CN111135800A - Biochar material for efficiently reducing arsenic pollution of soil and preparation method thereof - Google Patents
Biochar material for efficiently reducing arsenic pollution of soil and preparation method thereof Download PDFInfo
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- CN111135800A CN111135800A CN202010027917.6A CN202010027917A CN111135800A CN 111135800 A CN111135800 A CN 111135800A CN 202010027917 A CN202010027917 A CN 202010027917A CN 111135800 A CN111135800 A CN 111135800A
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- 239000002689 soil Substances 0.000 title claims abstract description 74
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 60
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 40
- 239000000661 sodium alginate Substances 0.000 claims abstract description 40
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 40
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000001291 vacuum drying Methods 0.000 claims abstract description 23
- 239000001110 calcium chloride Substances 0.000 claims abstract description 22
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 22
- 241001122767 Theaceae Species 0.000 claims abstract description 19
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000007873 sieving Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 13
- 230000002045 lasting effect Effects 0.000 abstract description 3
- 235000016709 nutrition Nutrition 0.000 abstract description 3
- 230000035764 nutrition Effects 0.000 abstract description 3
- 239000011573 trace mineral Substances 0.000 abstract description 2
- 235000013619 trace mineral Nutrition 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 28
- 238000012360 testing method Methods 0.000 description 15
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 14
- 240000003768 Solanum lycopersicum Species 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 108010010803 Gelatin Proteins 0.000 description 11
- 239000008273 gelatin Substances 0.000 description 11
- 229920000159 gelatin Polymers 0.000 description 11
- 235000019322 gelatine Nutrition 0.000 description 11
- 235000011852 gelatine desserts Nutrition 0.000 description 11
- 235000013399 edible fruits Nutrition 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229920001661 Chitosan Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 6
- 229920000053 polysorbate 80 Polymers 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 5
- ZTOKUMPYMPKCFX-CZNUEWPDSA-N (E)-17-[(2R,3R,4S,5S,6R)-6-(acetyloxymethyl)-3-[(2S,3R,4S,5S,6R)-6-(acetyloxymethyl)-3,4,5-trihydroxyoxan-2-yl]oxy-4,5-dihydroxyoxan-2-yl]oxyoctadec-9-enoic acid Chemical compound OC(=O)CCCCCCC/C=C/CCCCCCC(C)O[C@@H]1O[C@H](COC(C)=O)[C@@H](O)[C@H](O)[C@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](COC(C)=O)O1 ZTOKUMPYMPKCFX-CZNUEWPDSA-N 0.000 description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DLAXSPNHLGXZRI-UHFFFAOYSA-M [Fe]S Chemical compound [Fe]S DLAXSPNHLGXZRI-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000003306 harvesting Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000003900 soil pollution Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000287531 Psittacidae Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003876 biosurfactant Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002681 soil colloid Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a biochar material for efficiently reducing arsenic pollution of soil, which is prepared by the following steps: s1, drying and crushing the tea leaves, heating to 500-600 ℃, preserving heat for 2-3 hours, stopping heating, and grinding and sieving for later use; s2, adding the biochar obtained in the step S1 into a sodium alginate aqueous solution, stirring for 3-4 hours, and then slowly dropping CaCl2In the aqueous solution, continuously stirring for 6-8 h in the dropping process, filtering, washing with water, and vacuum drying for later use; s3, adding the product obtained in the step S2 into a cellobiose aqueous solution, standing for 3-4 hours, performing ultrasonic treatment for 30-60 min, filtering, and performing vacuum drying to obtain the biochar material, wherein the biochar material can maintain efficient and lasting adsorption and fixation effects on effective arsenic in soil, is natural in component material, cannot influence nutrition and trace elements in soil, and further cannot influence planted cropsCan effectively reduce the arsenic content in the planted crops.
Description
Technical Field
The invention belongs to the technical field of water and soil pollution treatment, and particularly relates to a biochar material for efficiently reducing arsenic pollution of soil and a preparation method thereof.
