CN109402105B - Floatable and easily degradable microbial carrier and preparation method and application thereof - Google Patents
Floatable and easily degradable microbial carrier and preparation method and application thereof Download PDFInfo
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- CN109402105B CN109402105B CN201811193708.8A CN201811193708A CN109402105B CN 109402105 B CN109402105 B CN 109402105B CN 201811193708 A CN201811193708 A CN 201811193708A CN 109402105 B CN109402105 B CN 109402105B
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/10—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/341—Consortia of bacteria
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
- C02F3/344—Biological treatment of water, waste water, or sewage characterised by the microorganisms used for digestion of mineral oil
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
- C12N11/04—Enzymes or microbial cells immobilised on or in an organic carrier entrapped within the carrier, e.g. gel or hollow fibres
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
Abstract
The invention discloses a floatable and easily degradable microbial carrier, a preparation method and application thereof. The preparation method comprises the following steps: 1) dissolving a natural polymer gel carrier in water to form an aqueous solution, and then sequentially adding a free radical scavenger and a strong oxidant into the aqueous solution to carry out an oxidation reaction to obtain a reaction solution of an aldehyde group-containing activated intermediate; 2) adding an oxidation terminating agent into the reaction liquid obtained in the step 1) to obtain a partial oxidation product of the natural polymer gel carrier; 3) carrying out reductive amination, alkyl grafting and alcohol precipitation separation on the partial oxidation product to obtain an amphiphilic product; 4) dissolving the amphiphilic product in water, and adding an organic polymer carrier, a cross-linking agent and petroleum degrading bacteria for cross-linking reaction to obtain the product. The floatable and easily degradable carrier material of the embedded petroleum degrading strain can be used for adsorbing and degrading petroleum, thereby being used for cleaning oil spill pollution.
Description
Technical Field
The invention relates to a floatable and easily degradable microbial carrier and a preparation method and application thereof.
Background
The biological method for treating petroleum pollution in water has the advantages of safety, environmental protection, reliability and the like, but still has many problems to be solved in the aspect of practical application at present. The free degrading bacteria and the indigenous microorganisms have antagonistic action, and have the defects of easy loss of bacteria, sensitivity to environmental condition change and the like. The immobilization technology of the petroleum degradation strain can preliminarily solve the problem, has certain effect on overcoming the antagonistic action of the free strain and the indigenous microorganism, still has the defects of low oil absorption rate, weak mechanical strength, poor degradability and the like of a carrier material, and limits the large-scale popularization of the treatment of the spilled oil by a biological method.
The selection of proper immobilized microorganism carrier is the key for realizing industrialization, and the quality of the carrier depends on the adsorption rate, mechanical strength, service life and activity of the embedded microorganism cells of the material. The ideal carrier material has the characteristics of high oil absorption rate, biodegradability, low price, rich pores and the like. The carrier material also has suspension property, and the suspension carrier material is beneficial to the propagation of microorganisms at an oil-water interface, so that the microorganisms are more easily contacted with oil spill. Many carrier materials have been reported for the remediation of spilled oil, however, it is not easy to find a material that has a high oil absorption and is buoyant. The activated carbon is the most widely applied immobilized carrier, and the prepared repairing agent has floatability but low adsorption rate on oil spill; the bacterial immobilization is completed by using the secondary crosslinking of polyvinyl alcohol-boric acid for sewage treatment, the embedding carrier has the advantages of high mechanical strength, low price and the like, but the product has no floatability and cannot be used for treating an oil film on the sea surface. The nitrifying bacteria immobilized bioactive filler of the polyurethane carrier has floatability, but polyurethane foam is not easy to degrade and is easy to cause secondary pollution. The natural organic high molecular carrier material has no toxicity to most microbes, good biocompatibility and low price. However, the natural organic polymer carrier has the defects of low mechanical strength, easy decomposition by microorganisms, short service life and the like if not subjected to other treatment. Aiming at the defects of the natural polymer carrier material, the organic polymer carrier material is synthesized and prepared, so that the inherent defects related to the natural polymer material can be overcome, and the natural organic carrier material can be replaced. The invention provides a floatable and easily degradable microbial carrier material for treating oily sewage.
