CN107916109A - A kind of method that Cadmium in Soil activator is prepared using active substance of plant - Google Patents

A kind of method that Cadmium in Soil activator is prepared using active substance of plant Download PDF

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Publication number
CN107916109A
CN107916109A CN201710958784.2A CN201710958784A CN107916109A CN 107916109 A CN107916109 A CN 107916109A CN 201710958784 A CN201710958784 A CN 201710958784A CN 107916109 A CN107916109 A CN 107916109A
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pineapple
magma
cadmium
solution
soil
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CN107916109B (en
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李廷强
宋宇超
刘南麟
宁友峥
罗继鹏
吴可人
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/14Soil-conditioning materials or soil-stabilising materials containing organic compounds only

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)

Abstract

The present invention relates to soil conditioner field, it is desirable to provide a kind of method that Cadmium in Soil activator is prepared using active substance of plant.This method comprises the following steps:Fresh pineapple bran is taken to crush to obtain pineapple magma;Ultra-pure water is added under agitation, is ultrasonically treated after stirring evenly, is filtered to take supernatant;Add chelating agent GLDA solution, biosurfactant Tea Saponin solution, oscillation treatment;Centrifugation takes supernatant, and it is 5 to adjust pH value, the closed preservation of lucifuge.Compared with prior art, novel heavy metal activator of the present invention, raw material sources are extensive, cheap.Preparation method is simple, takes short.The heavy metallic activation agent is environmentally protective, will not cause secondary pollution.

