CN114230380A - Utilization method of 7-aminocephalosporanic acid production waste - Google Patents
Utilization method of 7-aminocephalosporanic acid production waste Download PDFInfo
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- CN114230380A CN114230380A CN202111480353.2A CN202111480353A CN114230380A CN 114230380 A CN114230380 A CN 114230380A CN 202111480353 A CN202111480353 A CN 202111480353A CN 114230380 A CN114230380 A CN 114230380A
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- HSHGZXNAXBPPDL-HZGVNTEJSA-N 7beta-aminocephalosporanic acid Chemical compound S1CC(COC(=O)C)=C(C([O-])=O)N2C(=O)[C@@H]([NH3+])[C@@H]12 HSHGZXNAXBPPDL-HZGVNTEJSA-N 0.000 title claims abstract description 36
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 71
- 102000004190 Enzymes Human genes 0.000 claims abstract description 57
- 108090000790 Enzymes Proteins 0.000 claims abstract description 57
- OYIFNHCXNCRBQI-UHFFFAOYSA-N 2-aminoadipic acid Chemical compound OC(=O)C(N)CCCC(O)=O OYIFNHCXNCRBQI-UHFFFAOYSA-N 0.000 claims abstract description 56
- 240000006439 Aspergillus oryzae Species 0.000 claims abstract description 30
- 235000002247 Aspergillus oryzae Nutrition 0.000 claims abstract description 30
- 150000001413 amino acids Chemical class 0.000 claims abstract description 29
- HOKIDJSKDBPKTQ-GLXFQSAKSA-N cephalosporin C Chemical compound S1CC(COC(=O)C)=C(C(O)=O)N2C(=O)[C@@H](NC(=O)CCC[C@@H](N)C(O)=O)[C@@H]12 HOKIDJSKDBPKTQ-GLXFQSAKSA-N 0.000 claims abstract description 28
- 241000228245 Aspergillus niger Species 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 238000001728 nano-filtration Methods 0.000 claims abstract description 18
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 235000001674 Agaricus brunnescens Nutrition 0.000 claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 239000003337 fertilizer Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 239000001963 growth medium Substances 0.000 claims abstract description 10
- 238000000855 fermentation Methods 0.000 claims abstract description 8
- 230000004151 fermentation Effects 0.000 claims abstract description 8
- 239000000835 fiber Substances 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 7
- 239000003895 organic fertilizer Substances 0.000 claims abstract description 7
- 230000002255 enzymatic effect Effects 0.000 claims abstract description 6
- 239000000919 ceramic Substances 0.000 claims abstract description 5
- 239000000413 hydrolysate Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229930186147 Cephalosporin Natural products 0.000 claims abstract description 4
- 229940124587 cephalosporin Drugs 0.000 claims abstract description 4
- 150000001780 cephalosporins Chemical class 0.000 claims abstract description 4
- 239000012452 mother liquor Substances 0.000 claims abstract description 3
- HOKIDJSKDBPKTQ-GLXFQSAKSA-M cephalosporin C(1-) Chemical compound S1CC(COC(=O)C)=C(C([O-])=O)N2C(=O)[C@@H](NC(=O)CCC[C@@H]([NH3+])C([O-])=O)[C@@H]12 HOKIDJSKDBPKTQ-GLXFQSAKSA-M 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 102000012286 Chitinases Human genes 0.000 claims description 13
- 108010022172 Chitinases Proteins 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000012258 culturing Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000001954 sterilising effect Effects 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000012065 filter cake Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005273 aeration Methods 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229940088598 enzyme Drugs 0.000 description 41
- 230000000694 effects Effects 0.000 description 18
- 241000233866 Fungi Species 0.000 description 16
- 230000001580 bacterial effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 241001052560 Thallis Species 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 210000002421 cell wall Anatomy 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 108091005508 Acid proteases Proteins 0.000 description 4
- 108090000145 Bacillolysin Proteins 0.000 description 4
- 108091005507 Neutral proteases Proteins 0.000 description 4
- 102000035092 Neutral proteases Human genes 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229920002774 Maltodextrin Polymers 0.000 description 3
- 239000005913 Maltodextrin Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000009630 liquid culture Methods 0.000 description 3
- 229940035034 maltodextrin Drugs 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 108090000204 Dipeptidase 1 Proteins 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 102000006635 beta-lactamase Human genes 0.000 description 2
- 229940041514 candida albicans extract Drugs 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 2