Disclosure of Invention
In view of the disadvantages of the prior art, it is an object of the present invention to provide a floatable, easily degradable carrier material.
The floatable and easily degradable carrier material provided by the invention is prepared by the following steps: 1) dissolving a natural polymer gel carrier in water to form an aqueous solution, and then sequentially adding a free radical scavenger and a strong oxidant into the aqueous solution to carry out an oxidation reaction to obtain a reaction solution of an aldehyde group-containing activated intermediate;
2) adding an oxidation terminator into the reaction liquid of the aldehyde group-containing activated intermediate in the step 1), and reacting the oxidation terminator with the excessive strong oxidant in the step 1) to obtain a partial oxidation product of the natural polymer gel carrier;
3) dissolving partial oxidation product of the natural polymer gel carrier in phosphate buffer solution with pH of 7.0, adding carbonyl reducing agent to reduce carbonyl, and adding organic synthesis intermediate NH2R, reacting aldehyde group with amino group, reducing and hydrogenating to obtain a reaction system containing the hydrophobic alkyl product grafted on the natural polymer gel carrier, stirring at room temperature, adding methanol to form a precipitate product, centrifugally separating, and collecting the precipitate to obtain a solid (namely an amphiphilic product) of the hydrophobic alkyl product grafted on the natural polymer gel carrier; wherein, the NH2R in R is selected from C6Alkyl radical, C12Alkyl and C18Any one of alkyl groups;
4) and (2) dissolving the hydrophobic alkyl product solid grafted on the natural polymer gel carrier in water, and then adding an organic polymer carrier and a crosslinking agent into the natural polymer gel carrier to perform a crosslinking reaction to obtain the floatable and easily degradable carrier material.
In step 1), the natural polymer gel carrier is selected from any one of the following: sodium alginate, agar, cellulose and chitosan, preferably sodium alginate.
The free radical scavenger is selected from any one of the following: n-propanol, isopropanol, graphene, multi-walled carbon nanotubes, preferably n-propanol. The strong oxidant is selected from sodium periodate.
The oxidation reaction in the step 1) is carried out under the condition of keeping out of the sun, and the reaction condition of the oxidation reaction is 4 ℃ for 2 hours.
In step 2) of the above method, the oxidation terminator is selected from any one of: ethylene glycol, propylene glycol, hydroquinone, potassium permanganate, preferably ethylene glycol.
In the steps 1) and 2) of the method, the mass ratio of the natural polymer gel carrier to the radical scavenger to the strong oxidant to the oxidation terminator is (0.5-2.0): (1-5): (0.1-0.3): (1-2).
When the natural polymer gel carrier is Sodium Alginate (SA), the partial oxidation product of the natural polymer gel carrier is sodium alginate partial oxidation product (OSA).
In step 3), the carbonyl reducing agent is at least one selected from the group consisting of: NaCNBH3、NaBH4And PhSeH, etc., preferably NaCNBH3. NaCNBH is therefore preferred3Because it is more reactive than other reducing agents, in neutral solution, the imine can be rapidly coated with NaCNBH3Reducing and not reducing aldehyde group.
In the step 3), the mass ratio of the partial oxidation product of the natural polymer gel carrier, the carbonyl reducing agent and the organic synthesis intermediate is (0.5-2.0): (0.4-1): (0.4-2).
When the natural polymer gel carrier is Sodium Alginate (SA) and the organic synthetic intermediate is dodecylamine, the obtained hydrophobic alkyl product grafted on the natural polymer gel carrier is a hydrophobic alkyl product SAC grafted on the sodium alginate12。
In step 4), the organic polymer carrier is selected from any one of the following: polyacrylamide, polyvinyl alcohol, polyaluminium sulfate, photocrosslinking resin, silica gel and polyurethane, preferably polyvinyl alcohol (PVA).
The cross-linking agent is selected from any one of the following: calcium chloride, boric acid, hexamethylenediamine and glutaraldehyde, preferably boric acid.
The mass ratio of the hydrophobic alkyl product grafted on the natural polymer gel carrier, the organic polymer carrier and the cross-linking agent is (1-4): (0.5-2.5): (1-4).
