CN117138759A - Dark plum dreg xanthate material and preparation method and application thereof - Google Patents
Dark plum dreg xanthate material and preparation method and application thereof Download PDFInfo
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- CN117138759A CN117138759A CN202311120155.4A CN202311120155A CN117138759A CN 117138759 A CN117138759 A CN 117138759A CN 202311120155 A CN202311120155 A CN 202311120155A CN 117138759 A CN117138759 A CN 117138759A
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- 239000000463 material Substances 0.000 title claims abstract description 57
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000012991 xanthate Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 78
- 239000002689 soil Substances 0.000 claims abstract description 67
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 238000011282 treatment Methods 0.000 claims abstract description 30
- 238000004383 yellowing Methods 0.000 claims abstract description 28
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 25
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000005342 ion exchange Methods 0.000 claims abstract description 18
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 12
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 12
- 238000007493 shaping process Methods 0.000 claims abstract description 12
- 230000003113 alkalizing effect Effects 0.000 claims abstract description 10
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims abstract description 5
- 238000005063 solubilization Methods 0.000 claims description 65
- 230000007928 solubilization Effects 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 25
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 238000002386 leaching Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 238000010668 complexation reaction Methods 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000003640 drug residue Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 33
- 238000000746 purification Methods 0.000 description 15
- 239000002253 acid Substances 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 13
- 239000002131 composite material Substances 0.000 description 10
- 239000002699 waste material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000002028 Biomass Substances 0.000 description 6
- 101100345345 Arabidopsis thaliana MGD1 gene Proteins 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000003381 solubilizing effect Effects 0.000 description 5
- OHOTVSOGTVKXEL-UHFFFAOYSA-K trisodium;2-[bis(carboxylatomethyl)amino]propanoate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C(C)N(CC([O-])=O)CC([O-])=O OHOTVSOGTVKXEL-UHFFFAOYSA-K 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000005067 remediation Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003621 irrigation water Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XMZRVEIONXBCQB-REOHCLBHSA-N (2s)-2-(dicarboxyamino)propanoic acid Chemical compound OC(=O)[C@H](C)N(C(O)=O)C(O)=O XMZRVEIONXBCQB-REOHCLBHSA-N 0.000 description 1
- VKZRWSNIWNFCIQ-WDSKDSINSA-N (2s)-2-[2-[[(1s)-1,2-dicarboxyethyl]amino]ethylamino]butanedioic acid Chemical compound OC(=O)C[C@@H](C(O)=O)NCCN[C@H](C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-WDSKDSINSA-N 0.000 description 1
- ZOEHRTNFNALLOL-REOHCLBHSA-N 2-[[(1s)-1-carboxyethyl]amino]propanedioic acid Chemical compound OC(=O)[C@H](C)NC(C(O)=O)C(O)=O ZOEHRTNFNALLOL-REOHCLBHSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010948 quality risk assessment Methods 0.000 description 1
- 239000004172 quinoline yellow Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002195 synergetic 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
- B01J20/22—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
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/18—Prepolymers; Macromolecular compounds
- C09K17/32—Prepolymers; Macromolecular compounds of natural origin, e.g. cellulosic materials
-
- 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
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the technical field of soil treatment and provides a dark plum drug residue xanthate material and a preparation method and application thereof. The preparation method of the dark plum dreg xanthate material provided by the invention comprises the following steps: mixing the dark plum residue with a first sodium hydroxide solution, and alkalizing to obtain alkalized dark plum residue; mixing the alkalized dark plum dregs, a second sodium hydroxide solution and carbon disulfide, and carrying out yellowing; and after the yellowing, adding a magnesium sulfate solution into the obtained yellowing liquid, and performing ion exchange and shaping reaction to obtain the dark plum dreg xanthate material. The preparation method provided by the invention has the advantages that the dark plum dregs are alkalized, fibers in the dark plum dregs can be fluffed, and a large amount of hydroxyl groups are released; and then yellowing is carried out, and active groups are grafted onto dark plum residues through the fluffed hydroxyl groups, so that sites are provided for the complexation of subsequent heavy metals, and the heavy metal removal rate is improved.