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000012138 yeast extract Substances 0.000 description 2
- 241001019659 Acremonium <Plectosphaerellaceae> Species 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 108010073178 Glucan 1,4-alpha-Glucosidase Proteins 0.000 description 1
- 102100022624 Glucoamylase Human genes 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 101710163270 Nuclease Proteins 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 102000003929 Transaminases Human genes 0.000 description 1
- 108090000340 Transaminases Proteins 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000002924 anti-infective effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000002773 nucleotide Substances 0.000 description 1
- 125000003729 nucleotide group Chemical group 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C11/00—Other nitrogenous fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/20—Liquid fertilisers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a method for utilizing waste produced in 7-aminocephalosporanic acid production, which comprises the following steps: (1) regulating pH of fresh wet residue of cephalosporin C to 5.5-6.0 with alkali, adding complex enzyme preparation in certain proportion, and performing enzymolysis at 55-60 deg.C for 48-72 hr; (2) separating the calcium oxalate salt and part of fibers from the enzymatic hydrolysate by using a decanter centrifuge, wherein the calcium oxalate salt and part of the fibers can be used as organic fertilizer raw materials; (3) treating the centrifugate by using ceramic membrane ultrafiltration equipment, respectively collecting filtrate and filter residue, wherein one part of the ultrafiltration filter residue is used as a culture medium for fermentation preparation of aspergillus oryzae or aspergillus niger liquid enzyme, and the other part of the ultrafiltration filter residue is added into the next batch of cephalosporin fresh mushroom residue for secondary enzymolysis; (4) nanofiltration and concentration of ultrafiltrate; (5) and (4) adding alpha-amino adipic acid into the nanofiltration concentrated solution in the step (4) for blending to obtain an amino acid liquid fertilizer or a production raw material thereof, wherein the alpha-amino adipic acid is derived from 7-ACA extraction mother liquor.
Description
Technical Field
The invention relates to the technical field of environment-friendly wastewater treatment, and particularly relates to a utilization method of 7-aminocephalosporanic acid production waste.
Background
The cephalosporin medicine has good curative effect ¸, low allergy and about 40% of the market share of anti-infective medicine, and the 7-aminocephalosporanic acid (7-ACA) as the main raw material is produced by enzymatic cleavage of cephalosporin C. Producing cephalosporin C by fermenting and culturing acremonium, removing bacterium residue by ultrafiltration, and cutting alpha-amino adipic acid by immobilized cephalosporin C acylase to produce 7-ACA. Cephalosporin C bacterial residue and alpha-amino adipic acid are two main production wastes in 7-ACA production.
The cephalosporin C residues contain cephalosporin C residues, which are listed as dangerous wastes by the state and are strictly regulated by environmental protection departments. Three patents with the grant numbers of CN102392008B and CN108048519B and the publication number of CN101935682A respectively provide a technical scheme that the cephalosporin C fungus dregs replace part of the fermentation culture medium components for cyclic application, but only part of the fungus dregs can be applied; the patent of publication No. CN109776238A provides a technical scheme for producing amino acid fertilizer by decomposing cephalosporin C filter residue with strong acid, but has the disadvantages that part of kinds of amino acids are destroyed by strong acid, the nutrition of ¸ amino acids is incomplete, and the application range of a large amount of salts ¸ in the product is limited. At present, most of cephalosporin C fungus residues are dried and then used for producing organic fertilizers, so that the economic value is extremely low; the drying mode that adopts, a few producers utilize the plate frame to squeeze and remove partial moisture earlier and then dry, can save partial steam cost, but because there is a large amount of colloidal substance ¸ operability poor in the fungus sediment, can cause secondary pollution, so most producers adopt directly to carry out the mode of cylinder drying or spray drying with wet fungus sediment at present, no matter how dry the mode all need consume a large amount of energy, and cephalosporin C remains and is not thoroughly eliminated, has certain potential safety hazard.