Background
Soil is basic data of agricultural production, is an important environmental condition for crops to grow and develop, 97% of grain production in the world depends on soil, agriculture is continuously and healthily developed to obtain stably increased productivity, and firstly, the fertility and safety of the soil must be ensured, but in recent years, due to natural activities and human activities such as natural weathering, geochemical reaction, biological operation and the like, more and more detected soil contains heavy metal arsenic, so that the soil impacts the originally few farmlands in China, crops are planted in farmlands with accumulated and even exceeding arsenic content, the yield of the crops can be reduced, and the arsenic content of corresponding agricultural products can be increased and even exceed the standard. The arsenicals have high toxicity and can seriously affect the health of human bodies or animals, 0.1g of arsenic trioxide can kill human bodies, and long-term eating of food containing arsenic can cancerate human organs and cause the problem that the arsenic pollutes soil.
The biochar is a carbon-containing solid substance generated by biological residues under the condition of low-oxygen or anaerobic pyrolysis at high temperature (less than or equal to 700 ℃), has a compact microporous structure, a huge specific surface area and abundant surface oxygen-containing functional groups and adsorption sites, and is proved to be used as a novel environmental material for treating heavy metal pollution. However, the existing treatment of the biochar mainly aims at water body pollution, and the soil pollution is obviously different from the water body pollution, so that on one hand, the environment in the soil is complex and contains various organic matters and microorganisms, which all influence the adsorption efficiency of the biochar; on the other hand, the soil has larger buffer property, heavy metal ions adsorbed by the biochar can be slowly released from soil colloid or soil minerals, and the fixing effect of the biochar on arsenic is not durable. Therefore, at present, a few cases of treating arsenic pollution of soil by using biochar alone are available, the effect is limited, and other materials are usually required to be compounded to achieve a better effect. In order to enhance the adsorption effect of biochar on arsenic, biochar and ferric salt are compounded to prepare iron-based biochar in the prior art, the strong affinity of iron to arsenic is utilized to strengthen the effective fixation of arsenic in soil, but the planting soil needs to be fertilized regularly, the fertilizer contains iron elements required by soil, the application of the iron-based biochar inevitably increases the iron elements in the soil, the absorption of plants on other nutrient elements such as calcium and the like can be influenced due to too high content of iron in the soil, and the plants show poor growth, so the application of the biochar can be limited.
Disclosure of Invention
The invention aims to solve the technical problems and provides a biochar material for efficiently reducing arsenic pollution of soil and a preparation method thereof, wherein the biochar material can maintain efficient and lasting adsorption and fixation effects on effective arsenic in the soil, is natural in component materials, does not influence nutrition and trace elements in the soil, further does not influence growth of planted crops, and can effectively reduce the content of arsenic in the planted crops.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a method for preparing a biochar material capable of efficiently reducing arsenic pollution of soil, which comprises the following steps:
s1, drying and crushing the tea leaves, heating to 500-600 ℃, preserving heat for 2-3 hours, stopping heating, and grinding and sieving for later use;
s2, adding the biochar obtained in the step S1 into a sodium alginate aqueous solution, stirring for 3-4 hours, and then slowly dropping CaCl2In the aqueous solution, continuously stirring for 6-8 h in the dropping process, filtering, repeatedly washing with water, and performing vacuum drying at 50-60 ℃ for later use;
s3, adding the product obtained in the step S2 into a cellobiose water solution, standing for 3-4 hours, then carrying out ultrasonic treatment for 30-60 min, filtering, and carrying out vacuum drying at 50-60 ℃ to obtain the product.
As a preferable embodiment of the invention, the tea leaves in the S1 are kept at 550-580 ℃ for 2.5-3 h.
In a preferred embodiment of the present invention, the tea leaves heated in S1 are ground to have a particle size of 0.2 to 0.3 mm.
In a preferred embodiment of the invention, the concentration of the sodium alginate aqueous solution in the S2 is 1-1.5%, and the weight ratio of the biochar to the sodium alginate is 3-4: 1.
As a preferred embodiment of the present invention, CaCl in S2 is2The concentration of the aqueous solution is 4-5%, and the sodium alginate aqueous solution and CaCl are2The volume ratio of the aqueous solution is 1: 1-1.5.
In a preferred embodiment of the present invention, the concentration of the aqueous cellobiose solution in S3 is 10 to 15%.
