CN103113496B - A kind of process for cleanly preparing of chitin - Google Patents
A kind of process for cleanly preparing of chitin Download PDFInfo
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- CN103113496B CN103113496B CN201310056441.9A CN201310056441A CN103113496B CN 103113496 B CN103113496 B CN 103113496B CN 201310056441 A CN201310056441 A CN 201310056441A CN 103113496 B CN103113496 B CN 103113496B
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Abstract
The present invention relates to a kind of process for cleanly preparing of chitin, relate to processing of aquatic products waste ' s reclamation, food processing wastewater process and technical field of comprehensive utilization.This technology adopts shrimp, crab shell is raw material, carries out the pre-treatment of instantaneous high pressure steam explosion by high-density steam explosion device to raw material, by enzymolysis, food grade protolysate is made in proteolytic extraction most of in raw material; Enzymolysis residue soaks obtained high-quality chitosan successively through NaOH, hydrochloric acid; Waste lye, successively through cartridge filter, silicon carbide material ultra-filtration membrane, the process of alkaline-resisting NF membrane filtration, obtains feed grade protein powder and can the sig water of reuse; Acid steeps waste liquid through cartridge filter, silicon carbide material ultrafiltration membrane treatment, the neutral CaCl obtained
2clarified wastewater qualified discharge.Compared with prior art, the whole novel process of the present invention is clean, environmental protection, and separation purifying technique is simple, reasonable, operation is short, easy to operate, and resource obtains and fully utilizes fully simultaneously, avoid secondary pollution, remarkable in economical benefits improves, and has industrial applications and is worth.
Description
Technical field
The present invention relates to a kind of process for cleanly preparing of chitin, particularly based on a chitin clearer production technology for high-density steam explosion technology and membrane separation technique, belong to processing of aquatic products waste ' s reclamation, food processing wastewater process and technical field of comprehensive utilization.
Background technology
Chitin is the important source material of medicine, food service industry, and industrial is all generally adopt the shell of the crustaceans such as shrimp, crab as raw material, carries out deproteinated and sour decalcification technique, raw materials for production chitin by biological process or chemical method.In recent years because its course of processing produces a large amount of waste water, be restricted in the production of a lot of country, apparent availability sharply declines, and supply falls short of demand in market, and price raises gradually.The chitin source mill of upper scale at present, the traditional soda acid explained hereafter chitin of main employing, produces a large amount of waste water.Owing to containing a large amount of protein, acid, alkali, calcium etc. in waste water, its wastewater treatment difficulty is quite large, processing costs is quite on the other hand high, and the useful compositions such as a large amount of protein in waste water, residual alkali also result in the huge wasting of resources while contaminate environment.
The domestic treatment process for chitin plant effluent routine is concentrated spent acid and waste lye, mix after grid, process through natural sedimentation, polymerize aluminum chloride or bodied ferric sulfate and polyacrylamide flocculation, means of waste water reuse anaerobism or aerobic process again, water outlet COD after administering, generally at more than 1000mg/L, can not reach the sewage drainage standard of country.Meanwhile, due to the high salinity waste water formed after high density acid-base neutralisation, cannot process with general biochemical method, a large amount of manufacturers is because have no idea to process this type of waste water, and be mostly directly be discharged in environment to go, situation is quite severe at all.Not only bring causing property to destroy to ecotope, also make these enterprises face the circumstances of closing down simultaneously.
Another subject matter of current chitin industrial production wastewater is, conventional waste water treatment technology, is only process, and the callable various useful compositions contained in waste water, substantially consumed in vain, not only wasted resource, and processing costs and difficulty all quite high.Also have some researchs of reclaiming about protein in waste water for producing crust element or astaxanthin both at home and abroad although current, research is nearly all rest on laboratory stage, and does not pay close attention to the process problem extracting rear waste water.Can not recycle residual a large amount of high density spent acid or salkali waste, therefore raw material consumption is very high, and production cost and the wasting of resources are all quite serious.