Alpha-amino adipic acid is a main waste except cephalosporin C bacterial residue in 7-ACA production, and has no good market application, so that the alpha-amino adipic acid enters a sewage treatment plant along with 7-ACA extraction waste liquid basically at present, and the alpha-amino adipic acid is a main reason for causing the extraction waste liquid to become high-COD waste water.
Disclosure of Invention
The invention provides a method for utilizing waste produced by 7-aminocephalosporanic acid, aiming at the problems in the waste produced by the traditional 7-aminocephalosporanic acid.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
a utilization method of 7-aminocephalosporanic acid production waste comprises the following steps:
(1) regulating pH of fresh wet residue of cephalosporin C to 5.5-6.0 with alkali, adding complex enzyme preparation in certain proportion, and performing enzymolysis at 55-60 deg.C for 48-72 hr;
(2) separating the enzymatic hydrolysate from the calcium salt of herbicidal acid, partial fiber and other substances by a sedimentation centrifuge;
(3) treating the centrifugate with ceramic membrane ultrafiltration equipment, and respectively collecting filtrate and residue;
(4) concentrating the ultrafiltrate with nanofiltration membrane;
(5) and (4) adding alpha-amino adipic acid into the nanofiltration concentrated solution in the step (4) for blending to obtain an amino acid liquid fertilizer or a production raw material thereof, wherein the alpha-amino adipic acid is derived from 7-ACA extraction mother liquor.
Preferably, the complex enzyme preparation in the step (1) is one of aspergillus oryzae liquid enzymes or a mixture of the aspergillus oryzae liquid enzymes and the aspergillus niger liquid enzymes.
Further preferably, the complex enzyme preparation in the step (1) also comprises 4-20U/ml of chitinase;
preferably, the total amount of the aspergillus oryzae liquid enzyme and the aspergillus niger liquid enzyme in the complex enzyme preparation in the step (1) is 5-15%, the proportion of the aspergillus oryzae liquid enzyme and the aspergillus niger liquid enzyme is 80-100:0-20, and the optimal proportion is 85-90: 10-15%;
in the step (1), the liquefaction rate of the organic matters in the enzymolysis liquid is controlled to be more than or equal to 70 percent, and the thallus concentration of the enzymolysis liquid is controlled to be less than or equal to 20 percent;
preferably, the pore diameter of the ultrafiltration membrane in the step (2) is 10-50 nm;
preferably, the concentration of the nanofiltration liquid in the step (4) is controlled to be 15-20% of soluble solid content and 5-7% of amino acid content.
Preferably, the preparation step of the alpha-amino adipic acid added in the step (5) comprises the following steps: collecting 7-ACA extraction waste liquid; concentrating a nanofiltration membrane; regulating the pH of the concentrated solution to 5.0 with hydrochloric acid, crystallizing for 2h, and then continuously regulating the pH to 3.5, and crystallizing for 4 h; and (3) carrying out plate-frame filtration on the crystal liquid, carrying out top washing by deionized water, and carrying out vacuum drying on a filter cake to obtain the alpha-amino adipic acid.
Preferably, the Aspergillus oryzae and Aspergillus niger liquid enzyme culture medium in step 1 comprises: 15-50% of fresh cephalosporin C residues ¸ 0-15% of the ultrafiltration filter residues ¸ and inorganic salt ¸ 0.3.3-1% of quick-acting organic carbon source and nitrogen source in the proportion of the Chaochou culture medium in the step (3), wherein the maltodextrin, the enzymolysis liquid, the yeast extract powder and the like belong to the quick-acting organic carbon source and the nitrogen source.
Preferably, the preparation steps of aspergillus oryzae and aspergillus niger liquid enzyme in step 1 comprise: adjusting pH of the culture medium with liquid alkali to 5.5-6.5, sterilizing at 121 deg.C for 20-30 min, inoculating strain, and culturing at 28-32 deg.C for 30-42h under aeration.
Aspergillus oryzae is preferably AS3.042, Aspergillus niger is preferably AS 3.350.
