CN101705099B - Composite material used in soil remediation and preparation method thereof - Google Patents
Composite material used in soil remediation and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a composite material used in soil remediation and a preparation method thereof. The remediation material is a porous compound material with through pores, and formed by crosslinking carboxymethylcellulose or sodium salt components thereof and chitosan with the mass ratio of being 0.5-9.5:1; the average pore size of the pore is 20-200 mum; and the water absorption rate among the pores is 2000 percent to 8000 percent of the self weight of the material. In preparation, the carboxymethylcellulose or the sodium salt components thereof and the chitosan are mixed with water under the condition that pH is 2 to 5 and the temperature is 30 to 60 DEG C so as to form a clear and transparent sol system; then the system is arranged in a molding mold, the temperature is reduced to minus 20 DEG C for fully congealing; and finally the porous composite material is obtained after freeze drying. The porous composite material can be directly inoculated with phosphate-solubilizing bacterium and nitrogen-fixing bacterium, has the functions of water absorption and water maintenance properties and higher density for bearing the microorganisms of phosphate-solubilizing bacterium and/or nitrogen-fixing bacterium and the like, and good biocompatibility and biodegradability; and degradation products have no pollution to the environment, can be recycled for use in ecological environment, and can improve soil structure by mixing with soil so as to absorb and maintain water and enhance the soil fertility.
Description
Technical field
The present invention relates to a kind of soil remediation matrix material of agriculture usefulness, specifically is to have suction/water retaining function, and as the further functional composite material of microbe carriers such as load phosphate solubilizing bacteria, vinelandii, and this preparation methods.
Background technology
Normally a kind of functional high molecule material that contains strong hydrophilicity groups such as carboxyl, hydroxyl and have certain degree of crosslinking of high water absorbing and retaining material, it is water insoluble, but have very high suction, water retention capacity, be widely used at present in the fields such as health care, agriculture gardens, petrochemical complex, civil construction.As people such as Li Li at " preparation technology of natural polymer water-absorbing material and performance evaluation " (" Materials science and technology " [J] .2006,14 (5): reported 470-477) and will be applied in agricultural gardening aspect, can have higher water-intake rate with the high-absorbent material of preparations such as starch graft acrylic acid, acrylate, vinyl acetate, acrylic amine.But it is remaining in problem aspect preparation technology, production cost and the environmental protection.In addition, as the acrylic polymers of current high water absorbing and retaining material main product, its Biodegradable is poor, and ecotope is had very big disadvantageous effect, and its preparation raw material then depends on growing tension and exhausted petroleum resources, thereby is not more and more accepted by people.Research and development biodegradation type, environmentally friendly high water absorbing and retaining material come into one's own day by day.
Mierocrystalline cellulose is the natural high molecular substance of amount maximum on the earth, and is cheap, can water absorption and swelling in water, can be used as water-absorbing material, and especially it has the excellent biodegradability energy, and the degraded product environmental friendliness.The at present existing report that Mierocrystalline cellulose is prepared high-absorbent material by methods such as etherificate, esterification, crosslinked, graft copolymerizations, after particularly preparation of cellulose being become carboxymethyl cellulose, through the crosslinked high-absorbent material of making, its water-intake rate is moderate again, absorption speed is fast, can spontaneously degrade at occurring in nature.
Chitosan is a kind of polycation polysaccharide, often by chitin through deacetylated and get, have excellent biological compatibility and degradation property.Holding out broad prospects aspect the preparation high-absorbent material.
Composite material film by carboxymethyl cellulose and Preparation of Chitosan, but utilize it at the ventilation property carrying medicament and help property aspect the biology such as histocyte growth, in medical material as existing at present research of the application of guided tissue regeneration's film and report.
