CN106433659A - Repairing additive for treating soil heavy metal pollution - Google Patents
Repairing additive for treating soil heavy metal pollution Download PDFInfo
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- CN106433659A CN106433659A CN201610722898.2A CN201610722898A CN106433659A CN 106433659 A CN106433659 A CN 106433659A CN 201610722898 A CN201610722898 A CN 201610722898A CN 106433659 A CN106433659 A CN 106433659A
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- soil
- powder
- enzymolysis product
- flax
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- 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
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
Abstract
The invention provides a repairing additive which is short in repairing cycle, good in effect and environmentally friendly. The repairing additive mainly comprises, by weight, 99-125 parts of flax powder, 13-23 parts of sodium dihydrogen phosphate, 5-10 parts of histidine, 13-18 parts of organic acid, 27-38 parts of enzymatic hydrolysate A, 31-39 parts of enzymatic hydrolysate B and 13-18 parts of vitamin C.
Description
Technical field
The present invention relates to technical field of soil remediation is and in particular to one kind is used for processing heavy metal pollution of soil reparation
Agent.
Background technology
Heavy metal pollution of soil refers to due to mankind's activity, heavy metal be added in soil, causes heavy metal in soil to contain
Amount is apparently higher than its natural background content, and causes the phenomenon that ecological disruption and environmental quality deteriorate.At present, heavy metal pollution
The processing mode of soil mainly has engineering measure, chemical modifying, agronomic measures and biological prosthetic 4 big class, but a lot of process
Mode is required for improving repairing effect using organic renovation agent.Heavy metal pollution of soil has disguise, chronicity and can not
Inverse property, the holdup time in soil for the pollutant is long, and plant or microorganism can not be degraded, and heavy metal pollution does not only result in soil
The reduction of degeneration, crop yield and quality, and the life and health of the mankind may be jeopardized by directly contact, food chain.
Organic renovation agent is primarily referred to as a class compound of carbon containing, hydrogen, rise in the reparation of heavy metal pollution of soil complexing,
Dam, the effect of fixing heavy metal contaminants, and partly organic renovation agent also has certain detoxication to biological.With science and technology
Progress and the continuing to bring out of new technology, the new formulation being applied to soil pollution reparation is on the increase, in soil environment protection
In played important function.But, only many drawbacks are had by simple organic renovation agent to soil remediation, for example, reduce and make
The biomass of thing, the problems such as there is bio-toxicity, lead to soil element to run off.
Content of the invention
In view of this, the present invention provides that a kind of repairing efficiency is short, and effect is good, environmentally friendly soil-repairing agent.
The technical scheme is that：One kind is used for processing heavy metal pollution of soil renovation agent, described soil-repairing agent
Main component component meter by weight include：Flax powder 99-125 part, sodium dihydrogen phosphate 13-23 part, histidine 5-10 part, have
Machine acid 13-18 part, enzymolysis product A 27-38 part, enzymolysis product B 31-39 part, vitamin C 13-18 part.
Particularly, described organic acid be oxalic acid, malic acid, the combination of any one or more in citric acid.
In the present invention, sodium dihydrogen phosphate and organic acid have certain activation for the heavy metal in soil, more
Be conducive to the formation stable compound of the other components in renovation agent and heavy metal element.The combination of histidine being capable of heavy metal
Ion plays good chelation, forms stable compound, is adsorbed in sub- harl.
Further, the preparation method of described flax powder is：S1. flax is pressed 1:2 material-water ratio is in 1 mol L-1、
2-8h is soaked in the citrate buffer solution of pH4.0；S2. the flax soaked is standby after 80 DEG C of dryings；S3. flax is adopted
Pulverized with pulverizer, cross 40 mesh sieves, both obtained flax powder.
