CN107952792A

CN107952792A - A kind of method polluted using plant efficient repairing heavy metal in soil

Info

Publication number: CN107952792A
Application number: CN201711046915.6A
Authority: CN
Inventors: 薛红娟; 林茂兰
Original assignee: Changzhou Haotan Trading Co Ltd
Current assignee: Changzhou Haotan Trading Co Ltd
Priority date: 2017-10-31
Filing date: 2017-10-31
Publication date: 2018-04-24

Abstract

The present invention relates to soil pollution by heavy metal technical field, and in particular to a kind of method polluted using plant efficient repairing heavy metal in soil.It is of the invention that nano-apatite is first made with phosphate and calcium salt under hydrothermal conditions, and through amination modifying, the Chinese medicine containing metal chelating composition and the fruit rich in amino acid are blended again, together ferment to obtain tunning with nano-apatite, tunning is embedded to plantation hole, and the plant of enriching heavy metal is capable of in interval plantation in plantation hole, concentrate and destroy after plant completes enrichment, it can complete the reparation to heavy-metal contaminated soil, the activation of the secretions from plant roots of plantation causes the heavy metal ion in soil to be converted into the chelate of solubility, by plant root rich absorbent, the enrichment to heavy metal in soil is completed to remove, since the enrichment concentration of tunning is acted on so that root system of plant is easier to absorb heavy metal, rich absorbent speed accelerates, repair time shortens.

Description

A kind of method polluted using plant efficient repairing heavy metal in soil

Technical field

The present invention relates to soil pollution by heavy metal technical field, and in particular to one kind utilizes a plant efficient rehabilitating soil huge sum of money Belong to the method for pollution.

Background technology

With the high speed development of modern economy, the activity of the mankind causes the heavy metals such as cadmium, lead, zinc, chromium constantly to ring Discharge in border, accumulate in the soil, and harm is produced to human body by food chain, brought sternly to soil for the survival of mankind The pollution of weight.It is not easily decomposed, converts or is enriched with after enters soil due to heavy metal, and the complexity of soil system this body structure Property so that the improvement of heavy metal pollution of soil becomes very difficult.

At present, heavy metal pollution of soil governance way mainly has two kinds, when change heavy metal in the soil there are shape State, makes it switch to stable state by activated state；Second, heavy metal is removed from soil.Method mainly has gongwu chemical method, bag Include：Heavy metal pollution of soil, rinse complexometry, electronic chemical method, heat treating process etc., but is not suitable for the larger soil of contaminated area；Biology Repairing method includes：The effect of phytoremediation, microorganism remediation and animal reparation etc., plant and lower animal repairing method to soil remediation Fruit is less notable；Microorganism remediation utilizes the certain micro-organisms in soil to have absorption, precipitation, oxidation and reduction etc. to heavy metal Effect, so as to reduce the toxicity of heavy metal in soil.The technology can be such that heavy metal contaminants are removed from soil, to ring around Border influence is smaller, will not produce secondary pollution, the huge soil remediation potentiality having.But existing heavy-metal contaminated soil is micro- Bioremediation technology has some limitations, and such as microorganism remediation duration length, slowly effect, generally form complex compound reduction The harm of heavy metal, can not remove heavy metal from soil.

Phytoremediation technology is to utilize the absorption of plant and its rhizosphere microorganism to soil pollutant, volatilization, conversion, drop Solution, fixation and remove the recovery technique of pollutant in soil.Have now been found that many plants can be at the same time to an a variety of huge sum of moneys Category has powerful accumulation ability, but most plants restorative procedure effect is not notable, slowly effect, repair time length, repairing effect It is unstable, the improvement of large area soil is not suitable for, along with being influenced be subject to weather, soil environment so that these plants Accumulation of heavy metals amount is limited, so as to be above restricted in its application.

The content of the invention

Present invention mainly solves technical problem, for current most plants restoration of soil polluted by heavy metal method imitate Fruit not significantly, slowly effect, repair time length, repairing effect is unstable, the defects of not being suitable for the improvement of large area soil, there is provided A kind of method polluted using plant efficient repairing heavy metal in soil.