On the other hand, for satisfying nutritive elements such as the existence of plant or farm crop, the required nitrogen of growth, phosphorus, industrial chemical fertilizer is considered to realize in the agriculture production main path of this purpose always.But along with the increase of fertilizer amount, it is big to non-renewable energy consumption as the cost height, polluted air, soil and water quality, and food safeties such as harm husbandry, it is obvious day by day to destroy Soil structure and negative impacts such as micro-flora and diversity.Along with to requirement on environmental protection, to the understanding of nonrenewable resource crisis and to the understanding of sustainable agriculture importance, the research of seeking other fertilizer sources grows with each passing day.
The content of nitrogen is near 80% in the atmosphere, but most of plant can not directly absorb.Then can be as microorganisms such as azotobacters by the activity of nitrogenase in the body, the nitrogen of molecular conformation in the air is fixed and is transformed into can be the ammonia-state nitrogen of the direct utilization of organism, promptly so-called biological nitrogen fixation.Phosphorus is the same with nitrogen, all plays a crucial role in the metabolism activities such as energy transformation, breathing and photosynthesis of plant.But have now and studies show that the utilization ratio of the phosphate fertilizer in being manured into soil only is about 20%, the phosphorus of the overwhelming majority have all been formed insoluble phosphatization thing by soil fixing.Therefore, the utilization ratio of nitrogen-fixing microorganism quantity and phosphorus has important effect to plant-growth in the raising soil.Studies have shown that in a large number, phosphate solubilizing bacteria is inoculated in soil, the organic acid that utilizes its growth and breeding to produce can be a titanium pigment with insoluble phosphatization thing decomposition and inversion in the soil, can increase substantially available phosphorus contents in the soil, thereby improves the plain nutrition of phosphorus of crop.And phosphate solubilizing bacteria is to also having obvious facilitation between the breedings of vinelandii and the nitrogenase activity, and vinelandii equally also exist crucial biological effect to the sprouting of phosphate solubilizing bacteria and the formation of water-soluble phosphorus.But in the practical application, owing to lack the effective carrier of these microorganisms in the soil, therefore being difficult to bring into play it should have and maximum effect and effect, and the fertilizer component of discharging and/or forming also runs off with water easily, is difficult to play improve Soil structure, increase soil fertility and improve nutrition and somatotrophic effect to plant.
Summary of the invention
At above-mentioned situation, the present invention will provide a kind of can have suction/water retaining function, and all right as microorganism carriers such as further load phosphate solubilizing bacteria of energy and/or vinelandii, thereby can be used for the functional high molecule material of soil remediation.On this basis, the present invention further also will provide the preparation method of this used in soil remediation matrix material.
The matrix material of used in soil remediation of the present invention, be to be 0.5～9.5 by mass ratio: 1, be preferably 4～9: 1 carboxymethyl cellulose or its sodium salt composition with chitosan crosslinked become have the composite porous of connectivity pore texture, the mean pore size of hole is 20～200 μ m, and the water-intake rate of the moisture of attracting deposit in the hole is 2000%～8000% of a material sole mass.
Wherein, said carboxymethyl cellulose or sodium carboxymethyl-cellulose, it can be Mierocrystalline cellulose by various source formations, as the Mierocrystalline cellulose that obtains by raw materials such as common fiber crops, straw, straw, bagasse, handle (can with reference to the method for modifying as documents such as CN03117504.X) through carboxylated modification, the substitution value that particularly makes carboxymethyl cellulose after the modification is greater than 0.6 carboxymethyl cellulose (or sodium salt).The more carboxyls that have on its structure help improving that it is hydrophilic, suction and water retention property.
Said chitosan, normally by chitin through deacetylated and a kind of polycation polysaccharide that obtain has excellent biological compatibility, degradation property and water-absorbent.Experiment shows that the deacetylation of chitin is high more, and corresponding chitosan is soluble in water more.So employed chitosan in the above-mentioned matrix material of the present invention, what preferably adopt is to comprise that deacetylation is 70%～100% chitosan, and accordingly further by carboxymethyl, propyloic, hydroxyethyl, hydroxypropyls etc. replace the chitosan of form.Wherein the substituting group chain is long more, and soaking effect is poor more, cm-chitosan preferably, and perhaps as N-acetylated chitosan sugar, the water-soluble chitosan that N-propionyl chitosan etc. are commonly used.