Preferably, the nanofiltration concentrated solution in the step 4 can be further concentrated, evaporated to remove water and dried in vacuum to obtain amino acid solid powder.
Preferably, the calcium oxalate, fiber and the like in step 2 are centrifugally precipitated to be used as organic fertilizer raw materials.
Preferably, a part of the ultrafiltration residues in step 3 is used as a fermentation preparation culture medium for aspergillus oryzae or aspergillus niger liquid enzyme, and the other part of the ultrafiltration residues is added into the next batch of cephalosporin fresh residues for secondary enzymolysis.
The term "liquefaction rate" referred to in the present invention is defined as the mass percentage of the soluble small molecular substances decomposed by the complex enzyme into the cephalosporin C fungi residues to the total organic matter mass in the fresh fungi residues. The liquefaction rate is a main index for evaluating the catalytic effect of the complex enzyme and is also a key factor influencing whether the mechanical dehydration can be adopted.
The term "cell concentration" as referred to herein is defined as the difference between the volume of the supernatant as a percentage of the total volume and 100% of the total volume, by adding fresh mushroom grounds or enzymatic hydrolysate to a graduated tube, centrifuging for 10 minutes at 3000 rpm in a desktop centrifuge, transferring the supernatant to another graduated tube and reading the volume. "cell density" is an important index for evaluating the liquefaction effect of the enzymatic hydrolysate.
In the later fermentation stage of cephalosporin C, almost all thalli are broken into single round spores, after acidification and ultrafiltration, spore cell membranes are broken to release small molecular substances, but cell walls are kept complete and occupy a relatively large physical space, so that the viscosity of the fungus residues after ultrafiltration is extremely high, and the enzymolysis of macromolecular organic matters in cells or embedded on the cell walls is influenced. The basic skeleton of the fungal cell wall is chitin, and microorganisms such as aspergillus oryzae and the like can also produce certain chitinase activity through induction, but the cell wall is not enough to be quickly damaged so that other complex enzymes can quickly liquefy the fungi residues. Therefore, the activity of the chitinase becomes a bottleneck for limiting the enzymolysis speed and efficiency in the cephalosporin C fungus dreg treatment technology.
The invention has the beneficial effects that:
the invention screens out microbial strains with rich enzyme systems, and utilizes an optimized culture medium to carry out liquid culture to obtain a compound enzyme preparation which is rich in protease ¸ glucoamylase ¸ lipase ¸ nuclease ¸ cellulase ¸ chitinase ¸ beta-lactamase, the activity of the chitinase is particularly and pertinently strengthened in the enzymolysis process, the integrity of the cell walls of the thalli can be rapidly destroyed, the multienzyme synergistic effect is realized, the fungus residues are efficiently liquefied and decomposed, the physical volume of the thalli is greatly reduced, the viscosity of the enzymolysis solution and the concentration of the thalli are greatly reduced, a foundation is laid for the subsequent separation operation and high liquefaction yield, the problem that the single enzyme is poor in the effect of decomposing protein raw materials is thoroughly solved, particularly, the technical bottleneck that the liquefaction effect of mycelia in cephalosporin C fungus residues is poor is realized, and the amino acid liquid raw materials produced by a biological enzyme method have economy and feasibility. The decomposition of beta-lactamase and the long-time enzymolysis at high temperature of nearly 60 ℃, the antibiotic residues such as cephalosporin C and the like are completely inactivated, and the problem of potential safety hazard is synchronously solved.
The mushroom residue enzymolysis treatment liquid and alpha-amino adipic acid are combined for use, so that the problem of environment-friendly treatment of main wastes in 7-ACA production is thoroughly solved; except that a small amount of steam is used for disinfection in the preparation stage of the biological enzyme, the other stages adopt a nanofiltration and centrifugation mode to carry out mechanical dewatering, thereby greatly saving energy consumption, having low treatment cost and solving the contradiction between product cost and price in the environment-friendly treatment process of the waste produced in the 7-aminocephalosporanic acid production.