In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：

A kind of method polluted using plant efficient repairing heavy metal in soil, it is characterised in that concrete operation step is：

（1）The calcium nitrate solution that sodium dihydrogen phosphate and concentration that concentration is 1.5mol/L are 1.5mol/L is mixed, is obtained Mixed liquor, mixed liquor is fitted into hydrothermal reaction kettle, then hexamethylenetetramine is added into hydrothermal reaction kettle, it is stirred 15~ 20min；

（2）After treating above-mentioned be stirred, pH to 10.0~11.0 is adjusted with sodium hydroxide solution, closed hydrothermal reaction kettle is simultaneously Heat temperature raising, keeps the temperature hydro-thermal reaction, is separated by filtration and is precipitated, and is rinsed 3~5 times with absolute ethyl alcohol and water successively, and dry, obtains To nano-apatite；

（3）Count in parts by weight, weigh 15~20 portions of cordate houttuynias, 10~12 portions of Kiwi berrys, 10~15 parts of scutellarias and 15~20 It is put into after part lemon mixing in pulverizer, 1~2h of crushing obtains mixed powder and minces, and mixed powder is minced and nano-apatite mixes Obtain fermentation substrate；

（4）Above-mentioned fermentation substrate is fitted into fermentation tank, then spine spore Penicillium notatum bacteria suspension is added into fermentation tank, is sealed after stirring Tank mouth, is sealed by fermentation, obtains tunning after fermentation；

（5）Plantation hole is excavated in soil to be repaired, the above-mentioned fermentation that thickness is 1~2cm is added into each plantation hole and is produced Thing, then the soil that a layer thickness is 1cm is covered above tunning, obtain pretreatment plantation hole；

（6）Into above-mentioned pretreatment plantation hole by the plantation order of one celery of a leaf mustard by leaf mustard and celery into between-line spacing kind Plant, return the fixed plantation for completing leaf mustard and celery of soil, wait after the completion of planting, to diversion irrigation in soil is treated, make after irrigation Leaf mustard and celery are grown 2~3 weeks naturally, are uprooped leaf mustard and celery after growth and are harvested, and by the mustard of harvest Dish and celery, which are concentrated, to be destroyed, you can completes to repair the efficient of heavy metal pollution of soil.

Step（1）Described in concentration be 1.5mol/L sodium dihydrogen phosphate and concentration be 1.5mol/L calcium nitrate The mass ratio of solution is 3:5, the addition of hexamethylenetetramine is the 1% of mixed liquor quality.

Step（2）Described in the temperature of heat temperature raising be 165~180 DEG C, the time of hydro-thermal reaction be 20~24h, dry Dry temperature is 105~110 DEG C, and the dry time is 2~3h.

Step（3）Described in mixed powder mince with the mass ratio of nano-apatite be 2:1.

Step（4）Described in spine spore Penicillium notatum bacteria suspension addition be fermentation substrate quality 5%, spine spore Penicillium notatum The concentration of bacteria suspension is 10¹¹Cfu/mL, the temperature of sealing and fermenting is 25~35 DEG C, and the time of sealing and fermenting is 12~15 days.

Step（5）Described in the distance between rows and hills of plantation hole be 30cm × 40cm, the depth of plantation hole is 8~10cm.

Step（6）Described in irrigation volume be 70~90m³/ mu.