Chitin production wastewater is processed, only that terminal is administered, be difficult to realize cleaner production, only have by being optimized integration to whole process, consider every possible angle, cancel or reduce soda acid consumption, fully extract the main useful resources in raw material, reduce discharge of wastewater, really could reach the pattern of the sustainable health development of cleaner production and green manufacturing.Current developed country, because environmental issue, has mostly stopped producing chitin.Producing the developing countries such as the minority developed country of chitin and India, to study more for the mode of production (decalcification deproteinated) of chitin be utilize microbe fermentation method decalcification deproteinated, but decalcification and deproteinated incomplete, finally also need to use acid-base method process further, just can obtain chitin.For the acidic and alkaline waste water produced, still utilize and process to domestic similar traditional method, even directly discharge.The waste water that chitin is produced mixes process, not only has no idea up to standard, also can recycle, therefore without any future without any useful component simultaneously.
Carry out the pre-treatment of high-density steam explosion by prawn, crab husk as raw material, make the chitin of combining closely and protein and CaCO
3short texture is opened even completely, makes enzyme, acid, alkali etc. contact concurrent raw respective reaction easily with target substrates, reduces energy threshold, improves reaction efficiency, reduces reactant consumption amount.Due to the opening of crystallizing field of chitin, the solvability of chitin is improved, by chitin further de-acetyl prepare chitosan and become very easy with oligochitosan.By proteolytic enzyme, most proteolysis is become soluble proteins hydrolyzate, can collect and obtain food grade high-quality protolysate.And residual protein only just can more fully extract with a small amount of caustic soda by the residual shell removing most of albumen, greatly reduce the consumption of alkali.Comparatively clean and the residual shell of the calcic of short texture can with hydrochloric acid soln by CaCO
3remove completely, and hydrochloric acid consumption greatly reduces, the COD in acid bubble waste water also significantly reduces.The waste lye produced in the first soda boiling of chitin production process again acid leaching process and decalcification waste liquid are collected respectively, and reclaims the composition such as alkali and protein by growing membrane separation technique; General Cleaning Wastewater can carry out reuse by conventional sewage process.Realize the effective way that chitin cleaner production and resource high-efficiency fully utilize this purpose.
At present both at home and abroad not about high-density steam explosion technology pre-treatment shrimp, crab shell, and coupled enzymatic technology and membrane technique carry out the report of chitin cleaner production, inventor herein's early stage, authorized patent was also only limitted to by stainless steel membrane and alkaline-resisting nanofiltration membrane the recycling (ZL200810235932.9) of waste lye, belong to waste water terminal Treatment process, do not belong to process for cleanly preparing.High-density steam explosion technology pretreating raw material, with loose raw material imporosity, is the core key technology of this technique.SDSFE technology has 2 sections of articles to report recently and have unusual effect to opening crystallization of protein plot structure in technology such as extraction soybean protein, feather keratoprotein etc.; Steam explosion technology is more extensive in fiber papermaking sector application.
In sum, the environmental disruption of existing chitin production technology is serious, the treatment process of spent process water is extensive, processing cost is high, intractability is large, process after can not qualified discharge, cause ample resources to waste simultaneously, improve production cost.
Summary of the invention
Object of the present invention is exactly provide to overcome defect that above-mentioned prior art exists that a kind of technique is clean, environmental protection, separation purifying technique is simple, reasonable, operation is short, easy to operate, and resource obtains the process for cleanly preparing of the chitin fully utilized fully simultaneously.
Object of the present invention can be achieved through the following technical solutions: a kind of process for cleanly preparing of chitin, is characterized in that, the method comprises the following steps:
(5) dodge quick-fried: by shrimp shell and/or crab shell in high-density steam explosion device by steam pressurized to 0.1-10MPa, then moment pressure release, through the instantaneous steam explosion of 0.0875s, make shrimp shell and/or crab shell weave construction loosen expanded, the crystallizing field of chitin and protein is opened;
(6) enzymolysis: dodge quick-fried after shrimp shell and/or crab shell be transported in warm water tank, stir with the water soaking of 2-10 times of weight, regulate water temperature at 20-60 DEG C, add zymin, regulate pH3-11, enzyme digestion reaction 1-12h, 85 DEG C of enzymes that go out, coarse filtration;
(7) protein salvage: after the enzyme that goes out, enzymolysis solution coarse filtration liquid is after nanofiltration (NF) or reverse osmosis (RO) are concentrated to 8%-20%, sterilizing, drying obtain food grade hydrolyzed animal protein product;
(8) chitin preparation: enzymolysis solution filter residue is carried out successively soda boiling, acid bubble obtains chitin product, described soda boiling is soaked with the NaOH of 7%-10%, temperature 95-100 DEG C, 0.5-2h is stirred in air-blowing, bleeds off waste lye, filter residue is extremely neutral with tap water, described acid bubble be by soda boiling after material pass into the salt acid soak 1-12h of 6%-8%, air-blowing is stirred, and bleeds off spent acid solution, filter residue is extremely neutral with tap water, through natural air dry or warm air drying.