Because carboxymethyl cellulose (or sodium salt) is anionic polymer, chitosan is a cationic polymers, and all contains a large amount of as hydrophilic radicals such as hydroxyl, amino, kharophens on two kinds of polymer molecular chains.Test-results shows, in the above-mentioned matrix material of the present invention by the carboxyl on carboxymethyl cellulose (or sodium salt) and the chitosan crosslinked structural chain of forming, amino, hydrophilic radicals such as hydroxyl are many more, the performance of its suction/water conservation is strong more, good more, and can make this matrix material realization of the present invention and satisfy actual needed suction/water conservation and relevant performance by suitably adjusting its content ratio.
Above-mentioned said composite porous, not only have good suction/water retaining function, can also become microorganism carriers such as energy higher density ground load phosphate solubilizing bacteria, vinelandii.With phosphate solubilizing bacteria of using always and/or vinelandii with nitrogen fixation with phosphate solubilization, as phosphate solubilizing bacterias such as genus bacillus, false pseudomonas bacillus, edaphic bacillus and or as vinelandii direct inoculation such as root nodule bacterium, azospirillum, Alcaligenes faecaliss in above-mentioned matrix material.The inoculum size of phosphate solubilizing bacteria and/or vinelandii generally there is no too much requirement, by soil regime with need decide, for example, its separately the preferable range of inoculum size can reach 200,000,000/restrain.A large amount of perforation hole formula reticulated structures in the matrix material of the present invention help microorganism adhering growth and breeding and interaction successfully thereon for microbial reproduction provides three-dimensional solid space.Therefore matrix material of the present invention also further becomes the microorganism water absorption and water retention composite materials that load has phosphorus decomposing and/or vinelandii.
Microorganisms such as inoculation phosphate solubilizing bacteria and/or vinelandii are proven technique belonging at present on matrix material.Said phosphate solubilizing bacteria and/or vinelandii comprise the bacterial classification collection, and strain expanded culture etc. can adopt by present conventional bacterial classification and training method to obtain.Concrete grammar also can be with reference to as people such as Ding Chunmei " influence of vaccination ways pair cell rate of vaccination and distribution in three-dimensional material " (" biotechnology journal " [J] .2005,21 (4): the associated viscera 649-653).For example, a kind of mode wherein is to inoculate bacterial classification on by common bacteria substratum such as pancreas peptone soybean broths, puts in the incubator 25-30 ℃ and cultivates after 1-3 days and obtain corresponding phosphate solubilizing bacteria and/or vinelandii.
Preparation to the above-mentioned matrix material of the present invention, can with the carboxymethyl cellulose of said ratio or its sodium salt composition and chitosan in pH value 2～5, be preferably the pH value especially and be about under 3 and 30 ℃～60 ℃ conditions, to account for total mass ratio 1%～20%, be preferably 2%～10% amount and water thorough mixing.In thorough mixing, codissolved process, can fully contact, react and finish between the active group in its molecule and be cross-linked with each other with hydroxyl, make compound material have certain gel-strength, form the sol system (viscosity generally can be 200-5000mPas) of clear shape.This sol system material of finishing after crosslinked is placed forming mould, cool, it is fully congealed, and then, promptly obtain said composite porous through lyophilize to-20 ℃.
Carboxymethyl cellulose or its sodium salt composition and codissolved optimal way of mixing of chitosan, be earlier it to be made for the aqueous solution separately, both aqueous solution is slowly mixed (for example chitosan solution slowly being joined in the carboxymethyl aqueous solution), it is altogether molten and react to help the even thorough mixing of two kinds of compositions.
For guaranteeing that material can the thorough mixing reaction, often well-beaten condition need be arranged, and therefore have inclusion of air and make in the reaction mass system and form bubble.Test shows, bubble in the material system can be to the crosslinked and combination of two components in the product, and the water absorbing properties of products obtained therefrom constitutes influence, but reacted colloidal sol material is before carrying out condensation, still with earlier by as leave standstill etc. easy and usual way removed be condensed into again behind the bubble that exists in the system good.