The beneficial effects of the invention are as follows：

（1）It is of the invention that nano-apatite is first made with phosphate and calcium salt under hydrothermal conditions, and through amination modifying, then will contain The Chinese medicine of metal chelating composition and the fruit blending rich in amino acid, together ferment to obtain tunning with nano-apatite, Tunning is embedded to plantation hole, and the plant of enriching heavy metal is capable of in interval plantation in plantation hole, treats that plant completes enrichment Concentrate and destroy afterwards, you can the reparation to heavy-metal contaminated soil is completed, Chinese medicine and fruit are realized degraded by the present invention by fermentation, So that in Chinese medicine have chelated metal ions ability component dissolution, and fruit degrade during produce a large amount of active aminos and Carboxyl, these active groups are introduced in nano-apatite surface under the self-crosslinking of microorganism, and sequestering carboxyl draws Enter so that nano-apatite has metal ion-chelant attractability, will be enriched in the nanometer of effective component of chinese medicine and metal chelation abilities The tunning of apatite is applied in plantation hole, can receiving by effective component of chinese medicine in fermentate and metal chelation abilities Rice apatite collective effect, the heavy metal chelating in soil is gathered in plantation hole, then the secretions from plant roots through plantation Activation cause the heavy metal ion in soil to be converted into the chelate of solubility, by plant root rich absorbent, complete Enrichment to heavy metal in soil removes, since the enrichment concentration of tunning is acted on so that root system of plant is easier to absorb a huge sum of money Belong to, rich absorbent speed accelerates, and repair time shortens；

（2）The nano-apatite that the present invention uses can provide fertilizer nutrient for plant growth, in addition its nano material property Synergistic effect is played, can be in the effect of biological magnetic field since the small-size effect of nanometer base-material makes nano-apatite band magnetic effect Under make nutrient be more easy to be absorbed by plants, be conducive to plant growth, secondly, have many dangling bonds around its surface atom, have very High activity, due to skin effect, makes nano-apatite surface energy, Surface binding energy increase, beneficial to causing chelated metal ions Nano-apatite attracts to be enriched with by root system of plant in the soil, improves the efficiency of plant absorption heavy metal, nanostructured phosphorus ash Stone can also stimulate plant growth, improve the activity of a variety of enzymes in plant, improve the increase of secretions from plant roots, while two kinds Competition between different plants can also improve the increase of its root exudates so that metal activation efficiency becomes higher, further Improve remediation efficiency, in addition, the fungi microbe cell membrane contained in tunning of the present invention carries elecrtonegativity, can and with much money Belong to electrostatical binding, recycle microorganism that there is certain resistance and detoxication to heavy metal, can adsorb and convert heavy metal, Using itself and plant collective effect, remediation efficiency is improved again, only needs can complete to repair within 2~3 weeks, and there is wide answer Use prospect.

Embodiment

It is 3 in mass ratio:5 be 1.5mol/L by sodium dihydrogen phosphate and concentration that concentration is 1.5mol/L calcium nitrate Solution mixes, and obtains mixed liquor, mixed liquor is fitted into hydrothermal reaction kettle, then mixed liquor quality 1% is added into hydrothermal reaction kettle Hexamethylenetetramine, be stirred 15~20min；It is to be mixed after mixing, be 30% sodium hydroxide solution with mass fraction PH to 10.0~11.0 is adjusted, closed hydrothermal reaction kettle is simultaneously heated to 165~180 DEG C, keeps the temperature 20~24h of hydro-thermal reaction, Be separated by filtration and precipitated, rinsed 3~5 times with absolute ethyl alcohol and water successively, and be put into baking oven dry 2 at 105~110 DEG C~ 3h, obtains nano-apatite；Count in parts by weight, weigh 15~20 portions of cordate houttuynias, 10~12 portions of Kiwi berrys, 10~15 parts of scutellarias And be put into after the mixing of 15~20 portions of lemons in pulverizer, crush 1~2h and obtain mixed powder and mince, mixed powder is minced and nanometer Apatite is 2 in mass ratio:1 is mixed to get fermentation substrate；Fermentation substrate is fitted into fermentation tank, then hair is added into fermentation tank The concentration of ferment substrate quality 5% is 10¹¹The spine spore Penicillium notatum bacteria suspension of cfu/mL, tank mouth is sealed after stirring 3~5min, 25~ It is sealed by fermentation 12~15 days at 35 DEG C, obtains tunning after fermentation；By distance between rows and hills for 30cm × 40cm to be repaired Plantation hole is excavated in soil, it is 8~10cm to control plantation hole depth, and it is the above-mentioned of 1~2cm that thickness is added into each plantation hole Tunning, then the soil that a layer thickness is 1cm is covered above tunning, obtain pretreatment plantation hole；To pretreatment kind Plant in hole and plant leaf mustard and celery into between-line spacing by the plantation order of one celery of a leaf mustard, return soil it is fixed complete leaf mustard and The plantation of celery, is waited after the completion of planting, and is 70~90m by irrigation volume³/ mu makes leaf mustard to diversion in soil is treated after irrigation Grown naturally 2~3 weeks with celery, leaf mustard and celery uprooped after growth and harvested, and by the leaf mustard of harvest and Celery, which is concentrated, to be destroyed, you can completes to repair the efficient of heavy metal pollution of soil.

