CN1648070A - Method for preparing controlled release high molecular carbon source material for biological method to treat water - Google Patents
Method for preparing controlled release high molecular carbon source material for biological method to treat water Download PDFInfo
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- CN1648070A CN1648070A CNA2005100111202A CN200510011120A CN1648070A CN 1648070 A CN1648070 A CN 1648070A CN A2005100111202 A CNA2005100111202 A CN A2005100111202A CN 200510011120 A CN200510011120 A CN 200510011120A CN 1648070 A CN1648070 A CN 1648070A
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- 239000000463 material Substances 0.000 title claims abstract description 82
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title abstract description 17
- 238000010170 biological method Methods 0.000 title 1
- 238000013270 controlled release Methods 0.000 title 1
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 27
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- 229920002472 Starch Polymers 0.000 claims description 25
- 239000008107 starch Substances 0.000 claims description 25
- 229940088598 enzyme Drugs 0.000 claims description 24
- -1 poly(lactic acid) Polymers 0.000 claims description 23
- 235000019698 starch Nutrition 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
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- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 5
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 claims description 3
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- 229960004418 trolamine Drugs 0.000 claims description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims 1
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 8
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- 229910001628 calcium chloride Inorganic materials 0.000 description 8
- 229920002521 macromolecule Polymers 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 241000209140 Triticum Species 0.000 description 3
- 235000021307 Triticum Nutrition 0.000 description 3
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- 230000023556 desulfurization Effects 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 239000004375 Dextrin Substances 0.000 description 2
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- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 2
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- 229920001592 potato starch Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 239000010902 straw Substances 0.000 description 2
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- 235000020679 tap water Nutrition 0.000 description 2
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- 206010012735 Diarrhoea Diseases 0.000 description 1
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- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
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- 238000005297 material degradation process Methods 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
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Classifications
-
- Y02W10/12—
Landscapes
- Enzymes And Modification Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to the preparation process of controlled releasing high molecular carbon source material for biological water treating process, and belongs to the field of water treating technology. The preparation process includes the steps of consoluting solution, enzymolysis, mechanical mixing and repeated freezing formation. The main material includes natural high molecular material 10-80 wt%, artificially synthetic material 10-70 wt%, deoxidizing agent 0-3 wt%, pH regulator 0-3 wt%, cross-linking agent 0-1 wt%, and compatibilizing agent 0-25 wt%, as well as bioactive enzyme in 0-5 u/g of the natural high molecular material. The prepared carbon source material has high mechanical performance, is suitable for various water treating technological processes including in-situ biological underground water repair. Test shows that the carbon source material can release organic carbon effectively for long time.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the required carbon source material of biological process water treatment, belong to water-treatment technology field.
Background technology
The critical limitation factor in the underground water biology in situ denitrification and desulfurization technology is effective solution of carbon source material (electron donor).Underground water occupies consequence as the drinking water source in water supply, water quality condition produces directly or indirectly influence to HUMAN HEALTH.For a long time, the unreasonable use of the discharging of three industrial wastes, agricultural chemicals and chemical fertilizer causes pollutions such as large-area point-like in various degree or local planar groundwater azotate, nitrite, vitriol and is on the rise.Result of study confirms that the excessive meeting of nitrate causes the infant to suffer from siderosis albumen disease in the tap water, and nitrate, nitrite can be converted into nitrosamine in addition, produces and three cause (carcinogenic, cause prominent, teratogenesis) effect.And when sulfate concentration is too high in the tap water, can cause diarrhoea etc. to human body.Therefore, biological denitrification denitrification and desulfurization technology to solve groundwater azotate pollution, recover water quality, to improve function of water body significant.
