CN106305771A - Soil sterilizer and preparation method thereof - Google Patents

Soil sterilizer and preparation method thereof Download PDF

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Publication number
CN106305771A
CN106305771A CN201510346508.1A CN201510346508A CN106305771A CN 106305771 A CN106305771 A CN 106305771A CN 201510346508 A CN201510346508 A CN 201510346508A CN 106305771 A CN106305771 A CN 106305771A
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Prior art keywords
soil
potassium
acid
proportion
nitrogen
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符国栋
符扬
吴世斌
妥国栋
伊百成
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Beijing Yun Da Zhong Tian Environment Technology Co Ltd
Shanxi Yun Da Zhong Tian Environment Technology Co Ltd
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Beijing Yun Da Zhong Tian Environment Technology Co Ltd
Shanxi Yun Da Zhong Tian Environment Technology Co Ltd
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Abstract

The invention relates to a soil sterilizer with fertilizer efficiency and activated nutrients, and a preparation method of the soil sterilizer. The soil sterilizer comprises sodium chlorite as a precursor for generating chlorine dioxide, ammonium bisulfate (potassium bisulfate), acidic potassium phosphate, urea phosphate and citric acid which are used as activators of the sodium chlorite, and anhydrous calcium chloride and anhydrous magnesium sulfate which are used as stabilizers. Therefore, the soil sterilizer has a function of sterilizing and disinfecting soil, and is capable of supplying macro elements such as nitrogen, phosphorus and potassium, medium elements such as calcium, magnesium and sulfur and trace elements such as zinc, iron, manganese and copper in activated soil to plants.

Description

A kind of soil sterilants and preparation method thereof
Technical field
The invention belongs to agriculture field, be specifically related to a kind of soil sterilants and preparation method thereof, more particularly one has fertilizer Soil sterilants of effect and activation nutrient and preparation method thereof.
Technical background
Soil is the basis of plant growing, is also the sex pheromone main place that grows, breed, hide oneself.Same crop exists Same plot is planted year after year or repeats plantation, is referred to as continuous cropping or continuous cropping.Continuous cropping and continuous cropping can cause pathogen in soil to increase in a large number Adding, secretions from plant roots accumulates in a large number simultaneously, also can become the toxin of suppression plant growing owing to can not get degrading in time. China has a large population and a few land, and soil, almost without the chance lain fallow, adds that varieties of plant develops towards specialized direction in recent years, objective On add the difficulty of the rotation of crops, catch cropping, crop rotation so that continuous cropping obstacles and the continuous cropping disease in a lot of areas are the most serious.This is main Show as soil-borne disease frequently to break out, such as bacterial wilt, root rot, damping-off, anthrax, clubroot, black stem, soft rot Deng, make agricultural production suffer the biggest loss.
Soil disinfection is to prevent and treat soil-borne disease and eliminate the important measures of continuous cropping obstacle, and adoptable method mainly has two classes: physics Method and chemical method.
Physical method mainly takes the high temperature of steam or flame generation to disinfecting soil, owing to energy consumption is the highest, and needs Special equipment, expense cost is high, the most simply uses in European countries.
Chemical method mainly uses chemical agent to eliminate the pathogenic bacteria in soil and root-knot nematode.Mainly use bromomethane (i.e. methyl Bromine), chloropicrin, vikane, methyl mustard oil, the chemical agent such as calcium cyanamide.Wherein, when methyl bromide fumigation agent is to use Between the longest, best one kind of Disinfection Effect, but owing to it has destruction to ozone layer.1992, bromomethane " was covered Paul Tellier protocol Copenhagen amendment " it is classified as controlled substance, it is stipulated that and developed country eliminated in 2005, developing country All eliminated in 2015.China has added the international convention of disabling bromomethane, will disable before the end of the year 2015 the most comprehensively Bromomethane.