The crosslinking reaction conditions were room temperature.
Still another object of the present invention is to provide a floatable, easily degradable immobilized material for embedding petroleum degrading bacteria.
The floatable easily-degradable immobilized material of the embedded petroleum degradation strain provided by the invention is prepared according to the following method: 1) the operations of the steps 1) to 3) of the method for preparing the floatable and easily degradable carrier material are carried out,
2) dissolving the prepared hydrophobic alkyl product solid grafted on the natural polymer gel carrier in water, and adding an organic polymer carrier, a cross-linking agent and petroleum degrading bacteria for cross-linking reaction to obtain the gel;
wherein the mass ratio of the hydrophobic alkyl product grafted on the natural polymer gel carrier, the organic polymer carrier, the cross-linking agent and the petroleum degrading bacteria is (1-4): (0.5-2.5): (0.02-0.5): (0.4-0.5).
The petroleum degrading bacteria in the invention are selected from at least one of the following: the bacillus subtilis and the alcanivorax paradicus are preferably compounded with the alcanivorax paradicus, the bacillus subtilis, the alcanivorax dieselis, the marinobacter alcanivorax elegans, the pseudomonas spongiensis and the alcaligenes, and the mass ratio of the dried strains is 1:5:3:1 in sequence.
The inventor prepares the adsorbing material for degrading different oil components according to the characteristics of a target object by the thought of missile medicines. Based on the characteristics, the carrier material with specific adsorption performance is prepared to convey microorganisms to the suspended oil drops, so that the effect of adsorption degradation is achieved. The functional polymer carrier synthesized by targeting specific biomolecules or group affinity coordination principle, the material with strong lipophilicity and the oil drops are mutually attracted by the targeting group, and the carrier can become an ideal carrier for removing the pollution of oil spill and residual oil. The carrier with high adsorption performance can be prepared to synthesize an amphiphilic block copolymer with both hydrophobicity and hydrophilicity, and a physical amphiphilic material is constructed through hydrophobic effect to solve the problem. Modification of amphiphilic Sodium Alginate (SAC) with hydrophobic alkyl groups12) Reacting, constructing reversible three-dimensional cross-linking network by hydrophobic association of hydrophobic groups in the microsphere, and designing hydrophobic association structure to make the microsphere hydrophobicHydrophobic micro-regions formed by hydrophobic association of groups are cross-linking points, so that SAC (liquid Crystal display)12The PVA skeleton chain is crosslinked into a macro network to obtain a novel physical high-strength hydrophobic association carrier.
Drawings
FIG. 1 is a process flow diagram of the present invention for preparing a floatable and easily degradable carrier material.
Figure 2 is a schematic diagram of sodium alginate alkylation.
FIG. 3 shows the static contact angle and the growth of microorganisms of the floatable and easily degradable macroporous immobilization material for embedding bacterial strain prepared in example 1.
Detailed Description
The method of the present invention is illustrated by the following specific examples, but the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included within the scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The Alstonia palustris BNCC135077, Bacillus subtilis BNCC124990, Alstonia dieselis BNCC136655 and marinobacter hydrocarbonoclases BNCC220310 used in the examples described below were purchased from North Naphthora.
Example 1 preparation of a Strain-Embedded floatable, easily degradable macroporous immobilization Material
1) According to the flow of the figure 1, 2.0g of Sodium Alginate (SA) is taken, 100mL of water is added, the mixture is stirred and fully dissolved, 4mL of n-propanol is added into the solution to be used as a free radical trapping agent, so that the number of free radicals in an aqueous solution system is reduced, 0.21g of strong oxidant sodium periodate is added, the mixture is placed in a light-proof temperature-controlled shaking table, and oxidation reaction is carried out for 2 hours at 4 ℃ to obtain an aldehyde group-containing activated intermediate.
2) Adding 1mL of glycol serving as a reaction termination reagent into the reaction solution, stirring for 15min, carrying out oxidation reaction on the glycol and excessive sodium periodate, breaking carbon chains of the glycol to generate aldehyde, reducing the periodic acid into iodic acid, and freeze-drying to obtain a partial oxidation product OSA of the SA.