Description

A kind of method that Cadmium in Soil activator is prepared using active substance of plant
Technical field
The present invention relates to soil conditioner field, especially a heavy metal species soil activating agent, seek one kind derive from a wealth of sources, Novel activated dose using fruit residue as main body environmentally protective, of low cost, can realize the activation to Cadmium in Soil, not make Into environmental pollution, while realize utilization of waste as resource.
Background technology
China's heavy metal pollution of soil is serious, wherein the most prominent with cadmium pollution, it is (complete that point position exceeding standard rate is up to 7% State's Soil Pollution Investigation publication, 2014).Cadmium Pollution in Soils not only endangers agricultural production safety, can also influence people by food chain Body health.Therefore the reparation to cadmium pollution soil is extremely urgent with controlling.The reparation of heavy metal pollution of soil mainly includes at present Engineering measure, materialization measure, biological prosthetic and agronomic measures.Engineering measure need to spend substantial amounts of manpower and financial resources, and there is account for The problems such as with soil, materialization measure be easy to cause the negative effect such as leakage and secondary pollution, and carries out plant using plant and carry Reparation is taken to have the advantages that to disturb small, environmental-friendly, non-secondary pollution and be subject to academia favored.But due to weight in soil Metal validity is relatively low, causes plant extract efficiency to be difficult to improve, therefore is carried by adding heavy metallic activation agent come fortification of plants Take reparation very necessary.
Chelating agent can be combined with the heavy metal ion in the soil liquid, activating soil heavy metal.Chelating agent is divided into naturally Two kinds of chelating agent and artificial chelating agent.Ethylenediamine tetra-acetic acid (EDTA) is to apply a kind of wider artificial organic sequestering agent, counterweight Metal activation efficiency protrudes, but EDTA has phytotoxicity and biological degradability is very low, and the chelate formed with metal is easily It is dissolved in water and enters rivers and lakes, environmental risk is larger.Therefore some the green natural chelating agent such as GLDA that can be degraded by microorganisms and Caused if low molecular weight organic acid such as citric acid, oxalic acid etc. researcher's note that still these chelating agents there are price it is high, into The problems such as this is big, limits its popularization and application.
The content of the invention
The technical problem to be solved in the present invention is overcome deficiency of the prior art, there is provided one kind utilizes vegetable active thing The method that matter prepares Cadmium in Soil activator.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows:
A kind of method that Cadmium in Soil activator is prepared using active substance of plant is provided, is comprised the following steps:
(1) fresh pineapple bran is taken, is placed in mixer and crushes, obtains pineapple magma;
(2) ultrapure water fraction time is added in pineapple magma under agitation, the mass ratio of pineapple magma and water is 1: 8;Stir It is ultrasonically treated after mixing uniformly, then filters to take supernatant;
(3) chelating agent GLDA (glutamic acid N, four sodium of N- oxalic acid) solution, biosurfactant are added into supernatant Container, is then placed in reciprocating vibrating machine and carries out oscillation treatment by Tea Saponin solution;
The volume ratio of supernatant, GLDA solution and Tea Saponin solution is 15: 4: 1;Wherein, the quality of chelating agent GLDA solution Concentration is 0.7%, and the mass concentration of Tea Saponin solution is 4%;
(4) mixed liquor through oscillation treatment is centrifuged, it is 5 to take supernatant to adjust pH value, the closed preservation of lucifuge.
In the present invention, in step (2), it is 53kHz that when supersound process, which controls ultrasonic frequency, and temperature is 15 DEG C, processing Time is 20min;After supersound process, it is 80 mesh to filter the nylon wire specification used.
In the present invention, in step (3), oscillation treatment time control frequency of oscillation is 200r/min, time 36h, temperature For 20 DEG C.
In the present invention, in step (4), it is 5000r/min, time 15min that when centrifugal treating, which controls centrifugal rotational speed, temperature Spend for 20 DEG C.
In the present invention, in step (4), pH value is adjusted using the sodium hydroxide of 0.1mol/L.
Inventive principle describes:
The present invention seeks a kind of derive from a wealth of sources and environmentally protective of low cost is used as the novel activated of main body using fruit residue Agent, can realize the activation to Cadmium in Soil, not cause environmental pollution, while realize utilization of waste as resource.
Shown by research, surfactant is added in organic sequestering agent can improve the activation efficiency of heavy metal, tea Saponin is the representative thing for the biosurfactant that plant produces, into soil after can accelerate the desorption of heavy metal, it also has It is degradable, prepare easily, derive from a wealth of sources, lower-price characteristic.Pineapple is in itself rich in various active things such as citric acid, malic acid Matter, it is notable to the activation efficiency of heavy metal, and pineapple bran is that pineapple is discarded in the production process of processed can and fruit juice Thing, it is of low cost and environmentally protective.Therefore the present invention using ultrasonic method obtain containing the intracellular organic acid isoreactivity of pineapple into Point extracting solution, by being assembled with natural chelators and biosurfactant, prepare new heavy metallic activation agent, protecting The recycling of gurry is also achieved while demonstrate,proving activation efficiency certain to cadmium.
Heavy metal ion and content of organics polar region in ultra-pure water, play the interference and reduction for excluding heavy metal ion Organic matter is to the chelating complexing of the ion in extraction solution, and pH is relatively stable 6.8~7.
Compared with prior art, the beneficial effects of the present invention are:
(1) the invention novel heavy metal activator, raw material sources are extensive, cheap.
(2) the invention novel heavy metal activator preparation method is simple, takes short.
(3) the novel heavy metal activator belonging to invention is environmentally protective, will not cause secondary pollution.
Brief description of the drawings
Fig. 1 is comparison diagram of the different reagents to heavy metallic activation efficiency.
Block diagram is represented sequentially as in figure:Single chelating agent EDTA, pineapple bran extract, pineapple magma supernatant with GLDA solution and Tea Saponin solution press the mixture of different volumes ratio.
Embodiment
In order to make content of the present invention easily facilitate understanding, with reference to embodiment to of the present invention Technical solution is described further, but the present invention is not limited only to this.
The method that Cadmium in Soil activator is prepared using active substance of plant, is comprised the following steps:
(1) fresh pineapple bran is taken, is placed in mixer and crushes, obtains pineapple magma;