Further, described enzymolysis product A is Monochoria vaginalis enzymolysis product, and its preparation method is：S1. Monochoria vaginalis was pulverized
40 mesh sieves, dry to constant mass in 80 DEG C, standby；S2. Monochoria vaginalis powder pre-treating, with the sulfuric acid of concentration 0.5% at 80 DEG C,
By Monochoria vaginalis powder：Sulfuric acid=1:30 solid-to-liquid ratio stirring 30min, 5000rpm are centrifuged 5-10min, taking precipitate；S3. digest,
Enzymatic hydrolysis condition is:Above-mentioned sediment is pressed 1:3 solid-to-liquid ratio adds water, and adds cellulase, and enzyme dosage is 120U g-1, pH
Value 4.0,45 DEG C of hydrolysis temperature, reaction time 18h, reacts the enzyme 10min that terminates to go out in boiling water bath, obtains enzymolysis liquid；S4.
Above-mentioned enzymolysis liquid is passed through to be spray-dried and obtains enzymolysis product A.
Further, described enzymolysis product B is water lettuce enzymolysis product, and its preparation method is：S1. water lettuce was pulverized
40 mesh sieves, dry to constant mass in 80 DEG C, standby；S2. water lettuce powder pre-treating, with the sulfuric acid of concentration 0.5% at 80 DEG C,
By water lettuce powder：Sulfuric acid=1:20 solid-to-liquid ratio stirring 30min, 5000rpm are centrifuged 5-10min, taking precipitate；S3. digest,
Enzymatic hydrolysis condition is:Above-mentioned sediment is pressed 1:3 solid-to-liquid ratio adds water, and adds cellulase, and enzyme dosage is 100U g-1, pH
Value 4.0,45 DEG C of hydrolysis temperature, reaction time 34h, reacts the enzyme 10min that terminates to go out in boiling water bath, obtains enzymolysis liquid；S4.
Above-mentioned enzymolysis liquid is passed through to be spray-dried and obtains enzymolysis product B.
Find through numerous studies, Monochoria vaginalis and water lettuce, as a kind of super enriching plant, can have for heavy metal element
Suction-operated.Respectively its active component is obtained to Monochoria vaginalis and water lettuce enzymolysis, more effective heavy metal ion is carried out chela
Conjunction/complexing simultaneously absorbs, and can further improve the efficiency of Metal uptake.In addition, in the present invention, vitamin C can conduct
Small-molecule substance in enzymolysis product A and enzymolysis product B and the catalyst aid of heavy metal chelating.
In the present invention, described flax powder is to be combined closely by many fibre bundles to form, and the section of flax fiber is in not
The polygonal of rule, there is narrow cavity centre.Fiber surface has longitudinal stripe, at some positions of fiber, these striped meetings
There is transversion malposition, the width of cavity keeps constant.By this special fibre structure, the gold that can will chelate through renovation agent
Belong to compound effectively to adsorb, be fixed on flax fiber, so that the heavy metal concentration in soil is drastically reduced, and in soil protection
Microorganism；Meanwhile, the enzymolysis product of Monochoria vaginalis and water lettuce passes through crosslinked complex role, and macromolecular substances therein can be with soil
In earth, the tunning of microorganism is incorporated into metal composite surface and forms Molecularly Imprinted Polymer, and this Molecularly Imprinted Polymer can be to flax
Metal composite in fiber has and further wraps pollutant.
The beneficial effects of the present invention is：(1) it is different from traditional organic renovation agent, so that the metallic element in soil is run off
Or most microorganisms are killed, the soil-repairing agent of present invention preparation, by the metallic element complexing in soil, it is fixed on Asia
On fiber crops, the heavy metal concentration in soil is made to drastically reduce, and the microorganism in soil protection；(2) containing organic in renovation agent
Acid, Monochoria vaginalis enzymolysis product and water lettuce enzymolysis product, greatly improve stalk to the absorption of heavy metal in soil ion, complexing
Ability, simultaneously the small-molecule active substance in enzymolysis product can with soil microorganism occur reciprocation, improve soil
Fertility.(3) it is different from traditional plant reparation, without idle land；(4) raw material sources are wide, and low production cost can be real
The reasonable utilization of existing low value resource；（5）The soil-repairing agent repairing efficiency of the present invention is short, and effect is good, is conducive to correlation technique
Promotion and application.
Specific embodiment
With reference to embodiment, the invention will be further described, but protection scope of the present invention is not limited to this.