Example 1

It is 3 in mass ratio:5 be 1.5mol/L by sodium dihydrogen phosphate and concentration that concentration is 1.5mol/L calcium nitrate solution Mixing, obtains mixed liquor, mixed liquor is fitted into hydrothermal reaction kettle, then the six of mixed liquor quality 1% is added into hydrothermal reaction kettle Methine tetramine, is stirred 15min；It is to be mixed after mixing, with mass fraction for 30% sodium hydroxide solution adjust pH to 10.0, closed hydrothermal reaction kettle is simultaneously heated to 165 DEG C, keeps the temperature hydro-thermal reaction 20h, is separated by filtration and is precipitated, used successively Absolute ethyl alcohol and water rinse 3 times, and are put into baking oven dry 2h at 105 DEG C, obtain nano-apatite；Count, claim in parts by weight It is put into after taking 15 portions of cordate houttuynias, 10 portions of Kiwi berrys, 10 parts of scutellarias and 15 parts of lemon mixing in pulverizer, crushes 1h and mixed Crushed material, it is 2 in mass ratio that mixed powder, which is minced with nano-apatite,:1 is mixed to get fermentation substrate；Fermentation substrate is loaded and is sent out In fermentation tank, then the concentration of addition fermentation substrate quality 5% is 10 into fermentation tank¹¹The spine spore Penicillium notatum bacteria suspension of cfu/mL, stirring Tank mouth is sealed after 3min, is sealed by fermentation 12 days at 25 DEG C, obtains tunning after fermentation；By distance between rows and hills for 30cm × 40cm excavates plantation hole in soil to be repaired, and it is 8cm to control plantation hole depth, and thickness is added into each plantation hole and is The above-mentioned tunning of 1cm, then the soil that a layer thickness is 1cm is covered above tunning, obtain pretreatment plantation hole；To Pre-process in plantation hole and plant leaf mustard and celery into between-line spacing by the plantation order of one celery of a leaf mustard, return soil and fixed Into the plantation of leaf mustard and celery, wait after the completion of planting, be 70m by irrigation volume³/ mu makes to diversion in soil is treated after irrigation Leaf mustard and celery are grown 2 weeks naturally, are uprooped leaf mustard and celery after growth and are harvested, and by the leaf mustard of harvest and Celery, which is concentrated, to be destroyed, you can completes to repair the efficient of heavy metal pollution of soil.

Example 2

It is 3 in mass ratio:5 be 1.5mol/L by sodium dihydrogen phosphate and concentration that concentration is 1.5mol/L calcium nitrate solution Mixing, obtains mixed liquor, mixed liquor is fitted into hydrothermal reaction kettle, then the six of mixed liquor quality 1% is added into hydrothermal reaction kettle Methine tetramine, is stirred 18min；It is to be mixed after mixing, with mass fraction for 30% sodium hydroxide solution adjust pH to 10.5, closed hydrothermal reaction kettle is simultaneously heated to 175 DEG C, keeps the temperature hydro-thermal reaction 22h, is separated by filtration and is precipitated, used successively Absolute ethyl alcohol and water rinse 4 times, and are put into baking oven dry 2h at 108 DEG C, obtain nano-apatite；Count, claim in parts by weight It is put into after taking 18 portions of cordate houttuynias, 11 portions of Kiwi berrys, 13 parts of scutellarias and 18 parts of lemon mixing in pulverizer, crushes 1h and mixed Crushed material, it is 2 in mass ratio that mixed powder, which is minced with nano-apatite,:1 is mixed to get fermentation substrate；Fermentation substrate is loaded and is sent out In fermentation tank, then the concentration of addition fermentation substrate quality 5% is 10 into fermentation tank¹¹The spine spore Penicillium notatum bacteria suspension of cfu/mL, stirring Tank mouth is sealed after 4min, is sealed by fermentation 14 days at 30 DEG C, obtains tunning after fermentation；By distance between rows and hills for 30cm × 40cm excavates plantation hole in soil to be repaired, and it is 9cm to control plantation hole depth, and thickness is added into each plantation hole and is The above-mentioned tunning of 1cm, then the soil that a layer thickness is 1cm is covered above tunning, obtain pretreatment plantation hole；To Pre-process in plantation hole and plant leaf mustard and celery into between-line spacing by the plantation order of one celery of a leaf mustard, return soil and fixed Into the plantation of leaf mustard and celery, wait after the completion of planting, be 80m by irrigation volume³/ mu makes to diversion in soil is treated after irrigation Leaf mustard and celery are grown 2 weeks naturally, are uprooped leaf mustard and celery after growth and are harvested, and by the leaf mustard of harvest and Celery, which is concentrated, to be destroyed, you can completes to repair the efficient of heavy metal pollution of soil.