(2) ultrapure water fraction time is added in pineapple magma under agitation, the mass ratio of pineapple magma and water is 1: 8;Stir It is ultrasonically treated after mixing uniformly, then filters to take supernatant;
(3) chelating agent GLDA solution, biosurfactant Tea Saponin solution are added into pineapple magma supernatant, then Container is placed in reciprocating vibrating machine and carries out oscillation treatment;
The volume ratio of pineapple magma supernatant, GLDA solution and Tea Saponin solution is 15: 4: 1;Wherein, chelating agent GLDA is molten The mass concentration of liquid is 0.7%, and the mass concentration of Tea Saponin solution is 4%;
(4) mixed liquor through oscillation treatment is centrifuged, it is 5 to take supernatant to adjust pH value, the closed preservation of lucifuge.
It is 53kHz that ultrasonic frequency is controlled during supersound process, and temperature is 15 DEG C, processing time 20min;It is ultrasonically treated Afterwards, it is 80 mesh to filter the nylon wire specification used.Oscillation treatment time control frequency of oscillation is 200r/min, time 36h, temperature For 20 DEG C.It is 5000r/min that centrifugal rotational speed is controlled during centrifugal treating, and time 15min, temperature is 20 DEG C.Use 0.1mol/L Sodium hydroxide adjust pH value.
Here is the concrete application example of heavy metallic activation agent:
1st, orthogonal experiment determines the optimum experimental condition of heavy metal-polluted soil activation:
When activator of the present invention is applied to the cadmium activation process of the soil containing cadmium, following steps are specifically included:
When activator of the present invention is applied to the cadmium activation process of the soil containing cadmium, step is specifically included:Weigh soil sample about 1.000g in 50ml centrifuge tubes, take the plant source heavy metal-polluted soil activator 20ml for preparing of the present invention add it is corresponding from In heart pipe, vibration (200r/min, 36h, 20 DEG C) in vibrating machine is put into.Then by the centrifuge tube room temperature vibrated with 5000r/ Min is centrifuged 15 minutes, is taken supernatant addition 5ml concentrated nitric acids to disappear afterwards and is boiled resolution organic matter, disappears and 0.45 μm of filter membrane is crossed after boiling, utilize ICP-OES measures solution cadmium concentration.
At least 9 groups of identical and equivalent soil by cadmium pollution are taken, every group of soil carries out soil with the activator of equivalent Cadmium activation experiment, orthogonal is carried out according to solid-liquid ratio, ultrasonic temperature and ultrasonic time;Wherein, solid-liquid ratio refers to reality Test the mass ratio of middle pineapple magma and ultra-pure water;Ultrasonic temperature refers to temperature when being ultrasonically treated to pineapple magma, and ultrasonic time is Refer to the time being ultrasonically treated to pineapple magma;After experiment, highest one group of Cadmium in Soil activation rate is selected, by the feed liquid of the group It is set to optimum experimental condition than, ultrasonic temperature and ultrasonic time.According to the experimental result in table 1, the 1st group of soil in 9 groups of experiments The activation rate of cadmium is up to 60.14%, and then determines that optimum experimental condition is solid-liquid ratio 1:8th, 15 DEG C of ultrasonic temperature and ultrasound when Between 20min.
1 Orthogonal experiment results of table
2nd, under definite optimum experimental condition, EDTA, GLDA and each definite at least three of Tea Saponin compare concentration value, point Carry out not comparative experiments of the activator to cadmium activation effect.
a:Take at least 27 groups it is identical and equivalent by cadmium pollution soil, according to each definite comparison concentration value, adopt respectively It is to compare ethanedioic acid tetraacethyl (EDTA) 0.06mol/L, 0.08mol/L, 0.1mol/L of concentration value with solution concentration;Glutamic acid Four sodium of N, N- oxalic acid (GLDA) 0.5%, 0.6%, 0.7%;Tea Saponin 2%, 3%, 4% carries out the Cadmium in Soil of single activator Activation experiment, records the Cadmium in Soil activation rate of each group;
b:Take at least 15 groups it is identical and equivalent by cadmium pollution soil, according to each definite comparison concentration value, adopt respectively It is to compare the compound activator of concentration value with solution concentration, Cadmium in Soil activation experiment is carried out, wherein compound activator refers to: Pineapple magma is fixed as accounting for the 75% of activator volume, and glutamic acid N, four sodium of N- oxalic acid (GLDA) and Tea Saponin volume ratio are 8: 2、6:4、5:5、4:6、2:8 compound desorbing agent, and record the Cadmium in Soil activation rate after each group experiment;
c:The Cadmium in Soil activation rate after each group experiment in comparison step b, selects Cadmium in Soil activation rate highest one Group, the compound activator composition volume ratio and concentration of the group are the new type compound activator for being used to handle cadmium pollution soil Preparation result.
After experiment, determine that activator is by the volume ratio of pineapple magma supernatant, GLDA solution and Tea Saponin solution 15∶4∶1;Wherein, the mass concentration of chelating agent GLDA solution is 0.7%, and the mass concentration of Tea Saponin solution is 4%.
Biodegradable chelating agent GLDA used is purchased from Akzo Nobel N.V. in experiment, solids content about 47%, Density is 1.4g/cm3, average molecular weight 351.1, wherein No. CAS is 51981-21-6.
3rd, the preparation of heavy metallic activation agent and application result example
1) take the pineapple bran of 10g to be put into blender and stirred and uniformly obtain pineapple magma, then 80g ultra-pure waters and pineapple is former Slurry mixing, is transferred in plastic beaker.
2) beaker is put into Ultrasound Instrument with 53kHz ultrasounds, ultrasonic temperature is 15 DEG C, time 20min, in mistake after ultrasound The nylon wire of 80 mesh obtains the supernatant of coarse filtration.
3) take supernatant and mass concentration 0.7% GLDA solution and mass concentration 4% Tea Saponin solution respectively with body Product is mixed and made into 20ml intermixtures than 15: 4: 1, places into reciprocating vibrating machine and vibrates 36h at 20 DEG C with 200r/min.
4) after taking mixed liquor to centrifuge, the starting pH to 5 of mixed solution is adjusted with the sodium hydroxide of 0.1mol/L.
The soil of Treatment with activating agent high concentration cadmium pollution made from this method, the results showed that activation rate of the activator to cadmium For 60.39%.Volume ratio by pineapple magma supernatant, GLDA solution and Tea Saponin solution is respectively 15: 3: 2 and 15: 2.5: 2.5 repeat above-mentioned experiment, by the soil of the Treatment with activating agent high concentration cadmium pollution of acquisition, the results showed that activation of the activator to cadmium Rate is respectively 48.21% and 34.45%.
As can be seen from FIG. 1, the cadmium activation rate of single EDTA is 77.67%, the cadmium activation rate of single pineapple bran extract For 49.07%.Activator of the present invention is while certain efficient activation efficiency is ensured, it is thus also avoided that to the secondary of environment Pollution, and it is cheap easily prepared, realize the recycling of discarded object.

