cost is very high, and the Xie Ansuan-solubleness of hydrochloride crystal in water is very high, make the yield of Xie Ansuan reduce [Japanese Laid-Open Patent Application (Kokai) No.16,450/1981], this method is difficult to obtain big popularization in suitability for industrialized production.
2) synthesis method: a variety of synthesis methods are arranged at present, but the production cost height, reaction is complicated, and step is many, and by product is many, therefore, also is difficult to graft in industrialized production.
3) fermentation method: utilize Production by Microorganism Fermentation L-Xie Ansuan to have that raw materials cost is low, reaction conditions is gentle and realize advantage such as scale operation, it is a kind of very economical production method, therefore, present fermentation production of L-valine has obtained the extensive concern of Chinese scholars.The Xu Xudong of microorganism teaching and research room of China Medicine University in 1999, XT-4 is a starting strain with brevibacterium lactofermentum (Brevibacterium lactofermentum), adopt the NTG mutagenic treatment, obtain the mutant strain A15 (α-TAr+ α-ABr) of strain accumulation L-Xie Ansuan, this bacterial strain shakes bottle and produces sour 26.42g/L, behind the condition optimizing, can reach 33.1g/L.Once selection by mutation and the metabolic regulation of the good production of the used L-Xie Ansuan of fermentation method bacterium had been done some researchs abroad, and domestic still being in studied and the small-scale production stage, production level and output far can not be met the need of market.
(Complete Membrane Technology CMT), is the brand-new suggestion of process design that proposes around advanced film science and technology to full embrane method, mainly is that different membrane process is organically combined.At present, mainly full embrane method is applied to wastewater treatment both at home and abroad, general is water inlet with conventional water source or the bio-fermented liquid after conventional processing such as biochemistry, filtration, adopt the combination process of the technology of " micro-filtration, ultrafiltration, nanofiltration, reverse osmosis " four kinds of membrane sepn, respectively as removing thalline, removing purposes such as albumen, depigmentation, desalination, to reach efficient removal pollutent and advanced desalination purpose.
Full embrane method high efficiency extraction Xie Ansuan novel environment-friendly process is promptly in the extraction process process of whole Xie Ansuan, and a kind of new technology novel process that all adopts membrane module to finish is applied to notion that amino acid extracts with full embrane method and is initiative both at home and abroad.
Along with membrane technique is in recent years at home and abroad promoted widely, and the film cost is in continuous decline, and membrane separation and purification technology is applied in the Xie Ansuan leaching process will produce good economic benefit.Using membrane technique can not only improve the quality of products, and can also reduce the discharging of waste water, and the protection environment is realized automatization control and cleaner production, reduces production costs, and can also improve workman's Working environment, increases work efficiency.Application of membrane both at home and abroad at present adopts single film to move, and solves a certain particular problem, does not form the technology that a kind of full embrane method is extracted Xie Ansuan.
Summary of the invention the present invention seeks to solve prior art and has technical problems such as producing height, discharge of wastewater are many, working efficiency, provides a kind of method of all-film extraction of valine, to overcome the deficiencies in the prior art.
In order to realize purpose of the present invention, the present invention is undertaken by following processing step:
1) micro-filtrate membrane filtration: valine fermentation liquid is passed through microfiltration membrane, obtain the micro-filtration dialyzate and the tropina of fermented liquid, sell as the high-quality tropina after the tropina drying, the added value height, micro-filtration service temperature: 40-90 ℃, operating pressure: entrance pressure is 3-8bar, goes out to press to be 2-7bar, and pressure difference is 2.5-6bar;
2) ultrafiltration membrance filter: the micro-filtration dialyzate in the step 1) is passed through ultra-filtration membrane, obtain ultrafiltration dialysis liquid and concentrated solution, be used for producing feedstuff protein after the concentrated solution drying, expensive, can realize the higher value application of by product, ultrafiltration temperature: 30-50 ℃, operating pressure: entrance pressure is 5-32bar, go out to press to be 4-30bar, pressure difference is 4.5-28bar;
3) reverse osmosis membrane concentrates: with step 2) in ultrafiltration dialysis liquid pass through reverse osmosis membrane, obtain reverse osmosis concentrated liquid and pure water, the pure water direct reuse is in production, reverse osmosis membrane thickening temperature: 30-50 ℃, operating pressure: entrance pressure is 11-50bar, go out to press to be 10-49bar, pressure difference is 10.5-40bar;
4) condensing crystal: is 25-45% with the reverse osmosis concentrated liquid in the step 3) by vacuum concentration to valine content, reduces to room temperature then, the centrifugal Xie Ansuan crude product that obtains; Crude product is mixed with the solution that concentration is 5-8%, and with the injection active carbon decolouring, adding the charcoal amount is 0.5-3.0%; And then be concentrated into valine content 25-40%, reduce to room temperature then, the centrifugal Xie Ansuan crude product that obtains; Crude product is mixed with the solution that concentration is 5-8%, and with the injection active carbon decolouring, adding the charcoal amount is 0.1-1.0%; Be concentrated into valine content 20-35% then, reduce to room temperature then, centrifugal, drying obtains the Xie Ansuan product; Above decolorization condition is: pH5.5-7.5, temperature 50-80 ℃, time 0.5-3h, decolouring back feed liquid printing opacity 〉=99%;
5) regeneration of film: the acid of microfiltration membrane regeneration usefulness is 1-2% nitric acid, and alkali is the 1-2% liquid caustic soda; The acid of ultra-filtration membrane and reverse osmosis membrane regeneration usefulness is 0.5-1% hydrochloric acid, and alkali is the 0.5-1% liquid caustic soda; Merging intermediary in alkali cleaning water and the acid washing water and back is washed film soft water enter reverse osmosis, obtain concentrating salt and pure water, concentrated salt drying is made the crude salt reuse and is produced, and pure water is back to production.