The product of the invention has comprehensive amino acid nutrition, avoids the defect of serious damage to certain types of amino acids in the chemical production, and is rich in functional substances such as monosaccharide ¸ fatty acid ¸ nucleotide ¸ oligochitosan and the like; although alpha-aminoadipic acid is a non-protein amino acid, alpha-aminoadipic acid is ubiquitous in plant ¸ animals, is an important intermediate for synthesizing other amino acids, and can transfer an amino group to a keto acid metabolite under the catalysis of transaminase to produce the corresponding amino acid. Therefore, the amino acid liquid fertilizer has a far better using effect than products on the market.
Detailed Description
In order that the above objects, features and advantages of the present invention may be more clearly understood, the present invention will be further described with reference to specific embodiments. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and thus the present invention is not limited to the specific embodiments of the present disclosure.
Example 1
The embodiment provides a utilization method of 7-aminocephalosporanic acid production waste, which comprises the following steps:
(1) 500L of fresh mushroom dregs, 86 percent of detected thallus concentration and 15.3 percent of solid content, adjusting the pH value to 5.8 by using liquid caustic soda, adding 45L of prepared aspergillus oryzae liquid enzyme, adding 40g (10 ten thousand U/g) of chitinase, and performing enzymolysis for 70 hours at 58 ℃. The concentration of the bacteria in the enzymolysis liquid is 14 percent, the liquefaction rate of the organic matter is 83.6 percent, and the residue of the cephalosporin C is not detected.
(2) 31.2kg of the enzymolysis liquid is removed with a sedimentation centrifuge to remove calcium oxalate salt, partial fiber and other substances.
(3) Ultrafiltering with 50nm ceramic membrane, adding water for 2 times (100L each time), and collecting 625.5L filtrate and 88.5L residue respectively.
(4) The ultrafiltrate was concentrated with nanofiltration membrane to a volume of 289L. The content of the solid matter is detected to be 18.4 percent, and the content of the amino acid is detected to be 5.94 percent.
(5) 14.5kg of prepared alpha-amino adipic acid is added into the concentrated solution, and the pH is adjusted by alkali to be completely dissolved, so that the agricultural amino acid liquid fertilizer or the raw material for producing the amino acid liquid fertilizer is obtained.
Example 2
The embodiment provides a utilization method of 7-aminocephalosporanic acid production waste, which comprises the following steps:
(1) adding 920L of fresh mushroom dregs into 80L of the ultrafiltration residues collected in the step (3) in the embodiment 1, mixing, detecting that the concentration of the mushroom is 84.8 percent and the solid content is 15.1 percent, adjusting the pH value to be 5.8 by using liquid caustic soda, adding 88L of prepared aspergillus oryzae liquid enzyme and 10L of prepared aspergillus niger liquid enzyme, adding 60g (10 ten thousand U/g) of chitinase, and performing enzymolysis for 70 hours at 57 ℃. The concentration of the thalli of the enzymolysis liquid is 13.4 percent, the liquefaction rate of the organic matter is 85.9 percent, and the residue of the cephalosporin C is not detected.
(2) 72.3kg of substances such as calcium oxalate salt and fiber are removed from the enzymolysis solution by a continuous sedimentation centrifuge
(3) The centrifugate is ultrafiltered with 20nm ceramic membrane, and water is added for 2 times, 150L each time, and 1168.4L filtrate and 159.6L residue are collected respectively.
(4) Concentrating the ultrafiltrate to 562L by using a nanofiltration membrane, and detecting the solid content to be 19.2 percent and the amino acid content to be 6.13 percent.
(5) 28kg of prepared alpha-amino adipic acid is added into the concentrated solution, and the pH is adjusted by alkali to be completely dissolved, so that the agricultural amino acid liquid fertilizer or the raw material for producing the amino acid liquid fertilizer is obtained.