3) Dissolving 2.0g of OSA in 100mL of phosphate buffer solution (pH 7.0), adding 0.46g of sodium cyanoborohydride to reduce carbonyl, then adding 0.5g of dodecylamine, reacting aldehyde group with amino group, and then reducing and hydrogenating to obtain sodium alginate-grafted hydrophobic alkyl product SAC12(alkylation of sodium alginate is shown in FIG. 2), stirring at room temperature for 12h, adding methanol to form precipitate, centrifuging to obtain SAC12。
4) 1.75g of SAC was taken12Dissolved in 60mL of water, 0.75g of polyvinyl alcohol was added, 60mL of deionized water was added, and 1.0mL of NaCl was added2(mass concentration 2%) -saturated boric acid (mass 5%) mixed solution, adding 1.0mL of petroleum degrading bacteria (alcanivorax paraguayensis BNCC135077, bacillus subtilis BNCC124990, alcanivorax paradisianus BNCC136655 and marinobacter hydrocarbonocrea BNCC220310) (in the 1.0mL of petroleum degrading bacteria, the dry compound bacteria masses are 0.1g, 0.5g, 0.3g and 0.1g respectively) into the solution, mechanically stirring at the speed of 1000r/min, and performing crosslinking reaction for 1min to obtain the floatable strain-embedded easily-degradable macroporous immobilized material.
The static contact angle and the growth condition of the microorganism of the strain-embedded floatable and easily degradable macroporous immobilization material prepared in example 1 are shown in fig. 3.
According to the Young's equation, when theta is larger than 90 degrees, the liquid drop shrinks and is gathered into a bead shape along the surface of the mineral, the surface of the mineral is not easy to be wetted and is hydrophobic, and if the contact angle of the material is larger than 150 degrees, the material can show obvious super-hydrophobicity. The contact angle theta of the material carrier prepared by the method is 128.5 degrees. The carbon source is between 90 and 150 degrees and is close to 150 degrees, the carbon source is hydrophobic, petroleum is favorably adsorbed, a carbon source can be provided for petroleum degrading bacteria, and meanwhile, the structure which is not super-hydrophobic also ensures that the carrier can retain necessary moisture and nutrition for the growth of the bacteria. A large number of rod-shaped microorganisms are attached between the surface and the pores of the material, which shows that the microorganisms present good growth and proliferation states on the carrier, and the carrier material also shows good biocompatibility and is suitable for the growth and the propagation of the microorganisms.
The floatable and easily degradable macroporous immobilization material embedded with strains prepared in the embodiment 1 of the invention is used as a sample, and the oil absorption capacity of the material on heavy oil, crude oil and diesel oil is detected and calculated through a conventional test.
The oil absorption capacity is calculated according to the formulas (1) and (2):
in the formula: k is oil absorption rate, g/g; q is oil retention,%; m is1The mass of the sample before adsorbing the oil product; m is2The mass of the sample after being immersed in the solution, adsorbed, saturated, taken out and kept stand for about 30 s; m is3The mass of the sample after being taken out of the oil and continuously left for 15min is determined.
Parallel testing for 3 times, recording the experimental results, and taking the average value to obtain m1、m2And m3And calculating to obtain corresponding oil absorption rate k and oil retention rate q, and the result is shown in table 1.
Table 1 results of testing the adsorption properties of the material prepared in example 1 on different oils
From the above results, it can be seen that the floatable and easily degradable material of the present invention has high oil absorption and retention for dirty oil such as heavy oil, crude oil and diesel oil, and thus has the ability to adsorb and degrade dirty oil.