Example 3

It is 3 in mass ratio:5 be 1.5mol/L by sodium dihydrogen phosphate and concentration that concentration is 1.5mol/L calcium nitrate solution Mixing, obtains mixed liquor, mixed liquor is fitted into hydrothermal reaction kettle, then the six of mixed liquor quality 1% is added into hydrothermal reaction kettle Methine tetramine, is stirred 20min；It is to be mixed after mixing, with mass fraction for 30% sodium hydroxide solution adjust pH to 11.0, closed hydrothermal reaction kettle is simultaneously heated to 180 DEG C, keeps the temperature hydro-thermal reaction 24h, is separated by filtration and is precipitated, used successively Absolute ethyl alcohol and water rinse 5 times, and are put into baking oven dry 3h at 110 DEG C, obtain nano-apatite；Count, claim in parts by weight It is put into after taking 20 portions of cordate houttuynias, 12 portions of Kiwi berrys, 15 parts of scutellarias and 20 parts of lemon mixing in pulverizer, crushes 2h and mixed Crushed material, it is 2 in mass ratio that mixed powder, which is minced with nano-apatite,:1 is mixed to get fermentation substrate；Fermentation substrate is loaded and is sent out In fermentation tank, then the concentration of addition fermentation substrate quality 5% is 10 into fermentation tank¹¹The spine spore Penicillium notatum bacteria suspension of cfu/mL, stirring Tank mouth is sealed after 5min, is sealed by fermentation 15 days at 35 DEG C, obtains tunning after fermentation；By distance between rows and hills for 30cm × 40cm excavates plantation hole in soil to be repaired, and it is 10cm to control plantation hole depth, and thickness is added into each plantation hole and is The above-mentioned tunning of 2cm, then the soil that a layer thickness is 1cm is covered above tunning, obtain pretreatment plantation hole；To Pre-process in plantation hole and plant leaf mustard and celery into between-line spacing by the plantation order of one celery of a leaf mustard, return soil and fixed Into the plantation of leaf mustard and celery, wait after the completion of planting, be 90m by irrigation volume³/ mu makes to diversion in soil is treated after irrigation Leaf mustard and celery are grown 3 weeks naturally, are uprooped leaf mustard and celery after growth and are harvested, and by the leaf mustard of harvest and Celery, which is concentrated, to be destroyed, you can completes to repair the efficient of heavy metal pollution of soil.

Reference examples

Directly to plant leaf mustard and celery restoration of soil polluted by heavy metal as a comparison case

Heavy metal in soil removal effect after being repaired to the present invention is detected, and testing result is as shown in table 1：

Table 1

Detection project	Example 1	Example 2	Example 3	Reference examples
					Copper ion removal rate（%）	98.7	98.9	99.2	85.2
Manganese ion removal rate（%）	99.0	99.1	99.3	87.9
					Chromium ion removal rate（%）	99.2	99.3	99.3	89.2
Zinc ion removal rate（%）	98.6	99.0	99.3	82.6
					Process cycle（My god）	14	11	10	40

By being detected in upper table it can be seen from data, restorative procedure repairing effect provided by the invention is notable, quick, repair time It is short, have broad application prospects.