Description
Technical Field
The invention relates to the technical field of soil treatment, in particular to a dark plum dreg xanthate material and a preparation method and application thereof.
Background
The waste biomass source solubilizing agent material based on the chemical solubilizing method has the advantages of environmental friendliness, low cost, resource circulation and the like, overcomes the defects of soil structural damage (acid and alkali), soil nutrient loss, poor degradability (EDTA), high application cost (EDDS) and the like after the traditional inorganic and synthetic cleaning agent is used for repairing soil, and is regarded as an applicable emerging green low-carbon and sustainable mild repairing technology. However, current studies on the reduction of heavy metals by waste biomass source solubilizer materials are still very limited, mainly because of the problem of low efficiency of heavy metal removal in the existing waste biomass source solubilizer materials.
The soil can be effectively restored by the soil cleaning, and the treatment, recovery and reutilization of the elution waste liquid are effective ways for reducing the secondary pollution risk of surrounding soil and underground water, reducing the restoration cost and realizing the reutilization of waste resources. However, at present, the soil remediation research mainly focuses on the soil heavy metal cleaning process, the process of removing and recycling heavy metals in the soil elution waste liquid by taking the friendly waste biomass as a material has not been developed, and the solubilization and emission-increasing circulating chain type synergistic decrement remediation effect, microcosmic mechanism and soil environmental quality risk assessment mode of heavy metals in cultivated soil and eluent based on biomass solubilizer and leaching residues thereof have not been reported. This also creates a technical bottleneck limiting the technology in application of reduced remediation of heavy metal contaminated soil in cultivated lands. Therefore, the agricultural and forestry biomass adsorption material which is wide in source, economical and available and efficient in effect is screened, modified and optimized, and is very important for rapid and effective removal and recycling of heavy metals in elution waste liquid after farmland soil leaching.
Disclosure of Invention
In view of the above, the invention aims to provide a dark plum drug residue xanthate material, and a preparation method and application thereof. The dark plum dreg xanthate material obtained by the preparation method provided by the invention has high heavy metal removal rate and can be recycled.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of dark plum dregs xanthate material, which comprises the following steps:
mixing the dark plum residue with a first sodium hydroxide solution, and alkalizing to obtain alkalized dark plum residue;
mixing the alkalized dark plum dregs, a second sodium hydroxide solution and carbon disulfide, and carrying out yellowing;
and after the yellowing, adding a magnesium sulfate solution into the obtained yellowing liquid, and performing ion exchange and shaping reaction to obtain the dark plum dreg xanthate material.
Preferably, the mass concentration of the first sodium hydroxide solution is 10-30%, and the dosage ratio of the dark plum residue to the first sodium hydroxide solution is 10g:200 mL-10 g:400mL;
the alkalizing temperature is room temperature and the time is 12-48 h, the alkalizing is carried out under the stirring condition, and the stirring rotating speed is 100-250 rpm.
Preferably, the mass concentration of the second sodium hydroxide solution is 5-20%, and the dosage ratio of the dark plum residue to the second sodium hydroxide solution to the carbon disulfide is 10g:200mL:10 mL-10 g:400mL:10mL;
the temperature of the yellowing is room temperature and the time is 3-6 hours, and the yellowing is carried out under the condition of stirring.
Preferably, the mass concentration of the magnesium sulfate solution is 5-10%, and the dosage ratio of the dark plum dregs to the magnesium sulfate solution is 10g to 100mL to 10g to 150mL; the temperature of the ion exchange and shaping reaction is room temperature, and the time is 0.5-2 h; the ion exchange and shaping reaction is carried out under the condition of stirring.
Preferably, after the ion exchange and sizing reaction, the method further comprises: and sequentially carrying out suction filtration, water washing and drying on the obtained ion exchange and shaping reaction feed liquid.