For superseded methyl bromide, United Nations Environment Programme (UNEP) tissue various countries expert has set up that " methyl bromide substitute technology selects committee Member's meeting (MBTOC) ".The result that multiple succedaneum was estimated over many years by MBTOC is thought: up to now, there is no a kind of material Methyl bromide can be substituted completely, also do not have a kind of material can reach the application effect that methyl bromide is broad.International organization is still rousing at present Encourage various countries' practical situation according to oneself, actively find alternatives of methyl bromide and product.
The present inventor is intended to respond international community and advocates and country's ecological environmental protection needs, proposes a kind of soil disinfection respond well And the alternatives of methyl bromide of environmental sound and product.
Summary of the invention
The invention belongs to agricultural soil sterilization category, content includes a kind of soil sterilants and system thereof having fertilizer efficiency and activating nutrient Preparation Method.This disinfectant disappears to have the oxychloride agent strongly killing soil pathogenic bacteria and oxidative degradation soil harmful toxins as sterilization Poison component, uses sodium chlorite acidization reaction mechanism: when the pH value of sodium chlorite solution is less than 4, will be with certain speed Decompose and produce the chlorine dioxide that sterilizing performance is outstanding.It is the agricultural soil of plant growth in view of this disinfectant application, The present invention will have the organic acid of activating soil nutrient and per se with the acid compound of plant nutrient, swashing as sodium chlorite Agent alive.In order to make both the above component keep stable, prevent from occurring to early before use chemical reaction, in the disinfectant of the present invention With the addition of the stabilizer containing calcium and magnesium composition.
The preparation of this product comprises the following steps and main points:
1. material choice
A group raw material: sodium chlorite.Sodium chlorite, molecular formula: NaClO2;Molal weight: 90.44, is a kind of efficient oxidation Agent and bleach, be mainly used in linen-cotton association with pulp bleaching, food sterilization, water process, sterilization algae removal.The theory of sodium chlorite is effectively Chlorinity 157%, purity be more than 80% its available chlorine content of industrial goods also reach 130%, be equivalent to 7 times of bleaching powder.Heavier , in this product, it is as the presoma discharging the higher chlorine dioxide of disinfecting power.
B group raw material: organic acid and there is bisulfate or the acid phosphate of fertilizer character, specific as follows:
(1) citric acid, has another name called citric acid, molecular formula: C6H8O7, molal weight: 192.14, tricarboxylic classes of organic acids, have 3 Individual H+Can ionize, be the activator of sodium chlorite.Meanwhile, it also has the function of activating soil nutrient, is phosphorus and trace unit The activator of element, can prevent phosphorus fixation, and all have ferrum, manganese, zinc, copper metal ion good complexing and ion to protect Hold effect, the defect of the soil trace element active passivation that the Strong oxdiative disinfectant such as chlorine dioxide are caused can be overcome well.
(2) there is bisulfate and the acid phosphate of fertilizer character, specific as follows:
1. ammonium hydrogen sulfate: molecular formula is NH4HSO4, molal weight is 115.1, and nitrogen (N) content is 12.17%.
2. potassium acid sulfate: molecular formula is kHSO4, molal weight is 136.16, potassium (K2O) content is 34.57%.
3. potassium acid phosphate: molecular formula is KH5(PO4)2, molal weight is 234.07, and it is by 1 molecule phosphoric acid and 1 point The compound that sub-potassium dihydrogen phosphate combines, containing phosphorus potassium two kinds of nutrients, wherein phosphorus (P2O5) content is 43.8%, potassium (K2O) content It is 20%.
4. urea phosphate: molecular formula is CO (NH2)2·H3PO4, molal weight is 158.55, the complex of a kind of amino structure, nitrogen Content (N) is: 17.6%, phosphorus content (P2O5) it is 44.7%, it is the change combined by 1 molecule carbamide and 1 molecule phosphoric acid Compound.
Above-mentioned bisulfate and phosphate, all have stronger acids, can react with sodium chlorite, make sodium chlorite after meeting water Discharge chlorine dioxide, thus play effect of sterilizing.