Microfiltration membrane in the described step 1) is the ceramic material microfiltration membrane, and its molecular weight cut-off is 8000-500000MWCO, aperture 0.05-10 μ m; Step 2) ultra-filtration membrane in is a kind of in PAN, PVDF, PC, PES, PP, the PE composite membrane, and its molecular weight cut-off is 300-5000MWCO, aperture 5-100nm; Reverse osmosis membrane in the step 3) is a kind of in PAN, PVDF, PC, PES, PP, the PE composite membrane.
" full embrane method " among the present invention mainly is made up of three kinds of membrane separation techniques, be microfiltration membrane MF (Micro-Filtration), ultra-filtration membrane UF (Ultre filtratioan) and reverse osmosis membrane RO (Reverse Osmosis), mainly valine fermentation liquid be prepared into the high-quality Xie Ansuan crystalline mother solution that meets the demands by the advantage of integrating multistage film.
The present invention has mainly obtained following three kinds of products:
High purity high-quality tropina, feedstuff protein and high-quality Xie Ansuan.
The present invention can carry out recycling with the by product that produces in the Xie Ansuan production process, and energy-saving and emission-reduction, and therefore the high efficiency extraction for the Xie Ansuan product provides a kind of new friendly process.
This invented technology has following outstanding advantage:
1, realized the feed liquid cold concentration, saved cost in a large number, need not devices such as sheet frame, vacuum, supporting cost is low, and concentration process reduces steam consumption, and easy to operate, labour intensity is little;
2, the film device floor space is little, can realize serialization production, significantly enhances productivity, and operation and maintenance are simple, and work simplification simultaneously can improve product yield;
3, adopt micro-filtration to remove thalline, tropina can realize that 98% reclaims, and it is high by 20% to extract albumen than air supporting method in the traditional technology, need not to add flocculating aids or flocculation agent, improve the quality of tropina by product in the time of compliance with environmental protection requirements, increased the value of by product, high-valued obvious;
4, adopt ultrafiltration to remove pigment, colloid and macromolecular substance, the filtering accuracy height of film promotes postorder Xie Ansuan filtrate quality, is beneficial to Xie Ansuan and extracts, and improves product quality; By the control leaching requirement, yield improves and obtains quality filtrate preferably behind the membrane filtration, and the filtrate printing opacity reaches more than 90%;
5, adopt reverse osmosis method ultrafiltration concentration dialyzate, realize cold concentration, postorder concentrated saved a large amount of steam, but and produce the pure water direct reuse in the process in producing as the batching water, effects of energy saving and emission reduction is remarkable, can improve product concentration simultaneously;
6, the feed liquid printing opacity is higher behind the membrane filtration, and operation is not subjected to Temperature Influence, heat-sensitive substance do not destroy, and yield height, quality are good, do not undergo phase transition, and can preserve product property preferably, have quick, economic characteristics simultaneously;
7, whole film regeneration stage various film wash water comprehensive treating process does not almost have the discharging of waste water, really realizes green manufacturing reaching closed cycle;
8, compare with traditional technology, the present invention has thoroughly eliminated ion-exchange process, saves a large amount of soda acids, avoids the generation of high-concentration waste water.
The present invention has increased substantially quality product, reduce production cost, reduced the discharging of waste water, improved working efficiency, having realized automatization control and cleaner production in the extraction process process of whole Xie Ansuan, is a kind of new technology novel process that a kind of whole employing membrane module is finished.Simultaneously, comprehensive utilization acid, alkali cleaning water have been realized energy saving purposes in the whole process of the regeneration of film.
In a word, adopt " full embrane method " clarification and one step of degerming can be finished, gained filtrate is limpid bright, for the back abstraction process creates good conditions, significantly save the consumption of acid, alkali and water simultaneously, and improved product yield, all right high efficiente callback thalline, alleviate environmental protection pressure, compare with traditional technology, the economic benefit of full embrane method extraction process is mainly reflected in two aspects, and the one, the reduction of cost and the raising of quality product, therefore, the present invention has remarkable economic efficiency, social benefit and environmental benefit.