Preferably, the preparation method of the dark plum residue comprises the following steps:
mixing mume fructus with water, and leaching to obtain mume fructus residue;
mixing the dark plum residue with water, and extracting to obtain dark plum residue;
when the dark plum is leached, the dosage ratio of dark plum to water is 1g to 10mL to 1g to 30mL, the leaching temperature is 80 to 100 ℃ and the leaching time is 1 to 6 hours;
during the extraction, the dosage ratio of the dark plum residue to the water is 25 g:1L-100 g:1L, and the extraction mode is shaking table oscillation; the oscillating temperature of the shaking table is 22-28 ℃, the rotating speed is 120-180 rpm, and the time is 1-6 h.
The invention also provides the dark plum dreg xanthate material obtained by the preparation method.
The invention also provides application of the dark plum dreg xanthate material in heavy metal contaminated soil.
Preferably, the method comprises the following steps:
mixing the dark plum dreg xanthate material, heavy metal contaminated soil to be treated and a liquid solvent, and performing solubilization treatment;
the dosage ratio of the dark plum dreg xanthate material to the heavy metal contaminated soil to be treated to the liquid solvent is 1g:2g:40 mL-1 g:400mL;
the liquid solvent is water or filtrate obtained by solubilization treatment;
the time of the solubilization treatment is 0.5-3 h.
Preferably, after the solubilization treatment, the method further comprises: filtering the obtained solubilization treatment feed liquid to obtain filtrate; mixing the filtrate, the dark plum dreg xanthate material and the heavy metal contaminated soil to be treated, and performing solubilization treatment again to realize recycling of the filtrate.
The invention provides a preparation method of dark plum dregs xanthate material, which comprises the following steps: mixing the dark plum residue with a first sodium hydroxide solution, and alkalizing to obtain alkalized dark plum residue; mixing the alkalized dark plum dregs, a second sodium hydroxide solution and carbon disulfide, and carrying out yellowing; and after the yellowing, adding a magnesium sulfate solution into the obtained yellowing liquid, and performing ion exchange and shaping reaction to obtain the dark plum dreg xanthate material. The preparation method provided by the invention has the advantages that the dark plum dregs are alkalized, fibers in the dark plum dregs can be fluffed, and a large amount of hydroxyl groups are released; and then yellowing is carried out, and active groups are grafted onto dark plum residues through the fluffed hydroxyl groups, so that sites are provided for the complexation of subsequent heavy metals, and the heavy metal removal rate is improved.
Drawings
FIG. 1 is a flow chart of the preparation of a dark plum dreg xanthate material;
FIG. 2 is an SEM photograph and EDS map of dark plum residue;
FIG. 3 is an SEM photograph and EDS map of xanthate material of dark plum residue
FIG. 4 is a graph showing the effect of direct solubilization of solubilization liquid and its effluent on the removal of Cd from alkaline and acidic soils;
FIG. 5 is a graph showing the effect of the combined solubilization of the solubilization liquid and its effluent on the removal of Cd from alkaline and acidic soils.
Detailed Description
The invention provides a preparation method of dark plum dregs xanthate material, which comprises the following steps:
mixing the dark plum residue with a first sodium hydroxide solution, and alkalizing to obtain alkalized dark plum residue;
mixing the alkalized dark plum dregs, a second sodium hydroxide solution and carbon disulfide, and carrying out yellowing;
and after the yellowing, adding a magnesium sulfate solution into the obtained yellowing liquid, and performing ion exchange and shaping reaction to obtain the dark plum dreg xanthate material.
In the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
Fig. 1 is a flow chart of preparation of the dark plum residue xanthate material, and the preparation process of the dark plum residue xanthate material is described in detail below with reference to fig. 1.
The invention mixes dark plum dregs and a first sodium hydroxide solution, and alkalizes the dark plum dregs to obtain alkalized dark plum dregs.
In the invention, the preparation method of the dark plum dregs preferably comprises the following steps:
mixing mume fructus with water, and leaching to obtain mume fructus residue;
mixing the dark plum residue with water, and extracting to obtain dark plum residue.