Suction/the water retention of matrix material of the present invention is to realize by the crosslinked vesicular structure of hydrophilic radical in the material and the connectivity hole that is had.Test shows, carboxymethyl cellulose (or sodium salt) and chitosan are when thorough mixing is molten altogether, the usage ratio of chitosan is excessive, can make formed network structure relatively too closely knit, hydrophilic radicals such as hydroxyl in the structure and carboxyl are fettered, and are unfavorable for the raising of the water-intake rate and the water retention of matrix material.If the usage ratio of carboxymethyl cellulose (or sodium salt) is too high, then because the cross-linking set between itself and chitosan is very few, degree of crosslinking is on the low side, the network structure that forms is too loose, after the matrix material suction, be difficult to keep the certain shape and gel-strength, solvable composition increases in the matrix material, and its water-retaining capacity is obviously descended.
Experiment shows, above-mentioned said carboxymethyl cellulose (or sodium salt) and chitosan blended pH and temperature range, and it is favourable being total to molten and forming said sol system for its thorough mixing.Wherein, the conditioning agent as adjusting material system pH is preferably organic acids such as formic acid or acetate.
Sol system material after the crosslinking reaction in forming mould through the cooling freezing treatment after, moisture in the material can form space-occupying ice crystal, again after lyophilize, after ice crystal in the material distils in position and removes, promptly form desirable connectivity hole and cavity, by the carboxyl in the structure, amino, hydrophilic radicals such as hydroxyl just can suck water and remain in the hole.Test shows that in the refrigerated process of lowering the temperature, the cooling chilling rate that suitably slows down can help slowly forming uniform ice crystal in material, helps the final even more ideal hole of uniformity coefficient that forms in matrix material.Therefore in above-mentioned preparation method, when carrying out said cooling and handling, the mode that the multiple cooling rate that slows down can be arranged is as preferred.For example, can adopt in 20～24 hours and slowly reduce to-20 ℃ by room temperature, and at-20 ℃ of slow cooling methods that keep 12 hours at least; Or adopt after 4 ℃ of abundant coolings, be cooled to-10 ℃ again and also kept at least 8 hours, be cooled to-20 ℃ at last and also keep 8 hours gradient cooling mode at least; Maybe can also adopt after 4 ℃ of abundant coolings, be cooled to-20 ℃ of gradient cooling modes that also keep 8～12 hours at least etc. again, the effect that can obtain.
When carrying out lyophilize, preferred treatment temp is-40～-50 ℃ by the material after fully congealing.For example, use freeze drier freeze-drying commonly used at present can finish in 3～4 days, its freeze temperature can be-40～-50 ℃ usually, freeze-drying pressure 10～300Pa pressure.
Obtain said composite porous after, according to different needs, can be by present routine operation mode, with the said vinelandii direct inoculation that has the phosphate solubilizing bacteria of phosphate solubilization and/or have a nitrogen fixation on this matrix material.
As above-mentioned, Mierocrystalline cellulose is a large amount of natural high molecular substances that exist on the earth, and is cheap, and has the excellent biodegradability energy, the degraded product environmental friendliness.Chitosan also is a kind of material with excellent biological compatibility and degradation property.Therefore, the present invention through crosslinked form composite porous, can have excellent biological compatibility by carboxymethyl cellulose (or sodium salt) and chitosan, and can be used as with phosphate solubilizing bacteria and vinelandii are good compatible and can be with the carrier of higher density load.Compare with simple present other porous material by suction type load microorganism, the reticulated structure of the perforation hole formula in the matrix material of the present invention can provide and more help microbial reproduction and interactional three-dimensional space.Therefore; matrix material of the present invention is as the microorganism water absorption and water retention composite materials of load phosphorus decomposing of a kind of energy and/or vinelandii; can reach suction/water retaining function; the effect that can have the nomadic nitrogen in the fixed air again and decompose the insoluble phosphatization thing in the soil; with mixing with soil; can improve Soil structure; water-absorbing-retaining; increase soil fertility; thereby plant is produced tangible nutrition and growth promoting function; be a kind of matrix material of environmentally friendly used in soil remediation, be particularly conducive to the improvement of Desertification soil and the soil protection of arid area.Compare with traditional acrylic acid or the like high water absorbing and retaining material, improving crop yield and quality, help the recycle and the Sustainable development aspect of ecotope, significant superiority and significance are arranged, have great exploitation and be worth.