C group raw material: containing the dry stabilizer of calcium and magnesium composition, specific as follows:
1. anhydrous calcium chloride, molecular formula: CaCl2, molal weight: 110.98, multiduty desiccant, have with sodium chlorite Good 5 joining property, can strengthen its stability.Meanwhile, when disinfectant uses, calcium chloride can also strengthen pathogen Cell wall Permeability, improves sterilizing effect.
2. anhydrous magnesium sulfate, molecular formula: MgSO4, molal weight: 120.36, neutral compound, have with fertilizer acid compound There are good 5 joining property, are excellent desiccant, the free moisture in material can be fixed into water of crystallization, thus keep material Drying property and stability.
2, raw material pre-treatment
A group and B group raw material are carried out vacuum drying treatment respectively at temperature not higher than 60 degrees Celsius, makes the free water in raw material Divide and be down to less than 2%.
3, material metering proportioning
The percentage by weight of C group material accounts for 10%, and wherein C group 1. material anhydrous calcium chloride and C group 2. material anhydrous magnesium sulfate are each Account for 5%.The percentage by weight of A group+B group material accounts for 90%, the wherein ratio between A group sodium chlorite and B group acidulant material, Calculate according to following chemical equation:
(1) sodium chlorite and citric acid, the reaction equation of ammonium hydrogen sulfate:
5NaCIO2+C6H8O7+2NH4HSO4→4CIO2+Na2HC6H5O7+(NH4)2SO4+Na2SO4+NaCl+2H2O
(2) sodium chlorite and citric acid, the reaction equation of potassium acid sulfate:
5NaCIO2+C6H8O7+2KHSO4→4CIO2+Na2HC6H5O7+K2SO4+Na2SO4+NaCl+2H2O
(3) sodium chlorite and citric acid, the reaction equation of potassium acid phosphate:
5NaClO2+C6H8O7+KH5(PO4)2→4ClO2+Na2HC6H5O7+KH2PO4+Na2HPO4+NaCl+2H2O
(4) sodium chlorite and citric acid, the reaction equation of urea phosphate:
5NaClO2+C6H8O7+H3PO4·CO(NH2)2→4ClO2+Na2HC6H5O7+Na2HPO4+CO(NH2)2+NaCl +2H2O
(5) sodium chlorite and citric acid, urea phosphate, the reaction equation of potassium acid phosphate:
15NaClO2+2C6H8O7+2H3PO4·CO(NH2)2+2KH5(PO4)2→12ClO2+2Na2HC6H5O7+4Na2HPO4 +2CO(NH2)2+2KH2PO43+NaCl+6H2O
Owing to properly increasing solution acidity, the reaction that can make sodium chlorite release chlorine dioxide is more complete, can also increase simultaneously Nutrient content and raising phosphorus and the activity of Trace Elements in Soil.Therefore, in practical operation, acidulant addition is than theoretical The suitable excess calculated, wherein citric acid is to be advisable more than 10%, and the amount of exceeding of other acidulant controls to be advisable 5%.
4, raw material mixing
Use low speed Agravicmixer, respectively by A group sodium chlorite material and powdered anhydrous calcium chloride, B group activator material Mix homogeneously with anhydrous magnesium sulfate, make whole material mix homogeneously the most again.
5, pack
Use the clad aluminum foil packaging material that barrier property is excellent, the material metering of above-mentioned mix homogeneously is packed.
Advantages of the present invention
1, there is good sterilizing effect.By above-mentioned chemical reaction, sodium chlorite can be made to discharge chlorine dioxide, and two Chlorine monoxid is the disinfectant more powerful than sodium chlorite sterilizing ability, and it is confirmed as efficiently by World Health Organization (WHO) (WHO), safety Nontoxic A1 level disinfectant.Chlorine dioxide is substantially a kind of strong oxidizer, and its sterilizing mechanism is: with strong oxidation, penetrate The cell protein of pathogenic microorganism, fat and nucleic acid etc. reach the function of deactivation, can effectively kill the cause of disease in soil Microorganism, and nematicide is also had good inhibiting effect.