In the invention, the dosage ratio of the dark plum to the water is preferably 1g to 10mL to 1g to 30mL, and more preferably 1g to 15mL to 1g to 25mL; the temperature of the leaching is preferably 80-100 ℃, and more preferably 90 ℃; the time is preferably 1 to 6 hours, more preferably 3 hours. In the invention, the dosage ratio of the dark plum residue to the water is preferably 25g to 1L to 100g to 1L, more preferably 50g to 1L, and the extraction mode is preferably shaking table oscillation; the oscillating temperature of the shaking table is preferably 22-28 ℃; the rotation speed is preferably 120-180 rpm; the time is preferably 1 to 6 hours, more preferably 3 hours.
In the present invention, the mass concentration of the first sodium hydroxide solution is preferably 10 to 30%, more preferably 20%; the dosage ratio of the dark plum residue to the first sodium hydroxide solution is preferably 10g:200 mL-10 g:400mL, and more preferably 10g:250 mL-10 g:350mL.
In the present invention, the alkalizing temperature is preferably room temperature; the time is preferably 12 to 48 hours, more preferably 24 hours; the alkalization is preferably carried out under stirring; the rotation speed of the stirring is preferably 100 to 250rpm, more preferably 150 to 200rpm.
After the alkalization, the invention preferably further comprises filtering the obtained alkalized feed liquid, and washing and drying the obtained filter residues. In the present invention, the filtration is preferably a bag filtration. In the present invention, the washing reagent is preferably water, and the water is preferably distilled water; the number of times of washing is preferably 3. In the present invention, the temperature of the drying is preferably 60℃and the time is preferably 15 hours.
After the alkalized dark plum dregs are obtained, the alkalized dark plum dregs, a second sodium hydroxide solution and carbon disulfide are mixed for yellowing.
In the present invention, the mass concentration of the second sodium hydroxide solution is preferably 5 to 20%, more preferably 10 to 15%. In the invention, the dosage ratio of the dark plum residue, the second sodium hydroxide solution and the carbon disulfide is preferably 10g:200mL:10 mL-10 g:400mL:10mL.
In the present invention, the temperature of the yellowing is preferably room temperature; the time is preferably 3 to 6 hours; the yellowing is preferably carried out under stirring.
After the yellowing, the invention adds magnesium sulfate solution into the obtained yellowing liquid to carry out ion exchange and shaping reaction, thus obtaining the dark plum dreg xanthate material.
In the invention, the mass concentration of the magnesium sulfate solution is preferably 5-10%, and the dosage ratio of the dark plum dregs to the magnesium sulfate solution is preferably 10g to 100-10 g to 150mL. In the present invention, the temperature of the ion exchange and sizing reaction is preferably room temperature; the time is preferably 0.5 to 2 hours; the ion exchange and sizing reaction is preferably carried out under stirring.
After the ion exchange and sizing reaction, the invention preferably further comprises: and sequentially carrying out suction filtration, water washing and drying on the obtained ion exchange and shaping reaction feed liquid. The invention does not limit the dosage and times of the water washing reagent, and the washing is carried out until the pH value is near neutral. In the present invention, the temperature of the drying is preferably room temperature.
The invention also provides the dark plum dreg xanthate material obtained by the preparation method.
The invention also provides application of the dark plum dreg xanthate material in heavy metal contaminated soil.
In the present invention, when the dark plum dreg xanthate material is applied to heavy metal contaminated soil, the method preferably comprises the following steps:
mixing the dark plum dreg xanthate material, heavy metal contaminated soil to be treated and a liquid solvent, and performing solubilization treatment.
In the present invention, the liquid solvent is water or a filtrate obtained by solubilization treatment.
In the invention, the dosage ratio of the dark plum dreg xanthate material, the heavy metal contaminated soil to be treated and the liquid solvent is preferably 1g to 2g to 40mL to 1g to 400mL, and more preferably 1g to 20g to 40mL.
In the present invention, the time for the solubilization treatment is preferably 0.5 to 3 hours, more preferably 1 hour.
After the solubilization treatment, the present invention preferably further comprises: filtering the obtained solubilization treatment feed liquid to obtain filtrate; mixing the filtrate, the dark plum dreg xanthate material and the heavy metal contaminated soil to be treated, and performing solubilization treatment again to realize recycling of the filtrate.