Claims (8)
1. A preparation method of a floatable and easily degradable immobilized material for embedding petroleum degrading strains comprises the following steps:
1) dissolving a natural polymer gel carrier in water to form an aqueous solution, and then sequentially adding a free radical scavenger and a strong oxidant into the aqueous solution to carry out an oxidation reaction to obtain a reaction solution of an aldehyde group-containing activated intermediate;
2) adding an oxidation terminator into the reaction liquid of the aldehyde group-containing activated intermediate in the step 1), and reacting the oxidation terminator with the excessive strong oxidant in the step 1) to obtain a partial oxidation product of the natural polymer gel carrier;
3) dissolving partial oxidation product of the natural polymer gel carrier in phosphate buffer solution with pH of 7.0, adding carbonyl reducing agent to reduce carbonyl, and adding organic synthesis intermediate NH2R, reacting aldehyde group with amino group, reducing and hydrogenating to obtain a reaction system containing the hydrophobic alkyl product grafted on the natural polymer gel carrier, stirring at room temperature, adding methanol to form a precipitate product, centrifugally separating, and collecting the precipitate to obtain a solid hydrophobic alkyl product grafted on the natural polymer gel carrier; wherein, the NH2R of R is selected from C6Alkyl radical, C12Alkyl radical, C18Any one of alkyl groups;
4) dissolving the solid of the hydrophobic alkyl product grafted on the natural polymer gel carrier in water, and adding an organic polymer carrier, a cross-linking agent and petroleum degrading bacteria for cross-linking reaction to obtain the product;
the mass ratio of the hydrophobic alkyl product grafted on the natural polymer gel carrier, the organic polymer carrier, the cross-linking agent and the petroleum degrading bacteria is (1-4): (0.5-2.5): (0.02-0.5): (0.4-0.5);
the petroleum degrading bacteria are selected from composite oil-feeding bacteria prepared from paraffinum kansuensis, bacillus subtilis, diesel oil alkalophilic bacteria and marinobacter hydrocarbonoclavus according to the dried mass ratio of 1:5:3: 1;
in the step 1), the natural polymer gel carrier is selected from sodium alginate;
the free radical scavenger is selected from n-propanol;
the strong oxidant is selected from sodium periodate;
in the step 2), the oxidation terminator is selected from any one of the following: ethylene glycol, propylene glycol, hydroquinone, potassium permanganate;
in the step 3), the carbonyl reducing agent is selected from at least one of the following: NaCNBH3 、NaBH4 And PhSeH;
in the step 4), the organic polymer carrier is selected from: polyvinyl alcohol;
the cross-linking agent is selected from any one of the following: calcium chloride, boric acid, hexamethylenediamine and glutaraldehyde.
2. The method of claim 1, wherein:
the oxidation reaction in the step 1) is carried out under the condition of keeping out of the sun, and the reaction condition of the oxidation reaction is 4 ℃ for 2 hours.
3. The production method according to claim 1 or 2, characterized in that: in the step 2), the oxidation terminator is selected from ethylene glycol;
in the steps 1) and 2), the mass ratio of the natural polymer gel carrier to the radical scavenger to the strong oxidant to the oxidation terminator is (0.5-2.0): (1-5): (0.1-0.3): (1-2).
4. The method of claim 1, wherein: in the step 3), the carbonyl reducing agent is selected from NaCNBH3；
In the step 3), the mass ratio of the partial oxidation product of the natural polymer gel carrier, the carbonyl reducing agent and the organic synthesis intermediate is (0.5-2.0): (0.4-1.0): (0.4-2.0).
5. The method of claim 1, wherein: in the step 4), the crosslinking reaction condition is room temperature.
6. The floatable, easily degradable immobilized material embedded with petroleum degrading bacterial strain prepared by the method of any one of claims 1 to 5.
7. The use of the floatable, easily degradable immobilized material of buried oil degrading bacteria species as claimed in claim 6 in the field of water treatment.
8. The use of claim 7, wherein: the application is the application in the aspect of cleaning oil spill pollution.
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| CN110980960B (en) * | 2019-11-26 | 2022-04-08 | 浙江永续环境工程有限公司 | Oil removing microbial inoculum and sludge treatment method using same |
| CN112457877B (en) * | 2021-01-25 | 2021-04-06 | 东营市宝泽能源科技有限公司 | Preparation method of high-dehydration-rate oil field demulsifier |
| WO2022229225A1 (en) * | 2021-04-26 | 2022-11-03 | Novozymes A/S | Method of treating aquatic or marine animals using polymer supports |
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| CN103031298B (en) * | 2011-09-30 | 2014-07-30 | 中国科学院沈阳应用生态研究所 | Immobilized microorganism particle for degrading petroleum in water |
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