Described shrimp shell and/or crab shell first carried out pre-treatment before exploding technology, and described pre-treatment is: by the shrimp shell of fresh or drying or the coarse reduction of crab shell.
Zymin described in step (2) includes but not limited to the combination of several or more several enzyme of Sumizyme MP, stomach en-, papoid, neutral protease, trypsinase; The addition of zymin is 1 ‰-5% of shrimp shell and/or crab shell dry weight 30%.
The time preferably 1 ~ 2h of the soda boiling described in step (4), the temperature of acid bubble is room temperature; The number of times of soda boiling, acid bubble is 1 ~ 2 time.
The waste lye that alkali cooking process described in step (4) produces adopts following methods process: by waste lye successively after cartridge filter, silicon carbide material ultrafiltration membrance filter, be cooled to less than 60 DEG C, again through the process of alkaline-resisting NF membrane filtration, each step obtain containing protein concentrated solution through water-dialyzing dialysis or directly and the spent acid solution that produces of sour bubble process neutralize, drying, obtains feed grade albumen; NF filtrate is clarify clean sig water, wherein NaOH concentration 0-4%, recycle.
The spent acid solution that acid bubble process described in step (4) produces adopts following methods process: by spent acid solution through cartridge filter, silicon carbide material ultrafiltration membrane treatment, obtain high density containing a small amount of protein concentrated solution and merge with the waste lye that alkali cooking process produces neutralize, drying; What obtain contains CaCl simultaneously
2clarify neutral direct discharging of waste water to waste water treatment plant's harmless treatment.
Effective rete material of the membrane element that described ultra-filtration membrane uses is silicon carbide, and supporting layer is aluminum oxide, and membrane filtration pore diameter range is 20nm-100nm, filtration temperature 10-100 DEG C, working pressure 0.01-0.4MPa, filter type is cross flow filter, and Membrane Filtration Flux is 20-400Lm
-1h
-1.
Described NF film is membranous system, comprise membrane element, recycle pump, transferpump, electric, instrument, Controlling System, wherein the mould material of membrane element is composite high-molecular material, and membranous type is rolled film, the pH tolerance range of film is 0-14, the highest tolerance NaOH concentration is the molecular weight cut-off scope of 20%, NF film is 90Da-350Da, and filter operation temperature is 10 ~ 60 DEG C, working pressure is 0.1 ~ 4MPa, filter type is cross flow filter, and film surface velocity is 0.5 ~ 10m/s, and Membrane Filtration Flux is 5 ~ 50Lm
-1h
-1, cycles of concentration is 1 ~ 40 times.
Compared with prior art, the chitin that present invention process obtains more easily takes off acetyl and prepares chitosan and oligochitosan; The hydrolyzed animal protein product high value added product of high-quality can be obtained, significantly reduce alkali, acid consumption, complete recycling and the effective constituent comprehensive utilization of alkali waste water, non-alkali liquor is discharged in environment and goes, acid bubble liquid measure significantly reduces, and COD is reduced to below 50ppm in clarified wastewater, reach discharging standards.Whole novel process is clean, environmental protection, and separation purifying technique is simple, rationally, operation is short, easy to operate, and resource obtains and fully utilizes fully simultaneously, and avoid secondary pollution, environment protection significance is great, and remarkable in economical benefits improves, and has industrial applications and is worth.