For groundwater azotate pollution is administered, consider from groundwater environment (temperature-stable, anoxic or few oxygen), technology (the underground pollution blocking-up band constructing technology that is mature on the whole), economic aspect, adopt biological denitrification technology more reasonable.Therefore industrialized countries such as West Europe, North America adopt this method more.For heterotrophic denitrification, under the anoxybiotic situation, the first-selected nitrate radical of heterotrophic bacterium carries out respiration, with NO
3 -Be reduced to N
2Heterotrophic bacterium can be respectively by said process with carbon source material (being electron donor) oxidation, thereby obtain required energy.It is a lot of to can be used as the denitrifying carbon source material of heterotrophic bacterium, and commonly used in groundwater treatment have methyl alcohol, ethanol, acetic acid, a sucrose etc., is many with former three especially wherein.Report that this method can remove most of nitrate radical in water body although have abroad, when using small molecules electron-donating group matter, often encounter problems, if matrix is excessive, polluted-water then, as if the matrix deficiency, then anti-nitration reaction is not thorough.Also there is report to use sawdust, wheat straw stalk, straw, broken newspaper, short cellucotton, sodium acetate, whisky vinasse, soybean oil to make the report of carbon source, but excessive heterotrophic denitrification bacterium and gas blockage phenomenon in the stratum.Can separate the generation that alleviates this phenomenon with aerobic denitrification process by back flushing or with the anaerobic denitrifying process, but exist denitrification process to carry out problems such as not thorough equally.Effectively solve critical limitation sex factor-carbon source problem that azotate pollution underground water is administered just because of failing, make present research rest on ground biological denitrification denitrification process, i.e. extraction-treatment stage mostly.The existing operational conditions control research and extension that difficulty is big, expense is high, floor space limits biological denitrification technology greatly and is greatly used.
Summary of the invention
The objective of the invention is to prepare the carbon source material that is applicable in the biological process water treatment procedure, solve the nitrate denilrification procedure that exists in the present engineering application and carry out thorough, problems such as underground reservoir easily stops up, carbon source material controlled capability difference.Theory of the present invention comes from the following aspects: biological flora is non-limiting to the carbon source requirement, and promptly nearly all organic materials all can be used as the carbon source material of denitrifying bacteria; The specificity of bioactive enzyme; The controllability of biodegradable material degradation speed.
The present invention uses main raw material(s) to be natural macromolecular material.As everyone knows, natural macromolecular material comprises proteinaceous materials such as polyoses such as Mierocrystalline cellulose, starch, chitosan and hair, silk, is easy to microbiological degradation, is the ideal biodegradated polymer materal, and this class material price is cheap, material obtains easily.Simultaneously, this type of material can be made polymer composite by means such as blending and modifying and other material, regulates biodegradation rate and degree by the composition that changes mixture, therefore is suitable as very much carbon source material of the present invention.
Technical scheme of the present invention is as follows:
The preparation method who is used for the controlled high molecule carbon source material of biological process water treatment comprises that solution is miscible, enzymolysis, mechanical blending and freeze forming step repeatedly, the proportioning of main raw material in the dry weight mass percent (/ %),
Natural macromolecular material 10~80
Synthetic material 10~70
Oxygen scavenger 0~3
PH regulator agent 0~3
Linking agent 0~1
Compatilizer 0~25
In addition, bioactive enzyme is counted 0~5u/g with natural macromolecular material content;
Concrete steps are as follows:
1) natural macromolecular material and the oxygen scavenger with said ratio joins in the reactor that solvent is housed, and under agitation is heated to gelatinization or dissolving, and keeps 0.5h~5h;
2) in reactor, add the pH regulator agent of said ratio earlier, and then add the bioactive enzyme of said ratio, after fully stirring, be warming up to 90 ℃~120 ℃ rapidly, make the biological activity enzyme deactivation;
3) after the synthetic material dissolving with said ratio, add in the above-mentioned mixed system, add the linking agent and the compatilizer of said ratio simultaneously, constant temperature stirs down described mixed system is mixed;
4) get said mixture and inject mould, be transferred to the normal temperature and place freezingly in the cryostat, carry out freezing-course of defrosting 2~5 times repeatedly, obtain the controlled high molecule carbon source material of irreversible frozen glue form.
Transportation for convenience, can do further drying treatment to the controlled high molecule carbon source material of irreversible frozen glue form, the controlled high molecule carbon source material that is about to above-mentioned irreversible frozen glue form is transferred in the loft drier, is dried to constant weight and obtains block controlled high molecule carbon source material.
Natural macromolecular material of the present invention is starch, Mierocrystalline cellulose, chitin, and a kind of in the xylogen.