Claims (5)

  1. A kind of 1. method that Cadmium in Soil activator is prepared using active substance of plant, it is characterised in that comprise the following steps:
    (1) fresh pineapple bran is taken, is placed in mixer and crushes, obtains pineapple magma;
    (2) ultrapure water fraction time is added in pineapple magma under agitation, the mass ratio of pineapple magma and water is 1: 8;Stirring is equal It is ultrasonically treated after even, then filters to take supernatant;
    (3) chelating agent GLDA solution, biosurfactant Tea Saponin solution are added into pineapple magma supernatant, then will be held Device, which is placed in reciprocating vibrating machine, carries out oscillation treatment;
    The volume ratio of pineapple magma supernatant, GLDA solution and Tea Saponin solution is 15: 4: 1;Wherein, chelating agent GLDA solution Mass concentration is 0.7%, and the mass concentration of Tea Saponin solution is 4%;
    (4) mixed liquor through oscillation treatment is centrifuged, it is 5 to take supernatant to adjust pH value, the closed preservation of lucifuge.
  2. 2. according to the method described in claim 1, it is characterized in that, in step (2), when supersound process, controls ultrasonic frequency For 53kHz, temperature is 15 DEG C, processing time 20min;After supersound process, it is 80 mesh to filter the nylon wire specification used.
  3. 3. according to the method described in claim 1, it is characterized in that, in step (3), oscillation treatment time control frequency of oscillation is 200r/min, time 36h, temperature are 20 DEG C.
  4. 4. according to the method described in claim 1, it is characterized in that, in step (4), when centrifugal treating, controls the centrifugal rotational speed to be 5000r/min, time 15min, temperature are 20 DEG C.
  5. 5. according to the method described in claim 1, it is characterized in that, in step (4), the sodium hydroxide tune of 0.1mol/L is used Save pH value.
CN201710958784.2A 2017-10-16 2017-10-16 Method for preparing soil cadmium activator by using plant active substances Active CN107916109B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112974505A (en) * 2021-01-28 2021-06-18 中国电建集团江西省电力建设有限公司 Method for restoring rice field soil cadmium pollution by using activator and nitrogen-fixing blue algae
CN113575007A (en) * 2021-07-21 2021-11-02 广东禹兴建设工程有限公司 Farmland reclamation method
CN117337930A (en) * 2023-10-08 2024-01-05 中国科学院南京土壤研究所 Preparation method and application of composite leaching agent for removing heavy metals in peanut meal

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CN103706624A (en) * 2013-12-18 2014-04-09 广西大学 Remediation method of heavy metal contaminated soil
CN106833653A (en) * 2017-01-24 2017-06-13 广东植物龙生物技术股份有限公司 A kind of fast repairing method of heavy metal pollution

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112974505A (en) * 2021-01-28 2021-06-18 中国电建集团江西省电力建设有限公司 Method for restoring rice field soil cadmium pollution by using activator and nitrogen-fixing blue algae
CN112974505B (en) * 2021-01-28 2021-12-24 中国电建集团江西省电力建设有限公司 Method for restoring rice field soil cadmium pollution by using activator and nitrogen-fixing blue algae
CN113575007A (en) * 2021-07-21 2021-11-02 广东禹兴建设工程有限公司 Farmland reclamation method
CN117337930A (en) * 2023-10-08 2024-01-05 中国科学院南京土壤研究所 Preparation method and application of composite leaching agent for removing heavy metals in peanut meal

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