The invention also provides a preferable method for preparing the biochar material capable of efficiently reducing the arsenic pollution of the soil, which comprises the following steps:
s1, airing and crushing the tea leaves, heating to 560 ℃, preserving heat for 3 hours, stopping heating, grinding and sieving until the particle size is 0.2-0.3 mm for later use;
s2, adding the biochar obtained in the step S1 into a 1.2% sodium alginate aqueous solution, stirring for 4 hours, and slowly dropping 5% CaCl2In aqueous solution, sodium alginate aqueous solution and CaCl2The volume ratio of the aqueous solution is 1:1.2, stirring is continued for 6 hours in the dropping process, water is repeatedly used for washing after filtering, and vacuum drying is carried out at 55 ℃ for standby;
s3, adding the product obtained in the step S2 into a 12% cellobiose aqueous solution, standing for 3 hours, then carrying out ultrasonic treatment for 60min, filtering, and carrying out vacuum drying at 55 ℃ to obtain the product.
The biochar material prepared by the method is used for repairing and treating arsenic-polluted soil, wherein the weight ratio of the biochar material to the soil is 1: 100-500.
In summary, compared with the prior art, the invention has the following beneficial effects:
firstly, the biochar material prepared by taking tea leaves as a biomass source at a specific temperature and time is detected to have a density of 0.4cm3/cm3Wherein the total micropore volume comprises 22% of the total pore volume, the total mesopore volume comprises 28% of the total pore volume, and the balance is the total macropore volume, which is more conducive to the adsorption of arsenic in the soil in its available state due to the higher proportion of the total micropore volume.
The biochar prepared from the tea leaves is reacted with sodium alginate to prepare the sodium alginate modified biochar, and compared with unmodified biochar, the method can increase the pore surface and micropore volume of the biochar, enhance the permeability of the biochar in soil and improve the adsorption capacity of the biochar to the effective arsenic in the soil.
Thirdly, the biochar modified by the sodium alginate is placed in the biosurfactant cellobiose aqueous solution for ultrasonic treatment, impurities such as tar and the like are removed from the surface and among pores of the biochar, the soil solution is helped to permeate into the pore structure of the biochar, the fixing force of the effective arsenic in the soil is enhanced, and the adsorption effect of the biochar material on the arsenic is more stable and durable.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the scope of the above-described subject matter is not limited to the following examples, and any techniques implemented based on the disclosure of the present invention are within the scope of the present invention.
Comparison of adsorption Properties of one and different modified biochar
Comparative example 1
Unmodified biochar
The preparation method comprises the following steps: airing the tea leaves, weighing 10kg of the tea leaves, crushing, heating to 560 ℃, preserving heat for 3h, stopping heating, grinding and sieving until the particle size is 0.2-0.3 mm, and obtaining the biochar.
Comparative example 2
Iron-based biochar A
The preparation method comprises the following steps: s1, airing the chaff, weighing 10kg of the chaff, crushing, heating to 500 ℃, preserving heat for 9 hours, stopping heating, grinding and sieving until the particle size is 0.2-0.3 mm, and obtaining biochar;
s2, adding 250g of ferric sulfate solid into the biochar prepared in the S1 under the stirring condition, and stirring for reacting for 1 hour to obtain mixed powder;
s3, slowly and dropwise adding 500ml of 0.01 mass percent sodium borohydride aqueous solution into the mixed powder of S2, stirring for reaction for 2 hours, then slowly and dropwise adding 1000ml of 0.05 mass percent tween-80 aqueous solution, heating to 800 ℃, keeping the temperature for 2 hours, stopping heating, cooling, and crushing to obtain the iron-based biochar material.
Comparative example 3
Magnetic chitosan biochar
The preparation method comprises the following steps: s1, 0.6mol/LFeCl3·6H2O and FeCl2·4H2Dissolving O in 240mL of water, uniformly mixing, dropwise adding 1mol/L sodium hydroxide solution at 55 ℃ until the pH value is 9, stirring for 10min, adjusting the temperature to 65 ℃, then adding 0.8mL of Tween 80, stirring for 3omin, adjusting the pH value to be neutral, washing, performing ultrasonic treatment at 40 ℃ for 40min, and performing constant volume to obtain the magnetofluid;
s2, dissolving 2g of chitosan in 2% by volume of acetic acid solution to prepare 2% by mass of chitosan solution;
s3, dripping 10mL of magnetic fluid into the chitosan solution under the condition of stirring, stirring for 30min, adding 1g of the tea leaf residue biochar prepared in the comparative example 1, stirring for 60min, adding 4mL of 25% glutaraldehyde solution, stirring to form gel, adjusting the pH to 9 by using 1mol/L sodium hydroxide, continuing stirring for 2h, cooling the product, separating and washing, drying at 60 ℃, grinding, and sieving by a 150-mesh sieve to obtain the magnetic chitosan biochar.