Claims

A kind of 1. method polluted using plant efficient repairing heavy metal in soil, it is characterised in that concrete operation step is：

（1）The calcium nitrate solution that sodium dihydrogen phosphate and concentration that concentration is 1.5mol/L are 1.5mol/L is mixed, is obtained Mixed liquor, mixed liquor is fitted into hydrothermal reaction kettle, then hexamethylenetetramine is added into hydrothermal reaction kettle, it is stirred 15~ 20min；

（2）After treating above-mentioned be stirred, pH to 10.0~11.0 is adjusted with sodium hydroxide solution, closed hydrothermal reaction kettle is simultaneously Heat temperature raising, keeps the temperature hydro-thermal reaction, is separated by filtration and is precipitated, and is rinsed 3~5 times with absolute ethyl alcohol and water successively, and dry, obtains To nano-apatite；

（3）Count in parts by weight, weigh 15~20 portions of cordate houttuynias, 10~12 portions of Kiwi berrys, 10~15 parts of scutellarias and 15~20 It is put into after part lemon mixing in pulverizer, 1~2h of crushing obtains mixed powder and minces, and mixed powder is minced and nano-apatite mixes Obtain fermentation substrate；

（4）Above-mentioned fermentation substrate is fitted into fermentation tank, then spine spore Penicillium notatum bacteria suspension is added into fermentation tank, is sealed after stirring Tank mouth, is sealed by fermentation, obtains tunning after fermentation；

（5）Plantation hole is excavated in soil to be repaired, the above-mentioned fermentation that thickness is 1~2cm is added into each plantation hole and is produced Thing, then the soil that a layer thickness is 1cm is covered above tunning, obtain pretreatment plantation hole；

（6）Into above-mentioned pretreatment plantation hole by the plantation order of one celery of a leaf mustard by leaf mustard and celery into between-line spacing kind Plant, return the fixed plantation for completing leaf mustard and celery of soil, wait after the completion of planting, to diversion irrigation in soil is treated, make after irrigation Leaf mustard and celery are grown 2~3 weeks naturally, are uprooped leaf mustard and celery after growth and are harvested, and by the mustard of harvest Dish and celery, which are concentrated, to be destroyed, you can completes to repair the efficient of heavy metal pollution of soil.
A kind of 2. method polluted using plant efficient repairing heavy metal in soil according to claim 1, it is characterised in that： Step（1）Described in concentration be 1.5mol/L sodium dihydrogen phosphate and concentration be 1.5mol/L calcium nitrate solution matter Amount is than being 3:5, the addition of hexamethylenetetramine is the 1% of mixed liquor quality.
A kind of 3. method polluted using plant efficient repairing heavy metal in soil according to claim 1, it is characterised in that： Step（2）Described in the temperature of heat temperature raising be 165~180 DEG C, time of hydro-thermal reaction is 20~24h, dry temperature For 105~110 DEG C, the dry time is 2~3h.
A kind of 4. method polluted using plant efficient repairing heavy metal in soil according to claim 1, it is characterised in that： Step（3）Described in mixed powder mince with the mass ratio of nano-apatite be 2:1.
A kind of 5. method polluted using plant efficient repairing heavy metal in soil according to claim 1, it is characterised in that： Step（4）Described in spine spore Penicillium notatum bacteria suspension addition be fermentation substrate quality 5%, spine spore Penicillium notatum bacteria suspension Concentration is 10¹¹Cfu/mL, the temperature of sealing and fermenting is 25~35 DEG C, and the time of sealing and fermenting is 12~15 days.
A kind of 6. method polluted using plant efficient repairing heavy metal in soil according to claim 1, it is characterised in that： Step（5）Described in the distance between rows and hills of plantation hole be 30cm × 40cm, the depth of plantation hole is 8~10cm.
A kind of 7. method polluted using plant efficient repairing heavy metal in soil according to claim 1, it is characterised in that： Step（6）Described in irrigation volume be 70~90m³/ mu.