Accompanying drawing explanation
Fig. 1 is present invention process schema.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
With 100Kg shrimp shell and shrimp processing fent for raw material, without coarse reduction, be delivered directly in high-density steam explosion (HDSFE) device, by steam pressurized to 10MPa, then 0.0875s moment pressure release is dodged quick-fried; Dodge quick-fried after feedstock transportation to 316L stainless steel reaction tank, soak with 2 times of (w/w) tap water, be warmed up to 60 DEG C, stir and adjust pH to 6.5, add 30g neutral protease (100Kg × 30% × 1 ‰), stirring reaction 12h, 85 DEG C of enzymes that go out, coarse filtration, protein enzymatic hydrolyzate is concentrated into 20% through NF or RO film by filtrate, spraying dry, obtains about 25Kg protein hydrolysate powder.Filter residue 7%NaOH solution backheat to 100 DEG C, 1h is soaked in air-blowing, and discard waste lye, slag washes with water to neutrality, then stirs immersion 12h with 6% hydrochloric acid normal temperature air-blowing, discards spent acid solution, and it is dry that pulp water is washed till neutral rear natural air dry, obtains chitin 18Kg.Waste lye directly pumps into silicon carbide film systemic circulation tank, directly recycle pump is entered add 60 order cartridge filters before or after fresh feed pump after, there is provided after pressure and certain flow rate through recycle pump and enter silicon carbide film element, feed temperature is 90 DEG C-100 DEG C, working pressure is 0.3-0.4MPa, and film surface velocity is 2-5m/s, and film mean pore size is 20nm, film average flux 400LMH, terminates after concentrated 50 times.Filtrate cools to 50-60 DEG C through interchanger, nanofiltration system is pumped into by recycle pump, working pressure 3.5-4MPa, surface velocity 10m/s, retaining molecular weight 90Da, concentrated 40 times are terminated, film average flux 50LMH, concentrated solution adds the 3 times of deionized water classification dialysis of himself volume, and dialyzate is incorporated to NF diluted alkaline filtrate, concentrated solution spray is dry, obtains 4.5Kg feed grade protein powder; Sig water clear, NaOH concentration 2.4%, COD < 50ppm, collects reuse; Acid bubble waste water directly pumps into silicon carbide film systemic circulation tank, directly recycle pump is entered add 60 order cartridge filters before or after fresh feed pump after, there is provided after pressure and certain flow rate through recycle pump and enter silicon carbide film element, feed temperature is 20 DEG C-50 DEG C, working pressure is 0.1MPa, film surface velocity is 2-5m/s, film mean pore size is 20nm, film average flux 200LMH, terminate after concentrated 50 times, liquor C OD < 50ppm, directly discharges or is incorporated to municipal wastewater process pipe network, containing protein concentrated solution and salkali waste concentrated solution entirely and process.
Described HDSFE device is that instant steam dodges quick-fried device, is core technology of the present invention; Silicon carbide film element is tubular structure, comprises film supporting layer, rete, and the material of described film supporting layer is aluminum oxide, and the material of rete is silicon carbide, and film mean pore size is 20nm; Described nanofiltration membrane is rolling composite high-molecular material film, and molecular weight cut-off 90Da, can tolerate 20%NaOH alkali concn.
Embodiment 2
With 100Kg Alaska cod crab shell for raw material, be transported in HDSFE device after coarse reduction, by steam pressurized to 2MPa, then 0.0875s moment pressure release is dodged quick-fried; Dodge quick-fried after feedstock transportation to 316L stainless steel reaction tank, soak with 10 times of (w/w) tap water, be warmed up to 40 DEG C, stir and adjust pH to 11, add 1.5Kg Sumizyme MP (100Kg × 30% × 5%), stirring reaction 4h, 85 DEG C of enzymes that go out, coarse filtration, protein enzymatic hydrolyzate is concentrated into 8% through NF or RO film by filtrate, spraying dry, obtains about 28Kg protein hydrolysate powder.Filter residue 10%NaOH solution backheat to 95 DEG C, 0.5h is soaked in air-blowing, and discard waste lye, slag washes with water to neutrality, then stirs immersion 1h with 8% hydrochloric acid normal temperature air-blowing, discards spent acid solution, and it is dry that pulp water is washed till neutral rear natural air dry, obtains chitin 18.5Kg.Waste lye directly pumps into silicon carbide film systemic circulation tank, directly recycle pump is entered add 60 order cartridge filters before or after fresh feed pump after, there is provided after pressure and certain flow rate through recycle pump and enter silicon carbide film element, feed temperature is 10 DEG C, working pressure is 0.01MPa, and film surface velocity is 2m/s, and film mean pore size is 100nm, film average flux 20LMH, terminates after concentrated 30 times.Filtrate temperature 10 DEG C, pumps into nanofiltration system by recycle pump, working pressure 0.1MPa, surface velocity 0.5m/s, retaining molecular weight 350Da, concentrated 1 times is terminated, film average flux 5LMH, concentrated solution and the merging of acid bubble wastewater membrane concentrated solution neutralize, spray is dry, obtain 6Kg feed grade protein powder; Sig water clear, NaOH concentration 3.5%, COD < 50ppm, collects reuse; Acid bubble waste water directly pumps into silicon carbide film systemic circulation tank, directly recycle pump is entered add 60 order cartridge filters before or after fresh feed pump after, there is provided after pressure and certain flow rate through recycle pump and enter silicon carbide film element, feed temperature is 10 DEG C, working pressure is 0.4MPa, film surface velocity is 2-5m/s, film mean pore size is 20nm, film average flux 20LMH, terminate after concentrated 50 times, liquor C OD < 50ppm, directly discharges or is incorporated to municipal wastewater process pipe network, containing protein concentrated solution and salkali waste concentrated solution entirely and process.