In the invention, the dosage ratio of the filtrate, the dark plum dreg xanthate material and the heavy metal contaminated soil to be treated is preferably adjusted according to actual conditions.
The dark plum residue xanthate material, the preparation method and the application thereof provided by the invention are described in detail below with reference to examples, but are not to be construed as limiting the scope of the invention.
The main materials used in the following examples:
the tested soil is true heavy metal contaminated soil, and alkaline soil (Gansu silver dry land gray calcium soil: N36 DEG 31 '59', E104 DEG 9'6') and acid soil (Jiangsu Taicang farmland paddy soil: 31 DEG 22 '08' N,121 DEG 06 '48' E) are selected from the tested soil. The pH of the alkaline soil is 8.78, and the Cd content is 0.78mg/kg. The pH of the acid soil is 6.51, and the Cd content is 0.79mg/kg.
Dark plum was purchased from Bo Zhou and Entang Inc. of Anhui province.
Carbon disulfide (CS) 2 ) Purchased from the national drug group.
Dicarboxylalanine (MGDA) was purchased from shandongtai and water treatment limited.
Example 1
Preparation of dark plum dreg xanthate material:
10.00g of dark plum dregs (RPM) are sieved by a 10-mesh sieve, placed in a 1.00L large beaker, added into 200.00mL of NaOH solution with the mass concentration of 20.0%, stirred for 24 hours in a 200RPM electric stirrer (S212-90B, shanghai Shensheng biological technology Co., ltd.) for alkalization, filtered by a cloth bag and washed 3 times by distilled water after the alkalization is finished, and dried for 15 hours below 60 ℃ to obtain the alkalized dark plum dregs. Placing alkalized mume fructus residue in 1.00L beaker at normal temperature and pressure, adding 200.00mL NaOH solution with mass concentration of 10.0%, and adding 10.00mL CS 2 Stirring at normal temperature for 3h to yellow, and adding MgSO with mass concentration of 5.0% after the yellow is finished 4 100.0mL of solution, stirring for 30min, filtering, washing the obtained filter residue with water until the pH is near neutral, and drying at room temperature to obtain the dark plum residue xanthate material (RPMX).
The method for obtaining dark plum dregs comprises the following steps:
cleaning mume fructus, oven drying at 60deg.C, and pulverizing with 2mm sieve. The crushed dark plum is treated according to the traditional Chinese medicine decoction method, namely the liquid medicine ratio is 1:30 (g/v), respectively weighing 8g of crushed dark plum, placing into a 250mL conical flask, adding 240mL of deionized water, leaching at constant temperature of 90 ℃ for 3 hours by using a water bath heating method, standing, cooling, filtering after cooling, and drying to obtain dark plum residues.
Weighing 30.00g of dark plum residue, placing into 500.00mL plastic bottle, adding 300mL deionized water (dark plum residue to water ratio is 1:10), oscillating at 28deg.C in 180rpm shaker for 3 hr, filtering, and oven drying the obtained residue to obtain dark plum residue.
Test case
Characterization and adsorption performance of dark plum dreg xanthate material
Scanning electron microscope (SEM-EDS) analysis:
freeze-drying unmodified mume fructus Residue (RPM) and mume fructus residue xanthate material (RPMX), grinding to obtain powder, and collecting and analyzing morphology with cold field emission scanning electron microscope (HITACHI S-4800, SEM, japan) after spraying gold.
SEM and EDS are utilized to characterize microscopic morphology and element distribution change of dark plum dregs and dark plum dregs xanthate material, and knot is formedThe result is shown in fig. 2 and 3. Fig. 2 is an SEM image and EDS image of dark plum residue, and fig. 2 is an SEM image on the left and EDS image on the right. Fig. 3 is an SEM image and EDS image of the dark plum residue xanthate material, and fig. 3 is a left image and an EDS image. As can be seen from the left diagram of fig. 2: the surface structure of dark plum dregs (RPM) is orderly and smooth; as can be seen from the left diagram of fig. 3: compared with RPMX, the yellow original acid salt material (RPMX) of dark plum dregs has greatly changed structure, loose surface, more layers, more convex particles and increased specific surface area. The possible reason for this phenomenon is that part of hemicellulose and lignin in the dark plum dregs are removed during the alkalization and yellowing treatment, and the structure among individual fibers is loose. At the same time, the composition structure of the cellulose is changed, and xanthate groups, na are introduced + 、Mg 2+ All are successfully connected to the surface of the material, so that the adsorption capacity of RPMX to Cd in the discharged liquid is enhanced.