Below in conjunction with the embodiment of accompanying drawing illustrated embodiment, foregoing of the present invention is described in further detail again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made all should comprise within the scope of the invention.
Description of drawings
Fig. 1 is by carboxymethyl cellulose and the chitosan stereoscan photograph with the matrix material of the present invention that forms at 1: 1.
Fig. 2 is the inverted phase contrast microscope photo after the suction of Fig. 1 matrix material.
Embodiment
Embodiment 1
Xylo-Mucine 4g is dissolved in the 250g deionized water in 60 ℃.After chitosan (deacetylation 90%) 6g is dissolved in 2% acetic acid aqueous solution of 150g, add in the cmc soln gradually, obtain the sol system of clear shape behind the reaction 3h, leave standstill bubble, slowly reduce to-20 ℃ by room temperature in 20～24 hours, and kept at least 12 hours at-20 ℃, take out and put in the freeze drier (50 ℃, 10Pa) freeze-drying.After deionized water was washed till neutrality, surveying its water-intake rate was under 2613.5 ± 91.3%, 40 ℃ of air seasoning conditions, and water-retaining capacity is 40% o'clock water conservation time to be about 3.5h.The porosity of gained matrix material is 90%-95%.
After the composite porous ethane via epoxyethane sterilization of gained, inoculum density is respectively the false pseudomonas bacillus and the Alcaligenes faecalis of 100,000,000/gram simultaneously, cultivates down that centrifugation goes out bacterial plate counts after 1 day for 30 ℃ in the incubator, and density is 2,500,000,000/gram.
Embodiment 2
Xylo-Mucine 5g is dissolved in the 250g deionized water under 60 ℃.After chitosan (deacetylation is 95%) 5g is dissolved in 2% aqueous formic acid of 150g, add gradually in the carboxymethyl cellulose colloidal sol, obtain the sol system of clear shape behind the reaction 3h, leave standstill bubble, after 4 ℃ of abundant coolings, be cooled to-10 ℃ again and also kept at least 8 hours, be cooled to-20 ℃ at last and also kept at least 8 hours, taking-up put freeze-drying in the freeze drier (45 ℃, 10Pa).After deionized water was washed till neutrality, surveying its porosity was 90%-95%, and water-intake rate is under 1768.7 ± 127.6%, 40 ℃ of air seasoning conditions, and water-retaining capacity is 40% o'clock water conservation time to be about 3.5h.Matrix material ethane via epoxyethane sterilization, inoculum density are the false pseudomonas bacillus of 200,000,000/gram, cultivate down that centrifugation goes out bacterial plate counts after 1 day for 30 ℃ in the incubator, and density is 2,300,000,000/gram.
Inverted phase contrast microscope photo after the stereoscan photograph that the gained matrix material is handled and its suction, respectively as depicted in figs. 1 and 2.The water molecules center for forming of arrow indication among Fig. 2.
Embodiment 3
Carboxymethyl cellulose 6g, be dissolved under 60 ℃ in the 250g deionized water, cm-chitosan 4g is dissolved in the 150g aqueous solution, add gradually in the carboxymethyl cellulose colloidal sol, obtain the sol system of clear shape behind the reaction 3h, leave standstill bubble, after 4 ℃ of abundant coolings, be cooled to-20 ℃ and kept at least 8～12 hours again, take out put freeze-drying in the freeze drier (50 ℃, 8Pa).After deionized water was washed till neutrality, surveying its porosity was 90%-95%, and water-intake rate is under 2202.4 ± 128.6%, 40 ℃ of air seasoning conditions, and water-retaining capacity is 40% o'clock water conservation time to be about 3h.Matrix material ethane via epoxyethane sterilization, inoculum density is respectively the edaphic bacillus and the Alcaligenes faecalis of 100,000,000/gram simultaneously, cultivates down that centrifugation goes out bacterial plate counts after 1 day for 30 ℃ in the incubator, and density is 2,600,000,000/gram.