Described HDSFE device is that instant steam dodges quick-fried device, is core technology of the present invention; Silicon carbide film element is tubular structure, comprises film supporting layer, rete, and the material of described film supporting layer is aluminum oxide, and the material of rete is silicon carbide, and film mean pore size is 20nm and 100nm; Described nanofiltration membrane is rolling composite high-molecular material film, and molecular weight cut-off 350Da, can tolerate 20%NaOH alkali concn.
Embodiment 3
With 100Kg small lobsters shell for raw material, be transported in HDSFE device after coarse reduction, by steam pressurized to 4MPa, then 0.0875s moment pressure release is dodged quick-fried; Dodge quick-fried after feedstock transportation to 316L stainless steel reaction tank, soak with 5 times of (w/w) tap water, temperature 10 DEG C, stirs and adjusts pH to 3, adds 0.3Kg compound protease (containing papoid, trypsinase, stomach en-) (100Kg × 30% × 1%), stirring reaction 1h, 85 DEG C of enzymes that go out, coarse filtration, protein enzymatic hydrolyzate is concentrated into 18% through NF or RO film by filtrate, spraying dry, obtains about 26Kg protein hydrolysate powder.Filter residue 7%NaOH solution backheat to 95 DEG C, 2h is soaked in air-blowing, discard waste lye, slag washes with water to neutrality, then stirs immersion 12h with 8% hydrochloric acid normal temperature air-blowing, discards spent acid solution, after pulp water is washed till neutrality, repeat alkali, acid bubble 1 time, it is dry that pulp water is washed till neutral rear natural air dry, obtains chitin 15Kg.Waste lye directly pumps into silicon carbide film systemic circulation tank, directly recycle pump is entered add 60 order cartridge filters before or after fresh feed pump after, there is provided after pressure and certain flow rate through recycle pump and enter silicon carbide film element, feed temperature is 90 DEG C, working pressure is 0.1-0.25MPa, and film surface velocity is 5m/s, and film mean pore size is 40nm, film average flux 200LMH, terminates after concentrated 50 times.Filtrate heat exchange is cooled to 40 DEG C, pumps into nanofiltration system by recycle pump, working pressure 3MPa, surface velocity 3.5m/s, retaining molecular weight 150Da, concentrated 25 times are terminated, film average flux 15LMH, concentrated solution and the merging of acid bubble wastewater membrane concentrated solution neutralize, spray is dry, obtain 4Kg feed grade protein powder; Sig water clear, NaOH concentration 1.8%, COD < 50ppm, collects reuse; Acid bubble waste water directly pumps into silicon carbide film systemic circulation tank, directly recycle pump is entered add 60 order cartridge filters before or after fresh feed pump after, there is provided after pressure and certain flow rate through recycle pump and enter silicon carbide film element, feed temperature is 30 DEG C, working pressure is 0.2MPa, film surface velocity is 2-5m/s, film mean pore size is 40nm, film average flux 260LMH, terminate after concentrated 50 times, liquor C OD < 50ppm, directly discharges or is incorporated to municipal wastewater process pipe network, containing protein concentrated solution and salkali waste concentrated solution entirely and process.
Described HDSFE device is that instant steam dodges quick-fried device, is core technology of the present invention; Silicon carbide film element is tubular structure, comprises film supporting layer, rete, and the material of described film supporting layer is aluminum oxide, and the material of rete is silicon carbide, and film mean pore size is 40nm; Described nanofiltration membrane is rolling composite high-molecular material film, and molecular weight cut-off 150Da, can tolerate 20%NaOH alkali concn.