Synthetic material of the present invention is a kind of in polyvinyl alcohol, poly(lactic acid), polycaprolactone, polylactide, poly-acid anhydrides, polyoxyethylene glycol, polyacrylamide, polyethylene or the polypropylene.
Oxygen scavenger of the present invention is a kind of in saccharosonic acid, SODIUM ISOVITAMIN C, carbohydrazide, ethylidenehydroxylamine or the acetoxime.
Bioactive enzyme of the present invention is a kind of in high temperature resistant αDian Fenmei, middle temperature αDian Fenmei, βDian Fenmei, isoamylase, saccharifying enzyme, beta-glucanase, cellulase, high alkalinity cellulase or the polygalacturonase.
Compatilizer of the present invention is one or more in ethylene glycol, propylene glycol, glycerol, butyleneglycol, five glycol, the hexylene glycol.
PH regulator agent of the present invention comprises hydrochloric acid, sodium hydroxide, citric acid, acetate, trolamine, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, and ammonium chloride.
Linking agent of the present invention is a kind of in epoxy chloropropane, urea, formaldehyde or the phosphorus oxychloride.
In this was clearly demarcated, the solvent that reactor is equipped with comprised water, formic acid, ammoniacal liquor, chloroform, phosgene, acetone, ethanol, chloroform, methylene dichloride, and tetrahydrofuran (THF).
The purpose that the present invention adds oxygen scavenger is deoxygenation in the microenvironment of carbon source material surface, is beneficial to the carrying out of biological denitrification, and most denitrifying bacteriums are anerobe.Another purposes of adding oxygen scavenger is that the control aerobic bacteria is bred at material surface or inside, is beneficial to the growth of anerobe and the preservation of material.
It is the speed that discharges for the carbon source of controlling carbon source material that the present invention adds bioactive enzyme.Utilized the specificity and the high efficiency of bioactive enzyme, high-molecular weight natural materials such as amylolysis can have been become the component of a series of lower molecular weights, be beneficial to it and further discharge and biological utilisation.Can control the degree that the high molecular weight material decomposition is carried out by the amount and the reaction times of control interpolation bioactive enzyme.Another advantage of adding bioactive enzyme is its high efficiency and non-pollution, because the efficient specificity of bioactive enzyme, its additive capacity is very little, to other family macromolecule non-activity, bioactive enzyme is a kind of protein, after finishing, reaction can not cause secondary pollution by high-temperature denatured its inactivation that makes to environment.
The macromolecule carbon source material that the method for the invention is made comprises two kinds of forms of bulk and gel, all can do for carbon material at the biological process water treatment procedure.Carbon source material performance to preparation is tested, and by scanning electron microscopic observation, can see that starch granules is uniformly distributed in the material, and there is one deck coating film on its surface, and granular size is at 10~20U.The tensile strength Rm=24.84N/mm of the carbon source material of preparation
2, extension at break rule ε=139.07%.No matter be bulk or gel, mechanical property is preferably all arranged, be applicable to various water treatment process, comprise underground water biology in situ reparation use.Test shows, carbon source material can effectively discharge for a long time to organic carbon.
Embodiment
The invention provides a kind of preparation method who is used for the controlled high molecule carbon source material of biological process water treatment, comprise that solution is miscible, enzymolysis, mechanical blending and freeze forming step repeatedly, the proportioning of main raw material with the dry weight mass percent (/ %),
Natural macromolecular material 10~80
Synthetic material 10~70
Oxygen scavenger 0~3
PH regulator agent 0~3
Linking agent 0~1
Compatilizer 0~25
In addition, bioactive enzyme is counted 0~5u/g with natural macromolecular material content;
Concrete steps are as follows:
1) natural macromolecular material and the oxygen scavenger with said ratio joins in the reactor that solvent is housed, and under agitation is heated to gelatinization or dissolving, and keeps 0.5h~5h;
2) in reactor, add the pH regulator agent of said ratio earlier, and then add the bioactive enzyme of said ratio, after fully stirring, be warming up to 90 ℃~120 ℃ rapidly, make the biological activity enzyme deactivation;
3) after the synthetic material dissolving with said ratio, add in the above-mentioned mixed system, add the linking agent and the compatilizer of said ratio simultaneously, constant temperature stirs down described mixed system is mixed;
4) get said mixture and inject mould, be transferred to the normal temperature and place freezingly in the cryostat, carry out freezing-course of defrosting 2~5 times repeatedly, obtain the controlled high molecule carbon source material of irreversible frozen glue form.