2, the chlorine dioxide discharged in this disinfectant, with its strong oxidizing property, moreover it is possible to various harmful complexity in fast degradation soil Organic compound, serves purification and repair, thus eliminates the restraining factors to plant growing soil.To agricultural soil For earth, chlorine dioxide is a kind of dual-use function disinfectant with sterilizing and degraded soil poison.
The citric acid of the suitably excess 3, contained in this disinfectant, after reacting with sodium chlorite, reacts excess disodium citrate And free citric acid still has good complex activation effect, can continue the trace element in soil and phosphorus element are activated, Thus overcome class strong oxidizers such as chlorine dioxide to trace element activity such as produced zinc, ferrum, copper, manganese after soil disinfection The side effect declined, also can prevent phosphorus element by soil fixing so that the higher nutrient supply effectiveness of Soil conservation.
4, this disinfectant has good fertilizer efficiency function.Disinfectant reaction after, in remaining liquid in containing the most a high proportion of nitrogen, phosphorus, potassium, Sulfur, magnesium, these are all nutrients necessary to plant growing, are also the nutrient sources of soil beneficial microbe breeding.Therefore, This disinfectant, after carrying out soil disinfection, promptly can supplement nutrient to soil microorganism breeding and plant growing.
5, this disinfectant has preferable agronomy effect.This product, since within 2012, succeeding in developing, has compared for soil-borne disease Serious open country continuous cropping soil and plastic greenhouse soil, made to continue the field test of 3 years, and region relates to Guangxi, Yunnan, wide Several southern and northern provinces and regions, east, Zhejiang, Shanxi, Shandong, Shaanxi, Hebei, Beijing, Tianjin, Heilungkiang etc. ten, for studying thing Have Fructus Fragariae Ananssae, Citrullus vulgaris, Fructus Capsici, Fructus Lycopersici esculenti, Fructus Cucumidis sativi, Herba Apii graveolentis, Herba Alii fistulosi, Cucurbita pepo L., Rhizoma Zingiberis Recens, Oryza sativa L., Semen Maydis, Rhizoma Solani tuber osi, Twenties kinds of crops such as Fructus Solani melongenae, Fructus Musae, Citrus, Fructus Crataegi, Fructus Vitis viniferae, Nicotiana tabacum L..Test yields good result, its effect master It is reflected in: the soil-borne disease of (1) plastic greenhouse is effectively controlled.Common bacterial wilt, root rot, base rot disease, sudden The typical disease incidence of soil-borne disease such as disease, soft rot that falls is greatly reduced, and average fall is more than 70%.(2) company of open country Be eased as obstacle, common dead, the disease such as stiff Seedling, damping-off, epidemic disease, verticillium wilt averagely reduce more than 50%.Make After soil sterilants, plant growing way is substantially accelerated, robust plant.(3) Disinfection Effect ten sub-argument to nursery soil and substrate Think, especially to raising rice seedlings Seedling soil and Fructus Fragariae Ananssae seedling medium process after, in spite of illness rice shoot almost without.(4) sensitive to some continuous cropping Crop varieties, such as Citrullus vulgaris, Fructus Fragariae Ananssae, Fructus Solani melongenae, Fructus Lycopersici esculenti, Rhizoma Solani tuber osi etc., soil sterilants effect is especially notable, damping-off, The sickness rate such as anthrax, blight dis-ease, epidemic disease, clubroot averagely decline more than 60%, and root-knot nematode reproductive number is substantially pressed down System.
Accompanying drawing explanation
Accompanying drawing is this product processes flow chart.