Comparative example 4
Mercapto-iron based biochar
The preparation method comprises the following steps: s1, weighing 0.5ml of gamma-mercaptopropyl-trimethoxysilane, and preparing 10ml of gamma-mercaptopropyl-trimethoxysilane solution according to the volume ratio of gamma-mercaptopropyl-trimethoxysilane to ethanol to water to 0.5 to 9 to 0.5;
s2, weighing 40.4g Fe (NO)3)3·9H20 is dissolved in 1L of water to obtain 1L of 0.1mol/LFe (NO)3)3Solution 16g of sodium carbonate are weighed out and added to Fe (NO)3)3Stirring the solution for 2 hours, and then placing the solution in a dryer to age for 24 hours at 80 ℃ for later use;
s3, adding 4g of the tea leaf residue biochar prepared in the comparative example 1 into 200mL of deionized water, uniformly stirring, slowly adding 10mL of gamma-mercaptopropyl trimethoxy silane solution, and stirring for reacting for 2 hours;
s4, centrifuging the reaction liquid of S3, drying the obtained solid in a dryer at 105 ℃, calcining for 2h at 500 ℃, cooling, washing with deionized water, drying at 60 ℃, grinding, and sieving with a 100-mesh sieve to obtain the mercapto-iron-based biochar.
Comparative example 5
Magnetic gelatin biochar
The preparation method comprises the following steps: s1, weighing 2g of gelatin, adding the gelatin into 100mL of water, and stirring at 55 ℃ to form a gelatin solution;
s2, weighing 0.02mol of ferric oxide and 0.01mol of ferrous chloride, respectively dissolving in 200mL of water, simultaneously pouring the two solutions into a gelatin solution, continuously stirring at 80 ℃, then adding 120mL of ammonia water, stirring for 5min, then adding 2g of the biochar prepared in the comparative example 1, adding three drops of Tween 80, dispersing the gelatin, continuously stirring for 1h after uniformly mixing, precipitating the content by using a magnet, repeatedly washing the precipitate with deionized water to be neutral, then carrying out vacuum drying at 60 ℃ for 24h, and grinding through a 200nm sieve to obtain the magnetic gelatin biochar.
Comparative example 6
Sodium alginate biochar
The preparation method comprises the following steps: s1, dissolving 1.5g of sodium alginate in 100mL of water to prepare 1.5% sodium alginate solution, and adding 5g of CaCl2Dissolving in 100mL water to obtain 5% CaCl2A solution;
s2, adding 5.25g of biochar prepared in the comparative example 1 into 100mL of 1.5% sodium alginate solution, stirring for 4 hours, and slowly dropping the mixed solution into 120mL of 5% CaCl2And (3) continuously stirring for 6h in the dropping process in the aqueous solution, then filtering, washing with water, and vacuum-drying for 24h at 55 ℃ to obtain the sodium alginate biochar.
Test method
Selecting a piece of planting soil polluted by arsenic as test soil, respectively taking 2g of various biochar materials prepared in comparative examples 1-6, respectively adding the biochar materials into 50g of arsenic-polluted soil, adding deionized water according to the water-soil mass ratio of 2:1, stirring the mixture until the mixture is uniform, respectively taking out part of the soil after fixing for one month, three months, six months and twelve months, and measuring the effective arsenic in the soil, wherein the content of the effective arsenic in the soil before and after the processing of the biochar materials in the arsenic-polluted soil is shown in table 1 through detection.
TABLE 1 COMPARATIVE EXAMPLES 1-6 ARAs CONTENT IN ACTIVE STATE BETWEEN TREATMENT OF ARSENIC SOIL
Test results show that the biochar prepared by the conventional method has extremely weak effect of reducing the arsenic content in soil, and even can increase the content of the available arsenic in the soil, while the prepared iron-based biochar, magnetic chitosan biochar, sulfydryl-iron-based biochar, magnetic gelatin biochar, sodium alginate biochar and other different modified biochar materials can obviously reduce the arsenic content in the first month of treatment, but generally can only be maintained for the third month, the effective arsenic content in the soil begins to increase until the tenth month due to the weakening of adsorption and the occurrence of desorption phenomena, and the arsenic content is increased to a higher level again.