Embodiment 1
One kind is used for processing heavy metal pollution of soil renovation agent, the main component component meter bag by weight of described soil-repairing agent
Include：85 parts of flax powder, 27 parts of sodium dihydrogen phosphate, 12 parts of histidine, 9 parts of organic acid, 33 parts of enzymolysis product A, enzymolysis product B
17 parts, 9 parts of vitamin C.
Particularly, described organic acid is citric acid.
Further, the preparation method of described flax powder is：S1. flax is pressed 1:2 material-water ratio is in 1 mol L-1、
5h is soaked in the citrate buffer solution of pH4.0；S2. the flax soaked is standby after 80 DEG C of dryings；S3. flax is adopted
Pulverizer is pulverized, and crosses 40 mesh sieves, had both obtained flax powder.
Further, described enzymolysis product A is Monochoria vaginalis enzymolysis product, and its preparation method is：S1. Monochoria vaginalis was pulverized
40 mesh sieves, dry to constant mass in 80 DEG C, standby；S2. Monochoria vaginalis powder pre-treating, with the sulfuric acid of concentration 0.5% at 80 DEG C,
By Monochoria vaginalis powder：Sulfuric acid=1:30 solid-to-liquid ratio stirring 30min, 5000rpm are centrifuged 5-10min, taking precipitate；S3. digest,
Enzymatic hydrolysis condition is:Above-mentioned sediment is pressed 1:3 solid-to-liquid ratio adds water, and adds cellulase, and enzyme dosage is 120U g-1, pH
Value 4.0,45 DEG C of hydrolysis temperature, reaction time 18h, reacts the enzyme 10min that terminates to go out in boiling water bath, obtains enzymolysis liquid；S4.
Above-mentioned enzymolysis liquid is passed through to be spray-dried and obtains enzymolysis product A.
Further, described enzymolysis product B is water lettuce enzymolysis product, and its preparation method is：S1. water lettuce was pulverized
40 mesh sieves, dry to constant mass in 80 DEG C, standby；S2. water lettuce powder pre-treating, with the sulfuric acid of concentration 0.5% at 80 DEG C,
By water lettuce powder：Sulfuric acid=1:20 solid-to-liquid ratio stirring 30min, 5000rpm are centrifuged 5-10min, taking precipitate；S3. digest,
Enzymatic hydrolysis condition is:Above-mentioned sediment is pressed 1:3 solid-to-liquid ratio adds water, and adds cellulase, and enzyme dosage is 100U g-1, pH
Value 4.0,45 DEG C of hydrolysis temperature, reaction time 34h, reacts the enzyme 10min that terminates to go out in boiling water bath, obtains enzymolysis liquid；S4.
Above-mentioned enzymolysis liquid is passed through to be spray-dried and obtains enzymolysis product B.
Embodiment 2
One kind is used for processing heavy metal pollution of soil renovation agent, the main component component meter bag by weight of described soil-repairing agent
Include：70 parts of flax powder, 27 parts of sodium dihydrogen phosphate, 12 parts of histidine, 9 parts of organic acid, 38 parts of enzymolysis product A, enzymolysis product B
14 parts, 9 parts of vitamin C.
Particularly, described organic acid is oxalic acid and citric acid 1：1 mixed acid.
Further, the preparation method of described flax powder is：S1. flax is pressed 1:2 material-water ratio is in 1 mol L-1、
5 h are soaked in the citrate buffer solution of pH4.0；S2. the flax soaked is standby after 80 DEG C of dryings；S3. flax is adopted
Pulverized with pulverizer, cross 40 mesh sieves, both obtained flax powder.
Further, described enzymolysis product A is Monochoria vaginalis enzymolysis product, and its preparation method is：S1. Monochoria vaginalis was pulverized
40 mesh sieves, dry to constant mass in 80 DEG C, standby；S2. Monochoria vaginalis powder pre-treating, with the sulfuric acid of concentration 0.5% at 80 DEG C,
By Monochoria vaginalis powder：Sulfuric acid=1:30 solid-to-liquid ratio stirring 30min, 5000rpm are centrifuged 5-10min, taking precipitate；S3. digest,
Enzymatic hydrolysis condition is:Above-mentioned sediment is pressed 1:3 solid-to-liquid ratio adds water, and adds cellulase, and enzyme dosage is 120U g-1, pH
Value 4.0,45 DEG C of hydrolysis temperature, reaction time 18h, reacts the enzyme 10min that terminates to go out in boiling water bath, obtains enzymolysis liquid；S4.