Detailed description of the invention
Embodiment 1:
Prepare soil sterilants 1000 grams, technical specification (mass fraction, %): chlorine dioxide (ClO2) >=28%, ammonium nitrogen (N-NH4) >=2.5%, sulfur (S) >=8.5%, calcium (Ca) >=1.9%, magnesium (MgO) >=2.0%.Preparation process: first, weighs through being dried The commercial grade sodium chlorite 500 grams that purity is 80%, mix homogeneously with 40 grams of powdered anhydrous calcium chloride;Its two, then weigh Through the anhydrous citric acid 180 grams being dried and ammonium acid sulfate 220 grams, mix homogeneously with anhydrous magnesium sulfate 60 grams;Its three, After by whole material mix homogeneously, load clad aluminum foil packaging bag and seal.Using method: (1) takes packaging bag apart when using, will Material is poured in 100 times of clear water, is gently mixed dissolving with waddy, and standing and reacting generates yellow green mother solution after 30 minutes, the most again Mother solution and irrigation water are mixed with the ratio of 1: 20, waters and penetrate in soil.(2) disinfectant directly can also be sprinkled into soil Earth agrarian zone, then earthing is irrigated with water again.
Embodiment 2:
Prepare soil sterilants 1000 grams, technical specification (mass fraction, %): chlorine dioxide (ClO2) >=25%, potassium oxide (K2O) >=9.0%, sulfur (S) >=8.5%, calcium (Ca) >=1.9%, magnesium (MgO) >=2.0%.Preparation process: first, weighs through dry Purity is the commercial grade sodium chlorite 430 grams of 80%, mixs homogeneously with 40 grams of powdered anhydrous calcium chloride;Its two, then weigh through Cross the anhydrous citric acid 200 grams and potassium acid sulfate 270 grams being dried, mix homogeneously with anhydrous magnesium sulfate 60 grams;Its three, finally will All material mix homogeneously, load clad aluminum foil packaging bag and seal.Using method: same as in Example 1.
Embodiment 3:
Prepare soil sterilants 1000 grams, technical specification (mass fraction, %): chlorine dioxide (ClO2) >=28%, available phosphorus (P2O5) >=12.5%, potassium oxide (K2O) >=4.2%, calcium (Ca) >=1.9%, magnesium (MgO) >=2.0%.Preparation process: first, weigh through Cross the commercial grade sodium chlorite 500 grams that purity is 80% being dried, mix homogeneously with 40 grams of powdered anhydrous calcium chloride;Its two, Weigh again through dry anhydrous citric acid 180 grams and potassium acid phosphate 220 grams, mix homogeneously with anhydrous magnesium sulfate 60 grams;Its Three, finally by whole material mix homogeneously, load clad aluminum foil packaging bag and seal.Using method: same as in Example 1.
Embodiment 4:
Prepare soil sterilants 1000 grams, technical specification (mass fraction, %): chlorine dioxide (ClO2) >=30%, amidonitrogen (N-Urea) >=2.5%, available phosphorus (P2O5) >=6.5%, calcium (Ca) >=1.9%, magnesium (MgO) >=2.0%.Preparation process: first, Weigh through the commercial grade sodium chlorite 540 grams that dry purity is 80%, mix homogeneously with 40 grams of powdered anhydrous calcium chloride; Its two, then weigh through dry anhydrous citric acid 200 grams and urea phosphate 160 grams, mix homogeneously with anhydrous magnesium sulfate 60 grams; Its three, finally by whole material mix homogeneously, load clad aluminum foil packaging bag seal.Using method: same as in Example 1.
Embodiment 5:
Prepare soil sterilants 1000 grams, technical specification (mass fraction, %): chlorine dioxide (ClO2) >=29%, amide nitrogen (N-Urea) >=1.7%, available phosphorus (P2O5) >=13.1%, potassium oxide (K2O) >=2.9%, calcium (Ca) >=1.9%, magnesium (MgO) >=2.0%.Preparation Process: first, weighs through the commercial grade sodium chlorite 520 grams that dry purity is 80%, with powdered anhydrous calcium chloride 40 Gram mix homogeneously;Its two, then weigh through dry anhydrous citric acid 130 grams, urea phosphate 100 grams, potassium acid phosphate 150 Gram, mix homogeneously with anhydrous magnesium sulfate 60 grams;Its three, finally by whole material mix homogeneously, load clad aluminum foil packaging bag close Envelope.Using method: same as in Example 1.