Secondly, influence of the surfactant on adsorption stability of the modified charcoal
Comparative example 7
And (2) putting 8g of span 60 into 100mL of 95% ethanol, heating to dissolve the span 60 to prepare 8% span 60 alcohol solution, then soaking the mercapto-iron-based biochar prepared in the comparative example 4 into the span 60 alcohol solution to ensure that the biochar material is completely immersed, standing for 3h, then carrying out ultrasonic treatment for 60min, filtering, and carrying out vacuum drying at 55 ℃ for 24h to obtain the span-60 alcohol-based biochar.
Comparative example 8
And (2) putting 10g of sodium dodecyl sulfate into 100mL of water, stirring to dissolve the sodium dodecyl sulfate to prepare a 10% sodium dodecyl sulfate aqueous solution, then soaking the magnetic gelatin biochar prepared in the comparative example 5 into the sodium dodecyl sulfate aqueous solution to ensure that the biochar material is completely immersed, standing for 3 hours, then carrying out ultrasonic treatment for 60 minutes, filtering, and carrying out vacuum drying at 55 ℃ for 24 hours to obtain the magnetic gelatin biochar.
Comparative example 9
And (2) putting 5g of Tween 80 into 100mL of water, stirring for dissolving to prepare a 5% Tween 80 solution, then soaking the sodium alginate biochar prepared in the comparative example 6 into the Tween 80 solution to ensure that the biochar material is completely immersed, standing for 3h, then carrying out ultrasonic treatment for 60min, filtering, and carrying out vacuum drying at 55 ℃ for 24h to obtain the sodium alginate biochar.
Comparative example 10
Dissolving 10g of rhamnolipid in 100mL of water to prepare a 10% rhamnolipid solution, then soaking the sodium alginate biochar prepared in the comparative example 6 in the rhamnolipid solution to ensure that the biochar material is completely immersed, standing for 3h, then carrying out ultrasonic treatment for 60min, filtering, and carrying out vacuum drying at 55 ℃ for 24h to obtain the rhamnolipid.
Comparative example 11
Dissolving 12g sophorolipid in 100mL water to prepare 12% sophorolipid solution, then soaking the sodium alginate biochar prepared in the comparative example 6 in the sophorolipid solution to ensure that the biochar material is completely immersed, standing for 3h, then carrying out ultrasonic treatment for 60min, filtering, and carrying out vacuum drying at 55 ℃ for 24h to obtain the sophorolipid.
Comparative example 12
Dissolving 12g of cellobiose in 100mL of water to prepare 12% cellobiose solution, then soaking the magnetic gelatin biochar prepared in the comparative example 5 in the cellobiose solution to ensure that the biochar material is completely immersed, standing for 3h, then performing ultrasonic treatment for 60min, filtering, and performing vacuum drying at 55 ℃ for 24h to obtain the product.
Example 1
S1, airing and crushing the tea leaves, heating to 500 ℃, preserving heat for 3 hours, stopping heating, grinding and sieving until the particle size is 0.2-0.3 mm for later use;
s2, dissolving 1.5g of sodium alginate in 100mL of water to prepare 1.5% sodium alginate solution, and adding 5g of CaCl2Dissolving in 100mL water to obtain 5% CaCl2Adding 4.5g of biochar obtained in S1 into 100mL of sodium alginate aqueous solution, stirring for 4h, and slowly dropping 100mL of CaCl2In the aqueous solution, continuously stirring for 6h in the dropping process, repeatedly washing with water after filtering, and drying in vacuum at 50 ℃ for later use;
s3, dissolving 15g of cellobiose in 100mL of water to prepare 15% cellobiose solution, adding the product obtained in S2 into the cellobiose aqueous solution, standing for 3h, performing ultrasonic treatment for 60min, filtering, and performing vacuum drying at 50 ℃ to obtain the product.
Test method
As-contaminated planting soil used in the above-mentioned tests, 7 test cells were divided to test the treatment of soil with the biochar material prepared in comparative examples 7 to 12 and example 1, respectively, 20 square meters per cell, three replicates per treatment were set, the biochar material and soil were treated at a time in a ratio of 1:200, and tomatoes were planted on the soil, all four seasons, at the time of harvesting tomatoes every season, the content of arsenic in the soil in an available state was measured, and the concentrations of arsenic and iron in the tomato fruits were measured, and the results are shown in tables 2 to 4.