Embodiment 4
Carboxymethyl cellulose 8g, be dissolved under 60 ℃ in the 250g deionized water, chitosan (deacetylation is 85%) 2g is dissolved in 2% aqueous formic acid of 150g, add gradually in the carboxymethyl cellulose colloidal sol, obtain the sol system of clear shape behind the reaction 3h, leave standstill bubble, slowly reduce to-20 ℃ by room temperature in 20～24 hours, and kept at least 12 hours at-20 ℃, take out and put freeze-drying in the freeze drier.After deionized water was washed till neutrality, surveying its porosity was 90%-95%, and water-intake rate is under 3357.9 ± 182.3%, 40 ℃ of air seasoning conditions, and water-retaining capacity is 40% o'clock water conservation time to be about 5.5h.Matrix material ethane via epoxyethane sterilization, inoculum density is respectively the genus bacillus and the azospirillum of 100,000,000/gram simultaneously, cultivates down that centrifugation goes out bacterial plate counts after 1 day for 30 ℃ in the incubator, and density is 2,800,000,000/gram.
Embodiment 5
Xylo-Mucine 9g, be dissolved under 60 ℃ in the 250g deionized water, chitosan (deacetylation is 80%) 1g is dissolved in 2% acetic acid aqueous solution of 150g, add gradually in the carboxymethyl cellulose colloidal sol, obtain the sol system of clear shape behind the reaction 3h, leave standstill bubble, after 4 ℃ of abundant coolings, be cooled to-10 ℃ again and also kept at least 8 hours, be cooled to-20 ℃ at last and also kept at least 8 hours, take out and put freeze-drying in the freeze drier.After deionized water was washed till neutrality, surveying its porosity was 90%-95%, and water-intake rate is under 6676.0 ± 50.2%, 40 ℃ of air seasoning conditions, and water-retaining capacity is 40% o'clock water conservation time to be about 6.2h.Genus bacillus and Alcaligenes faecalis are inoculated in matrix material ethane via epoxyethane sterilization simultaneously, cultivate down that centrifugation goes out bacterial plate counts after 1 day for 30 ℃ in the incubator, and density is 5,200,000,000/gram.
Embodiment 6
Carboxymethyl cellulose 9.5g, be dissolved under 60 ℃ in the 250g deionized water, cm-chitosan 1g is dissolved in 2% aqueous formic acid of 150g, add gradually in the carboxymethyl cellulose colloidal sol, obtain the sol system of clear shape behind the reaction 3h, leave standstill bubble, slowly reduce to-20 ℃ by room temperature in 20～24 hours, and kept at least 12 hours at-20 ℃, take out and put freeze-drying in the freeze drier.After deionized water was washed till neutrality, surveying its porosity was 90%-95%, and water-intake rate is under 5576.3 ± 81.1%, 40 ℃ of air seasoning conditions, and water-retaining capacity is 40% o'clock water conservation time to be about 5.8h.False pseudomonas bacillus and azospirillum are inoculated in matrix material ethane via epoxyethane sterilization simultaneously, cultivate down that centrifugation goes out bacterial plate counts after 1 day for 30 ℃ in the incubator, and density is 3,200,000,000/gram.
Claims (10)
1. the matrix material of used in soil remediation, it is characterized in that by mass ratio being 0.5～9.5: 1 carboxymethyl cellulose or its sodium salt composition and chitosan crosslinked formed the composite porous of connectivity pore texture that have, the mean pore size of hole is 20～200 μ m, and the water-intake rate of the moisture of attracting deposit in the hole is 2000%～8000% of a material sole mass.