Claims (6)

1. the present invention relates to a kind of soil sterilants with fertilizer efficiency and activation nutrient and preparation method thereof, its component includes three groups of things Material: A) sodium chlorite, it is the presoma producing chlorine dioxide;B) citric acid and acidic fertilizier compound (ammonium acid sulfate, Acid potassium sulfate, potassium acid phosphate and urea phosphate), they are the activators of sodium chlorite;C) anhydrous calcium chloride and magnesium sulfate, They are the stabilizers preventing front two groups of materials from adverse chemical reaction occurring after mixing;These materials are mixed through dried, metering Close, pack after, become a kind of have fertilizer efficiency and activation nutrient soil sterilants.
2., according to a kind of soil sterilants with fertilizer efficiency and activation nutrient described in right 1 and preparation method thereof, it is characterized in that: Its chance water reacts and discharges chlorine dioxide, plays soil sterilization sterilizing function, N P and K can also be provided a large amount of to plant simultaneously The trace element such as zinc-iron copper-manganese in element and calcium and magnesium sulfur moderate-element and activating soil.
3. according to a kind of soil sterilants with fertilizer efficiency and activation nutrient described in right 1 and preparation method thereof, it is characterised in that: Three class material ratios (mass percent, %) in this disinfectant are: the general proportion of A group material is 10-90%, preferably Proportion is 45-55%, and optimal proportion is 43%;The general proportion of B group material is 7-70%, and preferred proportion scope is 35-50%, optimal proportion is 47%;The general proportion of C group material is 1-30%, and preferred proportion scope is 5-15%, most preferably Ratio is 10%.
4. according to a kind of soil sterilants with fertilizer efficiency and activation nutrient described in right 1 and preparation method thereof, it is characterised in that: In B group material, citric acid with the ratio (mass percent, %) of acidic fertilizier compound is: the general ratio model of citric acid Enclosing is 10-90%, and preferred proportion scope is 33-67%, and optimal proportion is 33%;The general proportion of acid fertiliser compounds is 10-90%: preferred proportion scope is 33-67%, optimal proportion is 67%.
5. according to a kind of soil sterilants with fertilizer efficiency and activation nutrient described in right 1 and preparation method thereof, it is characterised in that: In C group material, the ratio (mass percent, %) of anhydrous calcium chloride and anhydrous magnesium sulfate is: anhydrous calcium chloride typically than Example scope is 10-90%: preferred proportion scope is 30-50%, and optimal proportion is 40%;The general proportion of anhydrous magnesium sulfate is 10-90%;Preferred proportion scope is 50-70%, and optimal proportion is 60%.
6. according to a kind of soil sterilants with fertilizer efficiency and activation nutrient described in right 1 and preparation method thereof, it is characterised in that: On the premise of satisfied performance disinfection function, the N P and K a great number of elements kind contained by disinfectant, can be according to farming needs Have different combinations, be achieved especially by selecting different acidic fertilizier compound in B group material: 1) ammonium acid sulfate, Single nitrogen (ammonium nitrogen) nutrient can be provided;2) acid potassium sulfate, it is possible to provide single potassium attainment is divided;3) potassium acid phosphate, Can provide phosphorus potassium two kinds of nutrients;4) urea phosphate, it is possible to provide two kinds of nutrients of nitrogen (amide nitrogen) phosphorus;5) ammonium acid sulfate+acid phosphorus Acid potassium, it is possible to provide three kinds of nutrients of nitrogen (ammonium nitrogen) phosphorus potassium;6) potassium acid phosphate+urea phosphate, it is possible to provide nitrogen (amide nitrogen) phosphorus Three kinds of nutrients of potassium.
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Application publication date: 20170111