The preparation process of the aspergillus oryzae liquid enzyme in the example 1 and the example 2 is as follows:
(1) adding 10L of fresh mushroom dregs into a 50L fermentation tank, adding 30g of dipotassium hydrogen phosphate, 15g of magnesium sulfate heptahydrate, 15g of potassium chloride, 0.15g of ferrous sulfate, 150g of maltodextrin and 50g of yeast extract powder, fixing the volume to about 23L by using deionized water, and adjusting the pH value to 5.8 by using liquid alkali. Sterilizing at 121 deg.C for 20 min, cooling to 32 deg.C, inoculating 1.5L Aspergillus oryzae AS3.042 liquid culture seed, and controlling volume to about 30L. Ventilating and culturing for 36h, controlling dissolved oxygen at 20% or more in the whole course, and controlling pH at 6.0-6.2 with liquid alkali or acid in the whole course. The Aspergillus oryzae culture solution is used for detecting the activity of the neutral protease of 421.2U/ml and the activity of the chitinase of 0.64U/ml, thus obtaining the Aspergillus oryzae solution enzyme.
The preparation process of the aspergillus niger liquid enzyme in the example 2 is as follows:
(2) 12L of fresh mushroom dregs are added into a 50L fermentation tank, 3L of ultrafiltration dregs obtained in the step (3) of the embodiment 2 are added, 30g of dipotassium hydrogen phosphate, 15g of magnesium sulfate heptahydrate, 15g of potassium chloride, 0.15g of ferrous sulfate, 150g of maltodextrin and 0.5L of cephalosporin C enzymolysis liquid are added, deionized water is used for fixing the volume to about 23L, and the pH value is adjusted to 5.5 by liquid alkali. Sterilizing at 121 deg.C for 20 min, cooling to 30 deg.C, inoculating Aspergillus niger AS3.350 liquid culture seed 1.5L, and controlling volume at about 30L. Ventilating and culturing for 36h, controlling dissolved oxygen at 20% or more in the whole course, and controlling pH at 5.5-5.8 with liquid alkali or acid in the whole course. Detecting 324.7U/ml acid protease and 1.23U/ml chitinase activity by the Aspergillus niger culture solution, namely obtaining the Aspergillus niger liquid enzyme.
The preparation process of the alpha-amino adipic acid obtained in examples 1 and 2 is as follows:
(1) collecting 7-ACA extraction waste liquid 10000L, detecting alpha-amino adipic acid content of 0.83%, and concentrating with nanofiltration membrane to 984L.
(2) The concentrated solution is adjusted to pH5.0 by hydrochloric acid and crystallized for 2h, and then adjusted to pH3.5 and crystallized for 4 h.
(3) And (3) carrying out plate-frame filtration on the crystal liquid, carrying out top washing on 100L of deionized water, and carrying out vacuum drying on a filter cake to obtain alpha-amino adipic acid with the weight of 63.8kg and the content of 99.5%, wherein 7-ACA is not detected.
(4) And (3) collecting the filtrate, mixing the filtrate with the next 7-ACA extraction waste liquid, and extracting alpha-amino adipic acid.
Comparison experiment of enzymolysis effect:
(1) the neutral protease ¸ and the acid protease ¸ aspergillus oryzae liquid enzyme ¸ aspergillus niger liquid enzyme ¸ chitinase are used singly or in combination to carry out enzymolysis on fresh cephalosporin C bacterial dregs according to a certain enzyme activity unit.
(2) Neutral protease ¸ acid protease ¸ chitinase is a commercially available enzyme, Aspergillus oryzae solution enzyme is derived from the Aspergillus oryzae broth in this example, Aspergillus niger solution enzyme is derived from the Aspergillus niger broth in this example, Aspergillus oryzae solution enzyme is added in proportion to the activity of neutral protease, and Aspergillus niger solution enzyme is added in proportion to the activity of acid protease.
(3) The temperature is selected to be 55 ℃, the optimal PH enzymolysis condition is selected for each treatment, the enzymolysis time is selected to be 72h, and the specific parameters and results are as follows:
the results show that the enzymolysis effect is not ideal when the cephalosporin C fungus residue is treated by single enzyme; the Aspergillus oryzae or Aspergillus niger culture solution is rich in various complex enzymes, and the enzymolysis effect is obvious and good; chitinase is added into aspergillus oryzae and aspergillus niger liquid enzyme in an intensified manner, the enzymolysis effect is improved, the integrity of cell walls of thalli is thoroughly destroyed, and the liquefaction efficiency is greatly improved.