Adsorption performance of dark plum dreg xanthate material on Cd in waste liquid:
weigh 20.00mg CdCl 2 Adding into 1000mL volumetric flask, adding deionized water to desired volume, and preparing into 20mg/L CdCl 2 A solution. 20.00mL of prepared 20mg/L CdCl is taken 2 Adding the solution into 50mL centrifuge tube, adding 0.50g RPM and RPMX respectively, oscillating in centrifuge for 3h, centrifuging, filtering, measuring Cd content in the solution by ICP-MS, calculating the adsorption capacity of xanthate of mume fructus residue on Cd, and repeating the experiment three times.
The Cd adsorption capacity of the dark plum residue and the dark plum residue xanthate material on the self-prepared Cd solution is compared, and the result is shown in table 1.
TABLE 1 adsorption effect of Cd on the residue of dark plum residue extraction before and after modification
Note that: RPM: extracting residues from dark plum residue; RPMX: modified dark plum dregs xanthate.
As can be seen from table 1: compared with the Cd adsorption capacity of the dark plum dregs (RPM), the dark plum dreg xanthate material (RPMX) has the advantages that the Cd adsorption capacity is obviously improved, and the Cd adsorption removal efficiency is increased from 13.6% to 91.5%, so that the Cd adsorption capacity of the dark plum dregs can be effectively improved through the yellowing treatment. The adsorption capacity of RPMX to Cd is 6.40mg/g under the condition of the dosage of 1:40.
Example 3
Purifying effect and circulating mode of solubilization effluent
Preparing a dark plum dregs solubilizer: weighing 30.00g of dark plum fruit, putting into a 1.00L plastic bottle, adding 900.00mL of deionized water, putting into a water bath kettle at 90 ℃, leaching at constant temperature for 3 hours, filtering with a filter bag to obtain filter residues, naturally air-drying, and crushing to obtain dark plum fruit residues with the particle size of 2 mm; three groups of the extract were prepared in parallel to obtain 90.00g of dark plum residue. 15.00g of dark plum residue is weighed and put into a 500.00mL plastic bottle, 300mL of deionized water is added, and the mixture is oscillated for 3 hours in a shaking table at 28 ℃ and 180rpm to obtain dark plum residue solubilizer with the concentration of 50g/L, and the three groups are parallel to obtain 600mL of dark plum residue solubilizer in total.
The dicarboxymethylalanine (MGDA) and 50g/L dark plum dreg solubilizer are mixed according to the dosage ratio of 0.34g to 1L to obtain the biodegradable composite solubilizer (RPMG 3).
And (3) respectively carrying out solubilization treatment on alkaline soil and acid soil under the optimized solubilization condition (pH 5.0, liquid-soil ratio 2:1 and time 1 h) by using the biodegradable composite solubilizing agent RPMG3, centrifuging and filtering after the treatment is finished, and collecting waste liquid as solubilization discharge liquid.
Mixing RPMX and solubilization effluent according to a ratio of 1g to 40mL, oscillating for 3h in a shaking table at 180rpm for purification, and centrifugally filtering to obtain one-time solubilization and one-time purification effluent; the Cd concentration in the once solubilized and once purified effluent was measured.
The above process is called one solubilization and one purification, and the same solubilization and purification process is combined into a set of cyclic solubilization processes.
The primary solubilization and purification effluent was subjected to a recycling test under optimized solubilization conditions (pH 5.0, liquid-to-soil ratio 2:1, time 1 h) in two ways:
(1) Direct cycle: the once-solubilized and once-purified effluent is directly solubilized with untreated alkaline soil and acid soil, and the obtained solubilized effluent is mixed with RPMX for purification; the soil solubilization and effluent purification were repeated 2 times and 1 time, and they were noted as secondary solubilization, secondary purification, and tertiary solubilization, respectively.