Transportation for convenience, can do further drying treatment to the controlled high molecule carbon source material of irreversible frozen glue form, the controlled high molecule carbon source material that is about to above-mentioned irreversible frozen glue form is transferred in the loft drier, is dried to constant weight and obtains block controlled high molecule carbon source material.
According to the practical situation needs, the present invention can use the above main raw material of different content, also can add or reduce certain component as one sees fit.In addition, during preparation macromolecule carbon source material, the interpolation of material order in the preparation process can suitably be adjusted as the interpolation order of oxygen scavenger, linking agent, compatilizer.
Natural macromolecular material of the present invention is starch, Mierocrystalline cellulose, chitin, and a kind of in the xylogen.
Synthetic material of the present invention is a kind of in polyvinyl alcohol, poly(lactic acid), polycaprolactone, polylactide, poly-acid anhydrides, polyoxyethylene glycol, polyacrylamide, polyethylene or the polypropylene.
Oxygen scavenger of the present invention is a kind of in saccharosonic acid, SODIUM ISOVITAMIN C, carbohydrazide, ethylidenehydroxylamine or the acetoxime.
Bioactive enzyme of the present invention is a kind of in high temperature resistant αDian Fenmei, middle temperature αDian Fenmei, βDian Fenmei, isoamylase, saccharifying enzyme, beta-glucanase, cellulase, high alkalinity cellulase or the polygalacturonase.
Compatilizer of the present invention is one or more in ethylene glycol, propylene glycol, glycerol, butyleneglycol, five glycol, the hexylene glycol.
PH regulator agent of the present invention comprises hydrochloric acid, sodium hydroxide, citric acid, acetate, trolamine, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, and ammonium chloride.
Linking agent of the present invention is a kind of in epoxy chloropropane, urea, formaldehyde or the phosphorus oxychloride.
In this was clearly demarcated, the solvent that reactor is equipped with comprised water, formic acid, ammoniacal liquor, chloroform, phosgene, acetone, ethanol, chloroform, methylene dichloride, and tetrahydrofuran (THF).
Embodiments of the invention are as follows:
Embodiment 1
Starch, inorganic salt, water are joined in the reactor, under agitation be heated to 40 ℃~70 ℃, gelatinization 10~60min under steady temperature.Add hydrochloric acid and regulate about pH=4~7, add calcium chloride of a little and 1% SODIUM ISOVITAMIN C, fully after the stirring and dissolving, add the middle temperature αDian Fenmei of 0.1u/g (starch content meter), behind 0.5h~2h, stir down and be warming up to 80 ℃~120 ℃ rapidly.Add polyvinyl alcohol, linking agent, compatilizer constant temperature stir 1h down.Get mixture and inject mould, be transferred to the room temperature and place freezingly in the cryostat, spend the night, taking-up is thawed, and the back that thaws is freezing, and 3 materials of repeatable operation become irreversible frozen glue.To make material transfer to loft drier, and be dried to constant weight and get block controlled high molecule carbon source material.The main raw materials in proportion of preparation macromolecule carbon source material following (the dry weight mass percent ,/%):
Starch 80
Polyvinyl alcohol 10
SODIUM ISOVITAMIN C 1
Hydrochloric acid, calcium chloride 0.5
Epoxy chloropropane 0.5
Glycerol 8
In addition, middle temperature αDian Fenmei 0.1u/g (starch content meter)
5~20 times of water-starch;
Described starch comprises Zulkovsky starch, rice, corn, wheat, legume starch or potato starch, and treated starch such as dextrin, etherification starch, esterification starch, graft starch.