Above-mentioned enzymolysis liquid is passed through to be spray-dried and obtains enzymolysis product A.
Further, described enzymolysis product B is water lettuce enzymolysis product, and its preparation method is：S1. water lettuce was pulverized
40 mesh sieves, dry to constant mass in 80 DEG C, standby；S2. water lettuce powder pre-treating, with the sulfuric acid of concentration 0.5% at 80 DEG C,
By water lettuce powder：Sulfuric acid=1:20 solid-to-liquid ratio stirring 30min, 5000rpm are centrifuged 5-10min, taking precipitate；S3. digest,
Enzymatic hydrolysis condition is:Above-mentioned sediment is pressed 1:3 solid-to-liquid ratio adds water, and adds cellulase, and enzyme dosage is 100U g-1, pH
Value 4.0,45 DEG C of hydrolysis temperature, reaction time 34h, reacts the enzyme 10min that terminates to go out in boiling water bath, obtains enzymolysis liquid；S4.
Above-mentioned enzymolysis liquid is passed through to be spray-dried and obtains enzymolysis product B.
Embodiment 3
One kind is used for processing heavy metal pollution of soil renovation agent, the main component component meter bag by weight of described soil-repairing agent
Include：110 parts of flax powder, 27 parts of sodium dihydrogen phosphate, 12 parts of histidine, 9 parts of organic acid, 27 parts of enzymolysis product A, enzymolysis product B
21 parts, 9 parts of vitamin C.
Particularly, described organic acid is oxalic acid.
Further, the preparation method of described flax powder is：S1. flax is pressed 1:2 material-water ratio is in 1 mol L-1、
8h is soaked in the citrate buffer solution of pH4.0；S2. the flax soaked is standby after 80 DEG C of dryings；S3. flax is adopted
Pulverizer is pulverized, and crosses 40 mesh sieves, had both obtained flax powder.
Further, described enzymolysis product A is Monochoria vaginalis enzymolysis product, and its preparation method is：S1. Monochoria vaginalis was pulverized
40 mesh sieves, dry to constant mass in 80 DEG C, standby；S2. Monochoria vaginalis powder pre-treating, with the sulfuric acid of concentration 0.5% at 80 DEG C,
By Monochoria vaginalis powder：Sulfuric acid=1:30 solid-to-liquid ratio stirring 30min, 5000rpm are centrifuged 5-10min, taking precipitate；S3. digest,
Enzymatic hydrolysis condition is:Above-mentioned sediment is pressed 1:3 solid-to-liquid ratio adds water, and adds cellulase, and enzyme dosage is 120U g-1, pH
Value 4.0,45 DEG C of hydrolysis temperature, reaction time 18h, reacts the enzyme 10min that terminates to go out in boiling water bath, obtains enzymolysis liquid；S4.
Above-mentioned enzymolysis liquid is passed through to be spray-dried and obtains enzymolysis product A.
Further, described enzymolysis product B is water lettuce enzymolysis product, and its preparation method is：S1. water lettuce was pulverized
40 mesh sieves, dry to constant mass in 80 DEG C, standby；S2. water lettuce powder pre-treating, with the sulfuric acid of concentration 0.5% at 80 DEG C,
By water lettuce powder：Sulfuric acid=1:20 solid-to-liquid ratio stirring 30min, 5000rpm are centrifuged 5-10min, taking precipitate；S3. digest,
Enzymatic hydrolysis condition is:Above-mentioned sediment is pressed 1:3 solid-to-liquid ratio adds water, and adds cellulase, and enzyme dosage is 100U g-1, pH
Value 4.0,45 DEG C of hydrolysis temperature, reaction time 34h, reacts the enzyme 10min that terminates to go out in boiling water bath, obtains enzymolysis liquid；S4.
Above-mentioned enzymolysis liquid is passed through to be spray-dried and obtains enzymolysis product B.