Embodiment 4
With 100Kg Alaska cod crab shell for raw material, be delivered directly in HDSFE device without coarse reduction, by steam pressurized to 0.1MPa, then 0.0875s moment pressure release is dodged quick-fried; Dodge quick-fried after feedstock transportation to 316L stainless steel reaction tank, soak with 5 times of (w/w) tap water, temperature 45 C, stirs and adjusts pH to 5.5, adds 90g compound protease (containing neutral protease, trypsinase, stomach en-) (100Kg × 30% × 3 ‰), stirring reaction 6h, 85 DEG C of enzymes that go out, coarse filtration, protein enzymatic hydrolyzate is concentrated into 20% through NF or RO film by filtrate, spraying dry, obtains about 28Kg protein hydrolysate powder.Filter residue 7%NaOH solution backheat to 95 DEG C, 1h is soaked in air-blowing, and discard waste lye, slag washes with water to neutrality, then stirs immersion 8h with 6% hydrochloric acid normal temperature air-blowing, discards spent acid solution, and it is dry that pulp water is washed till neutral rear natural air dry, obtains chitin 18Kg.Waste lye directly pumps into silicon carbide film systemic circulation tank, directly recycle pump is entered add 60 order cartridge filters before or after fresh feed pump after, there is provided after pressure and certain flow rate through recycle pump and enter silicon carbide film element, feed temperature is 90 DEG C, working pressure is 0.1-0.25MPa, and film surface velocity is 5m/s, and film mean pore size is 40nm, film average flux 200LMH, terminates after concentrated 50 times.Filtrate heat exchange is cooled to 60 DEG C, nanofiltration system is pumped into by recycle pump, working pressure 3.5MPa, surface velocity 3.5m/s, retaining molecular weight 90Da, concentrated 20 times are terminated, film average flux 18LMH, concentrated solution adds the 3 times of deionized water dialysis of its volume, and water-dialyzing is merged into reuse in NF filtrate, and concentrated solution spray is so dry that to obtain 2Kg feed grade protein powder; Sig water clear, NaOH concentration 1.4%, COD < 50ppm, collects reuse; Acid bubble waste water directly pumps into silicon carbide film systemic circulation tank, directly recycle pump is entered add 60 order cartridge filters before or after fresh feed pump after, there is provided after pressure and certain flow rate through recycle pump and enter silicon carbide film element, feed temperature is 20 DEG C, working pressure is 0.4MPa, film surface velocity is 2-5m/s, film mean pore size is 40nm, film average flux 180LMH, terminate after concentrated 50 times, liquor C OD < 50ppm, directly discharges or is incorporated to municipal wastewater process pipe network, containing protein concentrated solution and salkali waste concentrated solution entirely and process.
Described HDSFE device is that instant steam dodges quick-fried device, is core technology of the present invention; Silicon carbide film element is tubular structure, comprises film supporting layer, rete, and the material of described film supporting layer is aluminum oxide, and the material of rete is silicon carbide, and film mean pore size is 40nm; Described nanofiltration membrane is rolling composite high-molecular material film, and molecular weight cut-off 90Da, can tolerate 20%NaOH alkali concn.
Chitin clearer production technology of the present invention, HDSFE pre-treatment is the key point of whole technique, makes simple, remarkably productive; The chitin obtained more de-acetyl prepares chitosan and oligochitosan; The proteolysate quality of enzyme-squash techniqued is high, remarkable in economical benefits; Separation purifying technique is simple, rationally, unit operation is convenient, and the alkali lye that separation obtains is clean, purity is high, the rate of recovery is high; Use silicon carbide film separation system one-time investment cost low, membrane lifetime is long, has that running cost is low, filtering accuracy is high, cycles of concentration is high, concentrated solution concentration advantages of higher; The nanofiltration membrane used has alkaline resistance properties and physical strength well, and membrane lifetime is long, and running cost is low, and separation accuracy is very high, and cycles of concentration is high, and concentrated solution concentration is high, is conducive to concentrated solution solidification recycling.Technical characterstic of the present invention is green manufacturing, the cleaner production of whole process, and solving over only can the wretched insufficiency of end treatment.