Example 3
Adding 15kg of plant straws or dried organic fertilizer raw materials into 72.3kg of the centrifugal fungus dregs in the embodiment 2, adjusting the water content, inoculating aspergillus oryzae ¸ aspergillus niger or organic fertilizer composite strains for stacking fermentation, turning the middle for 3-5 times to reduce the temperature, detecting the water content to be 21.6 percent after the temperature is reduced, spreading out and airing or drying until the water content is less than or equal to 15 percent, thus obtaining the organic fertilizer basic raw material.
Example 4
The nanofiltration concentrate of 100L, the solid content of 19.2 percent and the amino acid content of 6.13 percent in the step 4 in the example 2 are concentrated to 31.2L by a four-effect vacuum concentration device. 68.8kg of water is removed by evaporation, 22.2kg of steam is consumed, and the steam consumption ratio is 1: 3.1. And (3) drying the concentrated solution in vacuum to obtain 19.6kg of amino acid solid powder, wherein the steam consumption is 11.6kg, the steam consumption ratio is 1.5:1, and the comprehensive steam consumption ratio is 1: 2.4kg of steam, i.e. 1kg, can remove 2.4kg of water from the concentrate. If 77.9kg of water removed by nanofiltration is included, the integrated steam consumption ratio is 1: 4.77, only 1kg of steam is consumed for removing 4.77kg of water in the cephalosporin C fungus residue by adopting the technology.
A certain company utilizes strong acid to hydrolyze animal leftovers to produce amino acid solution (the amino acid content is 17.4 percent), and the delivery price of the product is 1900 yuan/ton; the raw material (amino acid content: 10.8%) of the amino acid liquid fertilizer in example 1 was estimated to be 1100-.
Comparative example 2
The mushroom dregs which are not processed by the method are dried by a traditional roller dryer, and the energy consumption results are as follows: 100L of cephalosporin C bacterial residue is dried by a roller dryer to obtain 16.7kg of dry bacterial residue powder, the water content is 8.8 percent, and the cephalosporin C residue is 835.4 ug/g. 127.3kg of steam was consumed, with a steam consumption ratio of 1.2: 1.
The receiving price of the dry cephalosporin C dregs in a certain organic fertilizer plant is about 450 yuan/ton.
Comparative example 3:
the energy consumption results obtained by drying the mushroom dregs which are not treated by the method by using a small spray dryer are as follows: 100L of cephalosporin C bacterial residue is dried by a small spray dryer to obtain 16.9kg of dry bacterial residue powder, the water content is 8.4 percent, and the cephalosporin C residue is 1432.7.4 ug/g. 367.1kg of steam was consumed, the steam consumption ratio was 3.7: 1.
comparing the comparative example 2, the comparative example 3, the example 2 and the example 4, it can be seen that the fungus dregs treated by the method can obviously reduce the steam consumption, the method only uses a small amount of steam for disinfection in the preparation stage of the biological enzyme, and adopts a nano-filtration and centrifugation mode to remove water by a mechanical method in the rest stages or adopts multi-effect vacuum concentration equipment with extremely high thermal efficiency, thereby greatly saving the energy consumption and having low treatment cost.
Meanwhile, the invention can effectively solve the contradiction between the product cost and the price in the treatment of the waste in 7-ACA production, and refer to example 5 and comparative example 4.
Example 5:
a production company producing 4 tons of 7-ACA daily generates 278 tons of 7-ACA extraction waste liquid every day, the content of alpha-amino adipic acid is 0.84 percent, alpha-amino adipic acid is extracted by adopting the technology of the invention, and is mixed with the mushroom residue treatment liquid prepared by adopting the technology of the invention to prepare an amino acid fertilizer raw material, and the market reference value of 2.3 tons of alpha-amino adipic acid is 8050 + 10350 yuan.
Comparative example 4
The 2.3 ton alpha-amino adipic acid is not extracted and is directly discharged into a sewage treatment plant along with the wastewater, and the environment-friendly treatment cost of 10248 yuan is brought by calculating the environment-friendly treatment cost of 3.66 ton COD according to the environment-friendly treatment cost of 1.4 yuan/kgCOD.