TABLE 2 test examples the content of available arsenic in soil before and after treatment of arsenic-contaminated soil
The test result shows that the biochar material treated by the surfactant solution can remove impurities such as tar, ash and the like on the surface and in pores of the biochar to a certain extent, can increase the adsorption performance of the biochar, and can stabilize and maintain the adsorption effect for a certain time, but the content of the effective arsenic in soil is increased when planted in the third season and the fourth season, while the sodium alginate biochar treated by the cellobiose solution can maintain the fixation effect on the effective arsenic for a long time, and the content of the effective arsenic in soil is at a lower level in the planting of vegetables in the four seasons.
TABLE 3 test examples arsenic content in tomato fruit of four seasons
The test results show that the results are consistent with the results of the content of the arsenic in the soil in an effective state, the difference of the content of the arsenic in the tomato fruits from the first season to the fourth season planted in the comparative examples 7-12 is large, the content of the arsenic in the tomato fruits is gradually increased along with the slow desorption and release of the arsenic fixed by the biochar, and the biochar material prepared by the invention can keep the stable adsorption of the arsenic for a long time, so that the content of the arsenic in the tomato fruits is almost unchanged.
TABLE 4 test examples iron content in four season tomato fruits
The test result shows that when the biochar material containing the iron base is used for soil treatment, the content of the iron element in the tomatoes is higher than that of the biochar material without the iron base, and the biochar material prepared by the method is natural in component and cannot influence the planting and nutrition of the tomatoes.
Influence of different preparation methods on performance of biochar material
Example 2
S1, airing and crushing the tea leaves, heating to 600 ℃, preserving heat for 2 hours, stopping heating, grinding and sieving until the particle size is 0.2-0.3 mm for later use;
s2, dissolving 1g of sodium alginate in 100mL of water to prepare 1% sodium alginate solution, and adding 4g of CaCl2Dissolving in 100mL water to obtain 4% CaCl2Adding biochar 4g obtained in S1 into 100mL sodium alginate aqueous solution, stirring for 3h, and slowly dropping 150mL CaCl2In the aqueous solution, continuously stirring for 8h in the dropping process, repeatedly washing with water after filtering, and vacuum drying at 60 ℃ for later use;
s3, dissolving 10g of cellobiose in 100mL of water to prepare 10% cellobiose solution, adding the product obtained in S2 into the cellobiose aqueous solution, standing for 4h, performing ultrasonic treatment for 30min, filtering, and performing vacuum drying at 60 ℃ to obtain the product.
Example 3
S1, airing and crushing the tea leaves, heating to 560 ℃, preserving heat for 3 hours, stopping heating, grinding and sieving until the particle size is 0.2-0.3 mm for later use;
s2, dissolving 1.2g of sodium alginate in 100mL of water to prepare 1.2% sodium alginate solution, and adding 5g of CaCl2Dissolving in 100mL water to obtain 5% CaCl2Adding 4.2g of biochar obtained in S1 into 100mL of sodium alginate aqueous solution, stirring for 4h, and slowly dropping 120mL of CaCl2In the aqueous solution, continuously stirring for 6h in the dropping process, repeatedly washing with water after filtering, and drying in vacuum at 55 ℃ for later use;
s3, dissolving 12g of cellobiose in 100mL of water to prepare 12% cellobiose solution, adding the product obtained in S2 into the cellobiose aqueous solution, standing for 3h, performing ultrasonic treatment for 60min, filtering, and vacuum drying at 55 ℃.
Comparative example 13
S1, crushing the corn straws, heating to 600 ℃, preserving heat for 8 hours, stopping heating, grinding and sieving until the particle size is 0.2-0.3 mm for later use;
s2, dissolving 1.2g of sodium alginate in 100mL of water to prepare 1.2% sodium alginate solution, and adding 5g of CaCl2Dissolving in 100mL water to obtain5% of CaCl2Adding 4.2g of biochar obtained in S1 into 100mL of sodium alginate aqueous solution, stirring for 4h, and slowly dropping 120mL of CaCl2In the aqueous solution, continuously stirring for 6h in the dropping process, repeatedly washing with water after filtering, and drying in vacuum at 55 ℃ for later use;
s3, dissolving 12g of cellobiose in 100mL of water to prepare 12% cellobiose solution, adding the product obtained in S2 into the cellobiose aqueous solution, standing for 3h, filtering, and vacuum-drying at 55 ℃.