2. the matrix material of used in soil remediation as claimed in claim 1 is characterized in that the mass ratio of said carboxymethyl cellulose or its sodium salt composition and chitosan is 4～9: 1.
3. the matrix material of used in soil remediation as claimed in claim 1 is characterized in that said chitosan is that deacetylation is at least a in the chitosan, cm-chitosan of 70%-100%.
4. as the matrix material of the described used in soil remediation of one of claim 1 to 3, it is characterized in that said composite porous in also inoculation phosphate solubilizing bacteria with phosphate solubilization and/or the vinelandii with nitrogen fixation are arranged.
5. the matrix material of used in soil remediation as claimed in claim 4 is characterized in that the said composite porous phosphate solubilizing bacteria of going up inoculation is genus bacillus, false pseudomonas bacillus, edaphic bacillus; Said vinelandii are root nodule bacterium, azospirillum, Alcaligenes faecalis.
6. the method for preparing the matrix material of the described used in soil remediation of claim 1, it is characterized in that the carboxymethyl cellulose of said ratio or its sodium salt composition and chitosan under pH value 2～5 and 30 ℃～60 ℃ conditions of temperature, after forming the sol system of clear shape with the amount that accounts for total mass ratio 1% to 20% and water thorough mixing, be placed in the forming mould, being cooled to-20 ℃ fully congeals, through lyophilize, obtain composite porous then.
7. preparation method as claimed in claim 6 is characterized in that the pH value when said carboxymethyl cellulose or its sodium salt composition and chitosan thorough mixing form said sol system is about 3.
8. preparation method as claimed in claim 6 is characterized in that the pH value when said carboxymethyl cellulose or its sodium salt composition and chitosan thorough mixing form said sol system is regulated with formic acid or acetate.
9. preparation method as claimed in claim 6, the sol system material that it is characterized in that said clear shape places forming mould to lower the temperature behind the removal bubble earlier again, employing was slowly reduced to-20 ℃ by room temperature in 20～24 hours, and at-20 ℃ of slow cooling methods that keep 12 hours at least; Or adopt after 4 ℃ of abundant coolings, be cooled to-10 ℃ again and also kept at least 8 hours, be cooled to-20 ℃ at last and also keep 8 hours gradient cooling mode at least; Or adopt after 4 ℃ of abundant coolings, be cooled to-20 ℃ again and also keep 8～12 hours gradient cooling mode at least.
10. as the described preparation method of one of claim 6 to 9, it is characterized in that obtain after the lyophilize composite porous on inoculation have the phosphate solubilizing bacteria of phosphate solubilization and/or have the vinelandii of nitrogen fixation.
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| CN106040183A (en) * | 2016-05-23 | 2016-10-26 | 常州大学 | Preparation for carboxymethyl cellulose/chitosan composite xerogel and application of carboxymethyl cellulose/chitosan composite xerogel in adsorption of methyl orange in water |
| CN106967435B (en) * | 2017-05-16 | 2022-03-29 | 厦门大学嘉庚学院 | Preparation method of multifunctional soil conditioner |
| CN110872518B (en) * | 2019-11-20 | 2021-10-08 | 广西金穗生态科技集团股份有限公司 | Acid soil conditioner and preparation method and application thereof |
| CN112779020A (en) * | 2021-01-07 | 2021-05-11 | 陈琴珠 | Saline-alkali soil remediation method |
| CN113072413A (en) * | 2021-03-27 | 2021-07-06 | 海南省农业科学院农业环境与土壤研究所 | Organic fertilizer for soil remediation and preparation method thereof |
| CN114752391B (en) * | 2022-04-06 | 2023-12-22 | 水利部牧区水利科学研究所 | Water-retaining material, preparation method thereof and application thereof in soil moisture retention |
| CN116328734A (en) * | 2023-04-27 | 2023-06-27 | 华南农业大学 | Composite material for synchronously removing heavy metal cadmium and arsenic in soil and preparation method and application thereof |
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