Appended drawings is a process flow diagram of the present invention.
Embodiment
Embodiment the present invention is a kind of Xie Ansuan extracting method based on full membrane technique, is to improve realization on the basis of existing technology, is undertaken by following processing step:
1, micro-filtration filters: the 1350kg valine fermentation liquid is filtered by micro-filtration, obtain 120kg concentrated solution and micro-filtration dialyzate 1530kg, comprising the 300kg elutriant, printing opacity is 4.8% before the fermented liquid filter, liquid is 90.7% behind the micro-filtration, the elutriant printing opacity is 88%, to filter the merging of back liquid and elutriant and be the micro-filtration dialyzate, transmittance is 89.8%, feed clarification behind the micro-filtration is transparent, there is not visible suspended substance, transparence is more than 89%, it is better that protein and macrobead suspended substance are held back effect, the active substance Xie Ansuan there is not crown_interception substantially, filter back albumen directly oven dry is exactly high-quality protein feed, and tropina can realize that 98.2% reclaims, it is high by 20% to extract albumen than air supporting method in the traditional technology, need not add flocculating aids or flocculation agent, improved the quality of tropina by product in the time of compliance with environmental protection requirements, after drying can be directly as the high-quality animal feeding-stuff containing somatic protein, high-valued obvious, it is that the aperture is the ceramic membrane of 50nm that micro-filtration filters used mould material, concrete processing condition are: service temperature is 50-60 ℃, and flow velocity is 20-30m3/ h, entrance pressure are 3-4bar, go out to press to be 1bar, and pressure difference is 2-2.5bar;
2, ultra-filtration filters: with gained micro-filtration dialyzate 1530kg in the step 1, get 140kg ultrafiltration and concentration liquid and ultrafiltration dialysis liquid 1790kg (comprising elutriant 400kg) by ultra-filtration filters, printing opacity is 88% before the filter, filter back liquid is 90.7%, the elutriant printing opacity is 91%, to filter the merging of back liquid and elutriant and be ultrafiltration dialysis liquid, printing opacity is 91%, the used mould material of ultrafiltration is that molecular weight cut-off is the ultra-filtration membrane of the PVDF of 3000MWCO, and its processing condition are: service temperature is 40 ℃, and entrance pressure is 7-8bar, go out to press to be 6-7bar, pressure difference is 6.5-7.5bar, flow velocity 30-40m3/h, and filter back feed clarification is transparent, printing opacity is more than 90%, filter back concentrated solution can be dried the back as the protein fodder sale, and protein recovery can reach 99.1%, is worth high;
3, reverse osmosis concentration: with gained ultrafiltration dialysis liquid 1790kg in the step 2, get the pure water of reverse osmosis concentrated liquid 470Kg and 1320Kg by osmosis filtration, but pure water direct reuse production, the used mould material of reverse osmosis is that to hold back NaCl be 97% PVDF reverse osmosis membrane, and working conditions is: service temperature is that service temperature is 40 ℃, and entrance pressure is 22bar, go out to press to be 20-21bar, pressure difference is 20.5-21.5bar,, flow velocity 30-40m3/ h adopts reverse osmosis concentration ultrafiltration dialysis liquid, has realized cold concentration, and postorder concentrated saved a large amount of steam, but and produce the pure water direct reuse in the process in producing as the batching water, effects of energy saving and emission reduction is remarkable;
4, condensing crystal: is 35% with the reverse osmosis concentrated liquid 360kg of step 3 reverse osmosis gained by vacuum concentration to valine content, reduces to room temperature then, the centrifugal Xie Ansuan crude product that obtains; It is 7% solution that crude product is mixed with concentration, adopt the decolouring of 767 type injection active carbons, adding the charcoal amount is 2.0%, decolorization condition is: pH5.5-7.5, temperature 50-80 ℃, time 0.5-3h, decolouring back feed liquid printing opacity 〉=99%, and then be concentrated into valine content 30%, reduce to room temperature then, the centrifugal Xie Ansuan crude product that obtains; It is 7% solution that crude product is mixed with concentration, adopt the decolouring of 767 type injection active carbons, adding the charcoal amount is 0.5%, decolorization condition is: pH5.5-7.5, temperature 50-80 ℃, time 0.5-3h, decolouring back feed liquid printing opacity 〉=99.5% is concentrated into valine content 25% then, reduce to room temperature then, centrifugal, drying obtains meeting pharmaceutical grade and requires the Xie Ansuan product;
4, film regeneration: micro-filtration and used acid washing water, alkali cleaning water and the quantitative soft water of ultrafiltration regeneration is mixed into reverse osmosis gets 10% reverse osmosis concentrated liquid and 90% pure water reuse is produced, get final product with quantitative soft water circular flow 30min flushing reverse osmosis membrane more at last, the pure water reuse of gained is produced.