Test method
As-contaminated planting soil used in the above-mentioned experiments, the treatment of soil with the biochar material prepared in examples 2-3 and comparative example 13 was tested in 3 test cells, each 20 square meters, each treatment was set to three replicates, the biochar material and soil were treated at once in a ratio of 1:200, and tomatoes were planted on the soil, all four seasons, at the time of harvesting tomatoes every season, the content of available arsenic in soil was measured, and the arsenic concentration in tomato fruits was measured, and the results are shown in tables 5-6.
TABLE 5 test examples the content of available arsenic in soil before and after treatment of arsenic-contaminated soil
TABLE 6 test examples arsenic content in tomato fruit of four seasons
Tests show that the biomass source and the preparation method have certain influence on the performance of the biochar material, the biochar prepared by the tea leaves at a specific temperature and time has stronger adsorption force and more lasting adsorption effect after the reaction with the sodium alginate and the cellobiose aqueous solution is stood and subjected to ultrasound.
Claims (9)
1. A method for preparing a biochar material for efficiently reducing arsenic pollution of soil comprises the following steps:
s1, drying and crushing the tea leaves, heating to 500-600 ℃, preserving heat for 2-3 hours, stopping heating, and grinding and sieving for later use;
s2, adding the biochar obtained in the step S1 into a sodium alginate aqueous solution, stirring for 3-4 hours, and then slowly dropping CaCl2In the aqueous solution, continuously stirring for 6-8 h in the dropping process, filtering, repeatedly washing with water, and performing vacuum drying at 50-60 ℃ for later use;
s3, adding the product obtained in the step S2 into a cellobiose water solution, standing for 3-4 hours, then carrying out ultrasonic treatment for 30-60 min, filtering, and carrying out vacuum drying at 50-60 ℃ to obtain the product.
2. The method for preparing the biochar material capable of efficiently reducing the arsenic pollution to the soil according to claim 1, wherein the tea leaves in the S1 are subjected to heat preservation at 550-580 ℃ for 2.5-3 hours.
3. The method for preparing the biochar material capable of efficiently reducing the arsenic pollution to the soil according to claim 1, wherein the tea leaves heated in the S1 are ground to have a particle size of 0.2-0.3 mm.
4. The method for preparing the biochar material capable of efficiently reducing arsenic pollution to soil according to claim 1, wherein the concentration of the sodium alginate aqueous solution in the S2 is 1-1.5%, and the weight ratio of the biochar to the sodium alginate is 3-4: 1.
5. The method for preparing the biochar material with high efficiency for reducing the arsenic pollution of the soil as claimed in claim 1, wherein the CaCl in S22The concentration of the aqueous solution is 4-5%, and the sodium alginate aqueous solution and CaCl are2The volume ratio of the aqueous solution is 1: 1-1.5.
6. The method for preparing the biochar material capable of efficiently reducing the arsenic pollution of the soil according to claim 1, wherein the concentration of the cellobiose aqueous solution in the S3 is 10-15%.
7. The method for preparing the biochar material for efficiently reducing the arsenic pollution of the soil according to claim 1, which is characterized by comprising the following steps of:
s1, airing and crushing the tea leaves, heating to 560 ℃, preserving heat for 3 hours, stopping heating, grinding and sieving until the particle size is 0.2-0.3 mm for later use;
s2, adding the biochar obtained in the step S1 into a 1.2% sodium alginate aqueous solution, stirring for 4 hours, and slowly dropping 5% CaCl2In aqueous solution, sodium alginate aqueous solution and CaCl2The volume ratio of the aqueous solution is 1:1.2, stirring is continued for 6 hours in the dropping process, water is repeatedly used for washing after filtering, and vacuum drying is carried out at 55 ℃ for standby;
s3, adding the product obtained in the step S2 into a 12% cellobiose aqueous solution, standing for 3 hours, then carrying out ultrasonic treatment for 60min, filtering, and carrying out vacuum drying at 55 ℃ to obtain the product.
8. The biochar material with high efficiency for reducing the arsenic pollution of soil prepared by the method according to any one of claims 1 to 7.
9. The application of the biochar material for efficiently reducing the arsenic pollution of the soil prepared by the method according to any one of claims 1-7 in soil treatment, wherein the weight ratio of the biochar material to the soil is 1: 100-500.
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