Comparative example 1
One kind is used for processing heavy metal pollution of soil renovation agent, the main component component meter bag by weight of described soil-repairing agent
Include：85 parts of flax powder, 27 parts of sodium dihydrogen phosphate, 12 parts of histidine, 9 parts of organic acid, 33 parts of enzymolysis product A, vitamin C 9
Part.
Particularly, described organic acid is citric acid.
Further, the preparation method of described flax powder is：S1. flax is pressed 1:2 material-water ratio is in 1 mol L-1、
5h is soaked in the citrate buffer solution of pH4.0；S2. the flax soaked is standby after 80 DEG C of dryings；S3. flax is adopted
Pulverizer is pulverized, and crosses 40 mesh sieves, had both obtained flax powder.
Further, described enzymolysis product A is Monochoria vaginalis enzymolysis product, and its preparation method is：S1. Monochoria vaginalis was pulverized
40 mesh sieves, dry to constant mass in 80 DEG C, standby；S2. Monochoria vaginalis powder pre-treating, with the sulfuric acid of concentration 0.5% at 80 DEG C,
By Monochoria vaginalis powder：Sulfuric acid=1:30 solid-to-liquid ratio stirring 30min, 5000rpm are centrifuged 5-10min, taking precipitate；S3. digest,
Enzymatic hydrolysis condition is:Above-mentioned sediment is pressed 1:3 solid-to-liquid ratio adds water, and adds cellulase, and enzyme dosage is 120U g-1, pH
Value 4.0,45 DEG C of hydrolysis temperature, reaction time 18h, reacts the enzyme 10min that terminates to go out in boiling water bath, obtains enzymolysis liquid；S4.
Above-mentioned enzymolysis liquid is passed through to be spray-dried and obtains enzymolysis product A.
Comparative example 2
One kind is used for processing heavy metal pollution of soil renovation agent, the main component component meter bag by weight of described soil-repairing agent
Include：85 parts of flax powder, 27 parts of sodium dihydrogen phosphate, 12 parts of histidine, 9 parts of organic acid, 17 parts of enzymolysis product B, vitamin C 9
Part.
Particularly, described organic acid is citric acid.
Further, the preparation method of described flax powder is：S1. flax is pressed 1:2 material-water ratio is in 1 mol L-1、
5h is soaked in the citrate buffer solution of pH4.0；S2. the flax soaked is standby after 80 DEG C of dryings；S3. flax is adopted
Pulverizer is pulverized, and crosses 40 mesh sieves, had both obtained flax powder.
Further, described enzymolysis product B is water lettuce enzymolysis product, and its preparation method is：S1. water lettuce was pulverized
40 mesh sieves, dry to constant mass in 80 DEG C, standby；S2. water lettuce powder pre-treating, with the sulfuric acid of concentration 0.5% at 80 DEG C,
By water lettuce powder：Sulfuric acid=1:20 solid-to-liquid ratio stirring 30min, 5000rpm are centrifuged 5-10min, taking precipitate；S3. digest,
Enzymatic hydrolysis condition is:Above-mentioned sediment is pressed 1:3 solid-to-liquid ratio adds water, and adds cellulase, and enzyme dosage is 100U g-1, pH
Value 4.0,45 DEG C of hydrolysis temperature, reaction time 34h, reacts the enzyme 10min that terminates to go out in boiling water bath, obtains enzymolysis liquid；S4.
Above-mentioned enzymolysis liquid is passed through to be spray-dried and obtains enzymolysis product B.
Implementation result is tested
By the soil-repairing agent in 2g embodiment 1-3 and comparative example 1-2 and 50g heavy metal (Hg2+、As3+) content is
1% contaminated soil mixing, adds 200mL water, is stirred at room temperature 2 hours, standing, the content of heavy metal ion in test solution,
Calculate removal of heavy metal ions rate as shown in the table.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, and do not carrying on the back
In the case of the spirit or essential attributes of the present invention, the present invention can be realized in other specific forms.Therefore, no matter from which
From the point of view of a bit, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention will by appended right
Ask rather than described above limits, it is intended that all changes that will fall in the implication and scope of the equivalency of claim
Include in the present invention.