Claims (6)
1. a process for cleanly preparing for chitin, is characterized in that, the method comprises the following steps:
(1) dodge quick-fried: by shrimp shell and/or crab shell in high-density steam explosion device by steam pressurized to 0.1-10MPa, then moment pressure release, through the instantaneous steam explosion of 0.0875s, make shrimp shell and/or crab shell weave construction loosen expanded, the crystallizing field of chitin and protein is opened;
(2) enzymolysis: dodge quick-fried after shrimp shell and/or crab shell be transported in warm water tank, stir with the water soaking of 2-10 times of weight, regulate water temperature at 20-60 DEG C, add zymin, regulate pH3-11, enzyme digestion reaction 1-12h, 85 DEG C of enzymes that go out, coarse filtration;
(3) protein salvage: after the enzyme that goes out, enzymolysis solution coarse filtration liquid is after nanofiltration (NF) or reverse osmosis (RO) are concentrated to 8%-20%, sterilizing, drying obtain food grade hydrolyzed animal protein product;
(4) chitin preparation: enzymolysis solution filter residue is carried out successively soda boiling, acid bubble obtains chitin product, described soda boiling is soaked with the NaOH of 7%-10%, temperature 95-100 DEG C, 0.5-2h is stirred in air-blowing, bleeds off waste lye, filter residue is extremely neutral with tap water, described acid bubble be by soda boiling after filter residue pass into the salt acid soak 1-12h of 6%-8%, air-blowing is stirred, and bleeds off spent acid solution, filter residue is extremely neutral with tap water, through natural drying or warm air drying;
The waste lye that alkali cooking process described in step (4) produces adopts following methods process: by waste lye successively after cartridge filter, silicon carbide material ultrafiltration membrance filter, be cooled to less than 60 DEG C, again through the process of alkaline-resisting NF membrane filtration, each step obtain containing protein concentrated solution through water-dialyzing dialysis or directly and the spent acid solution that produces of sour bubble process neutralize, drying, obtains feed grade albumen; NF filtrate is clarify clean sig water, wherein NaOH concentration 0-4%, recycle;
The spent acid solution that acid bubble process described in step (4) produces adopts following methods process: by spent acid solution through cartridge filter, silicon carbide material ultrafiltration membrane treatment, obtain high density containing a small amount of protein concentrated solution and merge with the waste lye that alkali cooking process produces neutralize, drying; What obtain contains CaCl simultaneously
2clarify neutral direct discharging of waste water to waste water treatment plant's harmless treatment.
2. the process for cleanly preparing of a kind of chitin according to claim 1, is characterized in that, described shrimp shell and/or crab shell first carried out pre-treatment before exploding technology, and described pre-treatment is: by the shrimp shell of fresh or drying or the coarse reduction of crab shell.
3. the process for cleanly preparing of a kind of chitin according to claim 1, is characterized in that, the zymin described in step (2) comprises the combination of several enzyme in Sumizyme MP, stomach en-, papoid, neutral protease, trypsinase; The addition of zymin is 1 ‰-5% of shrimp shell and/or crab shell dry weight 30%.
4. the process for cleanly preparing of a kind of chitin according to claim 1, is characterized in that, the time preferably 1 ~ 2h of the soda boiling described in step (4), and the temperature of acid bubble is room temperature; The number of times of soda boiling, acid bubble is 1 ~ 2 time.
5. the process for cleanly preparing of a kind of chitin according to claim 1, it is characterized in that, effective rete material of the membrane element that described ultra-filtration membrane uses is silicon carbide, supporting layer is aluminum oxide, membrane filtration pore diameter range is 20nm-100nm, filtration temperature 10-100 DEG C, working pressure 0.01-0.4MPa, filter type is cross flow filter, and Membrane Filtration Flux is 20-400Lm
-2h
-1
。
6. the process for cleanly preparing of a kind of chitin according to claim 1, it is characterized in that, described NF film is membranous system, comprise membrane element, recycle pump, transferpump, electrically, instrument, Controlling System, wherein the mould material of membrane element is composite high-molecular material, membranous type is rolled film, the pH tolerance range of film is 0-14, the highest tolerance NaOH concentration is 20%, the molecular weight cut-off scope of NF film is 90Da-350Da, filter operation temperature is 10 ~ 60 DEG C, working pressure is 0.1 ~ 4MPa, filter type is cross flow filter, film surface velocity is 0.5 ~ 10m/s, Membrane Filtration Flux is 5 ~ 50Lm
-2h
-1
, cycles of concentration is 1 ~ 40 times.
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| CN104059953A (en) * | 2013-09-29 | 2014-09-24 | 天津天狮生物发展有限公司 | Chitosan enzymatic hydrolysis method |
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