Claims (8)
1. A method for utilizing 7-aminocephalosporanic acid production waste is characterized by comprising the following steps:
the method comprises the following steps:
(1) regulating pH of fresh wet residue of cephalosporin C to 5.5-6.0 with alkali, adding complex enzyme preparation in certain proportion, and performing enzymolysis at 55-60 deg.C for 48-72 hr;
(2) separating the calcium oxalate salt and part of fibers from the enzymatic hydrolysate by using a decanter centrifuge, wherein the calcium oxalate salt and part of the fibers can be used as organic fertilizer raw materials;
(3) treating the centrifugate by using ceramic membrane ultrafiltration equipment, respectively collecting filtrate and filter residue, wherein one part of the ultrafiltration filter residue is used as a culture medium for fermentation preparation of aspergillus oryzae or aspergillus niger liquid enzyme, and the other part of the ultrafiltration filter residue is added into the next batch of cephalosporin fresh mushroom residue for secondary enzymolysis;
(4) nanofiltration and concentration of ultrafiltrate;
(5) adding alpha-amino adipic acid into the nanofiltration concentrated solution obtained in the step 4 for blending to obtain an amino acid liquid fertilizer or a production raw material thereof, wherein the alpha-amino adipic acid is derived from 7-ACA extraction mother liquor;
the complex enzyme preparation in the step (1) is one of aspergillus oryzae liquid enzymes or a mixture of the aspergillus oryzae liquid enzymes and the aspergillus niger liquid enzymes, the adding total amount of the aspergillus oryzae liquid enzymes and the aspergillus niger liquid enzymes in the complex enzyme preparation is 5% -15%, the proportion of the aspergillus oryzae liquid enzymes and the aspergillus niger liquid enzymes is 80-100:0-20, and the optimal proportion is 85-90: 10-15%.
2. The method for utilizing waste from the production of 7-aminocephalosporanic acid according to claim 1, wherein: the complex enzyme preparation in the step (1) also comprises 4-20U/ml chitinase.
3. The method for utilizing waste from the production of 7-aminocephalosporanic acid according to claim 1, wherein: in the step (1), the liquefaction rate of the organic matters in the enzymolysis liquid is controlled to be more than or equal to 70 percent, and the thallus concentration of the enzymolysis liquid is controlled to be less than or equal to 20 percent.
4. The method for utilizing waste from the production of 7-aminocephalosporanic acid according to claim 1, wherein: the pore diameter of the ultrafiltration membrane in the step (3) is 10-50 nm.
5. The method for utilizing waste from the production of 7-aminocephalosporanic acid according to claim 1, wherein: in the step (4), the concentration of the nanofiltration liquid is controlled to be 15-20% of soluble solid content and 5-7% of amino acid content.
6. The method for utilizing waste from the production of 7-aminocephalosporanic acid according to claim 1, wherein: the preparation method of the alpha-amino adipic acid added in the step (5) comprises the following steps: collecting 7-ACA extraction waste liquid; concentrating a nanofiltration membrane; regulating the pH of the concentrated solution to 5.0 with hydrochloric acid, crystallizing for 2h, and then continuously regulating the pH to 3.5, and crystallizing for 4 h; and (3) carrying out plate-frame filtration on the crystal liquid, carrying out top washing by deionized water, and carrying out vacuum drying on a filter cake to obtain the alpha-amino adipic acid.
7. The method for utilizing waste from the production of 7-aminocephalosporanic acid according to claim 1, wherein: the Aspergillus oryzae and Aspergillus niger liquid enzyme culture medium in the step 1 comprises: 15-50% of cephalosporin C fresh mushroom dregs ¸ 0-15% of ultrafiltration dregs ¸ in the step (3), inorganic salt ¸ 0.3-1% of quick-acting organic carbon source and nitrogen source.
8. The method for utilizing waste from 7-aminocephalosporanic acid production according to claim 7, wherein: the preparation method of the aspergillus oryzae and aspergillus niger liquid enzyme in the step 1 comprises the following steps: adjusting pH of the culture medium with liquid alkali to 5.5-6.5, sterilizing at 121 deg.C for 20-30 min, inoculating strain, and culturing at 28-32 deg.C for 30-42h under aeration.
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