The removal rate of cadmium in the solubilized effluent obtained after the solubilization treatment after the primary purification and the secondary purification is shown in Table 2.
TABLE 2 effect of RPMX on removal of solubilizing effluent Cd
Note that: lower case letters in the same column represent significant differences between the average values.
As can be seen from table 2: the removal efficiency of the yellow original acid salt material (RPMX) of the dark plum dregs on the Cd in the solubilization and discharge liquid of the alkaline soil and the acid soil can reach 97.0-99.4%, and the concentration of the Cd in the purified solubilization and discharge liquid reaches the standard value (Cd 0.01 mg/L) of agricultural irrigation water quality.
The removal rates of cadmium in alkaline soil and acid soil after the primary solubilization, secondary solubilization and tertiary solubilization treatments are shown in FIG. 4. As can be seen from fig. 4: the purified solubilization effluent still has certain removal capacity for Cd in untreated alkaline soil and acid soil. However, the removal efficiency of Cd is remarkably reduced compared with one solubilization, and as the solubilization times are increased, the removal efficiency of Cd is also continuously reduced, and the concentration of residual Cd in the soil still exceeds the screening value (Cd, 0.60 mg/kg). The main reason for this phenomenon is that the concentration of the active ingredients such as soluble organic carbon (DOC) and MGDA in the biodegradable composite solubilizing agent RPMG3 decreases with the increase of the number of cycles. Therefore, direct circulation solubilization of the purified solubilization effluent is not suitable for practical field applications.
(2) And (3) composite circulation: mixing the once-solubilized once-purified effluent with a biodegradable composite solubilizer (RPMG 3) according to volume ratios of 1:1, 1:1.5 and 1:2 respectively to obtain a mixed composite solubilizer; solubilizing the mixed composite solubilizing agent with untreated alkaline soil and acid soil, mixing the obtained solubilizing effluent with RPMX, and purifying; the soil solubilization and effluent purification were repeated 2 times and 1 time, and they were noted as secondary solubilization, secondary purification, and tertiary solubilization, respectively.
The removal rate of cadmium in the solubilization effluent obtained after the solubilization treatment after the primary purification and the secondary purification of the solubilization effluent is shown in Table 3. The removal rates of cadmium in alkaline soil and acid soil after the primary solubilization, secondary solubilization and tertiary solubilization treatments are shown in fig. 5.
TABLE 3 effect of RPMX on removal of solubilizing effluent Cd
Note that: lower case letters in the same column represent significant differences between the average values.
As can be seen from table 3 and fig. 5: after one solubilization, the Cd content in the discharge liquid is between 0.25mg/L and 0.26mg/L, and the Cd adsorption removal effect of RPMX on the solubilization discharge liquid can be stabilized to be more than 93.4%. After RPMX purification, the Cd content in the discharged liquid is not detected, and meets the standard value of agricultural irrigation water quality (Cd 0.01mg/L, GB 5084-2021). When the purified discharge liquid is mixed with RPMG3 stock solution according to the proportion of 1:1, 1:1.5 and 1:2, the removal efficiency of the secondary solubilization and the tertiary solubilization to Cd is lower than that of the primary solubilization, but the removal efficiency of the biodegradable composite solubilizing agent to the soil Cd is relatively stable between 26.3 percent and 30.1 percent along with the increase of the solubilization times, and the residual Cd content of the soil is reduced to be lower than a screening value, so that the soil can reach the safety production and utilization standard. Under the condition that the volume ratio of the discharged liquid to the RPMG3 stock solution is 1:2, the composite circulation solubilization has the best efficiency of removing Cd in soil, and the method is mainly characterized in that the amount of substances which can carry out complexation reaction with Cd in the solution is directly supplemented by adding the stock solution into the discharged liquid, and the removal efficiency of Cd is also obviously improved along with the increase of the supplementing ratio.
Table 4 gives the field application costs of MGDA in the compounding cycle.