Moreover, it will be appreciated that although this specification is been described by according to embodiment, not each embodiment only comprises one
Individual independent technical scheme, only for clarity, those skilled in the art should will say this narrating mode of specification
Bright book can also form those skilled in the art permissible through appropriately combined as an entirety, the technical scheme in each embodiment
The other embodiment understanding.For the ins and outs of not detailed descriptions all in the present invention, all can be arbitrary existing by this area
Technology is had to realize.
Claims (4)
1. one kind be used for processing heavy metal pollution of soil renovation agent it is characterised in that：The main component of described soil-repairing agent
Component meter by weight includes：Flax powder 99-125 part, sodium dihydrogen phosphate 13-23 part, histidine 5-10 part, organic acid 13-18
Part, enzymolysis product A 27-38 part, enzymolysis product B 31-39 part, vitamin C 13-18 part.
2. soil-repairing agent according to claim 1 is it is characterised in that the preparation method of described flax powder is：S1. will
Flax presses 1:2 material-water ratio is in 1 mol L-1, pH4.0 citrate buffer solution in soak 2-8h；S2. by the Asia soaked
Fiber crops are standby after 80 DEG C of dryings；S3. flax is pulverized using pulverizer, cross 40 mesh sieves, both obtained flax powder.
3. soil-repairing agent according to claim 1 it is characterised in that described enzymolysis product A be Monochoria vaginalis enzymolysis product,
Its preparation method is：S1. Monochoria vaginalis was pulverized 40 mesh sieves, dried to constant mass in 80 DEG C, standby；S2. Monochoria vaginalis powder
Pretreatment, with the sulfuric acid of concentration 0.5% at 80 DEG C, by Monochoria vaginalis powder：Sulfuric acid=1:30 solid-to-liquid ratio stirring 30min, 5000rpm
Centrifugation 5-10min, taking precipitate；S3. digest, enzymatic hydrolysis condition is:Above-mentioned sediment is pressed 1:3 solid-to-liquid ratio adds water, and adds fine
The plain enzyme of dimension, enzyme dosage is 120U g-1, pH value 4.0,45 DEG C of hydrolysis temperature, reaction time 18h, reaction terminates after boiling water
Go out in bath enzyme 10min, obtains enzymolysis liquid；S4. above-mentioned enzymolysis liquid is passed through to be spray-dried and obtain enzymolysis product A.
4. soil-repairing agent according to claim 1 it is characterised in that described enzymolysis product B be water lettuce enzymolysis product,
Its preparation method is：S1. water lettuce was pulverized 40 mesh sieves, dried to constant mass in 80 DEG C, standby；S2. water lettuce powder
Pretreatment, with the sulfuric acid of concentration 0.5% at 80 DEG C, by water lettuce powder：Sulfuric acid=1:20 solid-to-liquid ratio stirring 30min, 5000rpm
Centrifugation 5-10min, taking precipitate；S3. digest, enzymatic hydrolysis condition is:Above-mentioned sediment is pressed 1:3 solid-to-liquid ratio adds water, and adds fine
The plain enzyme of dimension, enzyme dosage is 100U g-1, pH value 4.0,45 DEG C of hydrolysis temperature, reaction time 38h, reaction terminates after boiling water
Go out in bath enzyme 10min, obtains enzymolysis liquid；S4. above-mentioned enzymolysis liquid is passed through to be spray-dried and obtain enzymolysis product B.
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| CN201610722898.2A CN106433659A (en) | 2016-08-25 | 2016-08-25 | Repairing additive for treating soil heavy metal pollution |
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| CN107254322A (en) * | 2017-08-18 | 2017-10-17 | 中山市绿浪助剂有限公司 | A kind of soil-repairing agent containing microbial bacterial agent |
| CN107523305A (en) * | 2017-08-02 | 2017-12-29 | 郭婷 | One heavy metal species soil-repairing agent |
| CN108440077A (en) * | 2018-01-16 | 2018-08-24 | 刘肖俊 | A kind of novel ecological afforestation soil remediation inorganic agent |
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Cited By (3)
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Application publication date: 20170222 |