Embodiment 2
Mierocrystalline cellulose, ammoniacal liquor, water are joined in the reactor, under agitation be heated to 40 ℃~70 ℃, under steady temperature, stir.Add hydrochloric acid and regulate about pH=4~7, add calcium chloride of a little and 2% saccharosonic acid, fully after the stirring and dissolving, add the cellulase of 0.2GCU/g (content of cellulose meter), behind 0.5h~2h, stir down and be warming up to 80 ℃~120 ℃ rapidly.Add polyvinyl alcohol, linking agent, compatilizer constant temperature stir 1h down.Get mixture and inject mould, be transferred to the room temperature and place freezingly in the cryostat, spend the night, taking-up is thawed, and the back that thaws is freezing, and 3 materials of repeatable operation become irreversible frozen glue.To make material transfer to loft drier, and be dried to constant weight and get block controlled high molecule carbon source material.The main raw materials in proportion of preparation macromolecule carbon source material following (the dry weight mass percent ,/%):
Mierocrystalline cellulose 10
Polyvinyl alcohol 70
Saccharosonic acid 2
Hydrochloric acid, calcium chloride 1
Epoxy chloropropane 1
Glycerol/ethylene glycol=1/1 16
In addition, cellulase 0.1GCU/g (content of cellulose meter)
Ammoniacal liquor, water cellulose element 5~20 times;
Described Mierocrystalline cellulose comprises cotton, fiber crops, wood cellulose and chemical modification product thereof, as etherificate, esterification, grafted cellulose.
Embodiment 3
Poly(lactic acid) is dissolved in the chloroform poly(lactic acid) solution of preparation 5%, adds linking agent, compatilizer constant temperature stirs 1h down.An amount of chitosan is dissolved in 5% aqueous formic acid, joins in the reactor, under agitation be heated to 30 ℃~80 ℃.Add formic acid and regulate about pH=2~5, add calcium chloride of a little and 1% carbohydrazide, fully stirring and dissolving.Stir then down and dropwise splash into poly(lactic acid) solution, transfer to cryogenic freezing in the mould after being uniformly dispersed rapidly, spend the night, taking-up is thawed, and will make material transfer to loft drier, is dried to constant weight and gets block controlled high molecule carbon source material.The main raw materials in proportion of preparation macromolecule carbon source material following (the dry weight mass percent ,/%):
Chitosan 30
Poly(lactic acid) 50
Carbohydrazide 1
Hydrochloric acid, calcium chloride 0.5
Formaldehyde 0.5
Glycerol/ethylene glycol=1/1 18
In addition, 10~25 times in formic acid, chloroform, water material dry weight,
Do not use bioactive enzyme in this example; Described chitin comprises chitin, chitosan and derivative thereof.
Embodiment 4
Xylogen, ammoniacal liquor, water are joined in the reactor, under agitation be heated to 40 ℃~70 ℃, under steady temperature, stir.Add hydrochloric acid and regulate about pH=4~7, add calcium chloride of a little and 2% ethylidenehydroxylamine, fully after the stirring and dissolving, add the zytase of 0.2GCU/g (content of lignin meter), behind 1h~3h, stir down and be warming up to 80 ℃~120 ℃ rapidly.Add polyvinyl alcohol, linking agent, compatilizer constant temperature stir 1h down.Get mixture and inject mould, be transferred to the room temperature and place freezingly in the cryostat, spend the night, taking-up is thawed, and the back that thaws is freezing, and 3 materials of repeatable operation become irreversible frozen glue.To make material transfer to loft drier, and be dried to constant weight and get block controlled high molecule carbon source material.The main raw materials in proportion of preparation macromolecule carbon source material following (the dry weight mass percent ,/%):
Xylogen 20
Polyvinyl alcohol 60
Ethylidenehydroxylamine 2
Hydrochloric acid, calcium chloride 1
Urea 1
Glycerol/polyoxyethylene glycol=1/1 16
In addition, zytase 0.1GCU/g (content of lignin meter)
Ammoniacal liquor, water xylogen 5~20 times
Embodiment 5
Starch, water are joined in the reactor, under agitation be heated to 40 ℃~70 ℃, under steady temperature, behind gelatinization 1h~3h, be warming up to 80 ℃~120 ℃ rapidly.Add polyvinyl alcohol, the dissolving back is continued constant temperature and is stirred 1h down.Get mixture and inject mould, be transferred to the room temperature and place freezingly in the cryostat, spend the night, taking-up is thawed, and repeatable operation is freezing-thaws 3 times, material becomes the controlled high molecule carbon source material of irreversible frozen glue form.The main raw materials in proportion of preparation macromolecule carbon source material following (the dry weight mass percent ,/%):
Starch 30
Polyvinyl alcohol 70
5~20 times of water-starch
Do not use oxygen scavenger, compatilizer, pH regulator agent, linking agent and bioactive enzyme in this example.