Table 4 cost of field application of MGDA in combined cycle
From table 4, it can be found that: the 1:1 composite circulation solubilization can ensure that the alkaline soil and the acid soil meet the production conditions of safe utilization, and can reduce the field application cost by 50% (930.90 yuan to 465.45 yuan) when the second mu of polluted farmland soil is restored. With the increase of the repair area, the average repair cost per mu of land is also continuously reduced. Therefore, the compound traditional Chinese medicine residue solubilizing agent and the compound circulating soil purified by the discharged liquid thereof are economical, efficient, simple, convenient and have potential application prospect.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the dark plum dreg xanthate material is characterized by comprising the following steps of:
mixing the dark plum residue with a first sodium hydroxide solution, and alkalizing to obtain alkalized dark plum residue;
mixing the alkalized dark plum dregs, a second sodium hydroxide solution and carbon disulfide, and carrying out yellowing;
and after the yellowing, adding a magnesium sulfate solution into the obtained yellowing liquid, and performing ion exchange and shaping reaction to obtain the dark plum dreg xanthate material.
2. The preparation method according to claim 1, wherein the mass concentration of the first sodium hydroxide solution is 10-30%, and the dosage ratio of the dark plum residue to the first sodium hydroxide solution is 10g:200 mL-10 g:400mL;
the alkalizing temperature is room temperature and the time is 12-48 h, the alkalizing is carried out under the stirring condition, and the stirring rotating speed is 100-250 rpm.
3. The preparation method of claim 1, wherein the mass concentration of the second sodium hydroxide solution is 5-20%, and the dosage ratio of the dark plum residue to the second sodium hydroxide solution to the carbon disulfide is 10g:200mL:10 mL-10 g:400mL:10mL;
the temperature of the yellowing is room temperature and the time is 3-6 hours, and the yellowing is carried out under the condition of stirring.
4. The preparation method of claim 1, wherein the mass concentration of the magnesium sulfate solution is 5-10%, and the dosage ratio of the dark plum dregs to the magnesium sulfate solution is 10g:100 mL-10 g:150mL; the temperature of the ion exchange and fixation reaction is room temperature, and the time is 0.5-2 h; the ion exchange and shaping reaction is carried out under the condition of stirring.
5. The method according to claim 1 or 4, wherein after the ion exchange and the setting reaction, the method further comprises: and sequentially carrying out suction filtration, water washing and drying on the obtained ion exchange and shaping reaction feed liquid.
6. The preparation method according to claim 1, wherein the preparation method of the dark plum residue comprises the following steps:
mixing mume fructus with water, and leaching to obtain mume fructus residue;
mixing the dark plum residue with water, and extracting to obtain dark plum residue;
when the dark plum is leached, the dosage ratio of dark plum to water is 1g to 10mL to 1g to 30mL, the leaching temperature is 80 to 100 ℃ and the leaching time is 1 to 6 hours;
during the extraction, the dosage ratio of the dark plum residue to the water is 25 g:1L-100 g:1L, and the extraction mode is shaking table oscillation; the oscillating temperature of the shaking table is 22-28 ℃, the rotating speed is 120-180 rpm, and the time is 1-6 h.
7. The dark plum residue xanthate material obtained by the preparation method of any one of claims 1 to 6.
8. The use of the dark plum residue xanthate material of claim 7 in heavy metal contaminated soil.
9. The use according to claim 8, characterized by the steps of:
mixing the dark plum dreg xanthate material, heavy metal contaminated soil to be treated and a liquid solvent, and performing solubilization treatment;
the dosage ratio of the dark plum dreg xanthate material to the heavy metal contaminated soil to be treated to the liquid solvent is 1g:2g:40 mL-1 g:400mL;
the liquid solvent is water or filtrate obtained by solubilization treatment;
the time of the solubilization treatment is 0.5-3 h.
10. The use according to claim 9, characterized in that after the solubilization treatment, it further comprises: filtering the obtained solubilization treatment feed liquid to obtain filtrate; mixing the filtrate, the dark plum dreg xanthate material and the heavy metal contaminated soil to be treated, and performing solubilization treatment again to realize recycling of the filtrate.
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