Described starch comprises Zulkovsky starch, rice, corn, wheat, legume starch or potato starch, and treated starch such as dextrin, etherification starch, esterification starch, graft starch.
The carbon source material of the method for the invention preparation is specially adapted to water treatment procedures such as biological process denitrogenation, desulfurization as electron donor, as is applied to for the reduction of carbon deficiency, underground water original position repair process nitric nitrogen or removal etc.
Claims (9)
1. be used for the preparation method of the controlled high molecule carbon source material of biological process water treatment, it is characterized in that, this preparation method comprises that solution is miscible, enzymolysis, mechanical blending and freeze forming step repeatedly, and the proportioning of main raw material is in the dry weight mass percent,
Natural macromolecular material 10~80
Synthetic material 10~70
Oxygen scavenger 0~3
PH regulator agent 0~3
Linking agent 0~1
Compatilizer 0~25
In addition, bioactive enzyme is counted 0~5u/g with natural macromolecular material content;
Concrete steps are as follows:
1) natural macromolecular material and the oxygen scavenger with said ratio joins in the reactor that solvent is housed, and under agitation is heated to gelatinization or dissolving, and keeps 0.5h~5h;
2) in reactor, add the pH regulator agent of said ratio earlier, and then add the bioactive enzyme of said ratio, after fully stirring, be warming up to 90 ℃~120 ℃ rapidly, make the biological activity enzyme deactivation;
3) after the synthetic material dissolving with said ratio, add in the above-mentioned mixed system, add the linking agent and the compatilizer of said ratio simultaneously, constant temperature stirs down described mixed system is mixed;
4) get said mixture and inject mould, be transferred to the normal temperature and place freezingly in the cryostat, carry out freezing-course of defrosting 2~5 times repeatedly, obtain the controlled high molecule carbon source material of irreversible frozen glue form.
2. preparation method according to claim 1 is characterized in that: the controlled high molecule carbon source material of above-mentioned irreversible frozen glue form is transferred in the loft drier, is dried to constant weight and obtains block controlled high molecule carbon source material.
3. preparation method according to claim 1 is characterized in that: described natural macromolecular material is starch, Mierocrystalline cellulose, chitin, and a kind of in the xylogen.
4. preparation method according to claim 1 is characterized in that: described synthetic material is a kind of in polyvinyl alcohol, poly(lactic acid), polycaprolactone, polylactide, poly-acid anhydrides, polyoxyethylene glycol, polyacrylamide, polyethylene or the polypropylene.
5. preparation method according to claim 1 is characterized in that: described oxygen scavenger is a kind of in saccharosonic acid, SODIUM ISOVITAMIN C, carbohydrazide, ethylidenehydroxylamine or the acetoxime.
6. preparation method according to claim 1 is characterized in that: described bioactive enzyme is a kind of in high temperature resistant αDian Fenmei, middle temperature αDian Fenmei, βDian Fenmei, isoamylase, saccharifying enzyme, beta-glucanase, cellulase, high alkalinity cellulase or the polygalacturonase.
7. preparation method according to claim 1 is characterized in that: described compatilizer is one or more in ethylene glycol, propylene glycol, interior triol, butyleneglycol, five glycol, the hexylene glycol.
8. preparation method according to claim 1 is characterized in that: described pH regulator agent comprises hydrochloric acid, sodium hydroxide, citric acid, acetate, trolamine, Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC, and ammonium chloride.
9. preparation method according to claim 1 is characterized in that: described linking agent is a kind of in epoxy chloropropane, urea, formaldehyde or the phosphorus oxychloride.
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