CN1201661C - Copper-bearing sepiolite, palygorskite solid and suspension liquid fungicide and its preparation method - Google Patents

Abstract

The present invention discloses copper bearing sepiolite and palygorskite as a solid and suspension liquid fungicide and a preparation method thereof. The fungicide is magnesite and paligorskite containing exchangeable copper ions, wherein the content of copper as an element in the magnesite and paligorskite is from 0.5 to 6.5% according to percentage by weight. The preparation method of the fungicide comprises: utilizing the ion exchange capacity of clay minerals to implant Cu<2+> with the capacity of killing bacteria and fungi in magnesite and paligorskite crystal lattices to obtain copper bearing magnesite and paligorskite containing active copper ions; drying and grinding or spray-drying the copper bearing magnesite and paligorskite containing active copper ions to obtain solid powder or a suspension liquid agent. The method has the advantages of simple technological process, low production cost and easy popularization and application. The fungicide prepared by the method of the present invention can be widely applied to the environment, common facilities and commodities for disinfection and antisepsis processing, can be used as a feed additive for preventing and controlling infectious diseases of digestive tracts of animals, can be used as an antisepsis filling material in industries of plastics, paper, cosmetics, textiles, etc., can be used for preparing antisepsis paint and antisepsis membrane, etc.

Description

Copper-loaded sepiolite, palygorskite bactericide and preparation method thereof

Technical field

The invention relates to a fungicide for copper-loaded sepiolite and palygorskite and a preparation method thereof.

Background technique

Copper-based fungicides and fungicides have been widely used in agriculture, aquaculture and other fields. Compared with organic synthetic bactericides and fungicides, copper inorganic compounds have the advantages of high safety, wide antibacterial range, and long validity period, such as copper sulfate and copper hydroxide. However, in application, direct use of copper-containing compounds consumes a large amount of copper, which is not conducive to reducing production costs. In addition, excessive copper may remain in the soil and cause environmental pollution.

Therefore, objectively need a kind of preparation method of new copper-based bactericide/fungicide. Compared with traditional products, the biological activity and duration of action of such preparations should be significantly improved, and should have lower production costs. The copper content in the preparations should be significantly lower than traditional products, so as to be beneficial to environmental protection. The present invention is developed at this objective requirement.

Contents of Invention

The object of the present invention is to provide a kind of copper-loaded sepiolite, palygorskite fungicide and preparation method thereof.

The bactericide is sepiolite and palygorskite containing exchangeable copper ions, and the content of copper element in the sepiolite and palygorskite is 0.5-6.5% by weight percentage.

The steps of preparation method are as follows:

1) Add water to the separated and purified natural sepiolite and palygorskite to prepare a slurry with a concentration of 8-12%;

2) Slowly add industrial hydrochloric acid or industrial sulfuric acid, and keep stirring to stabilize the pH value of the pulp at 2.0-3.0, and continue stirring for about 3-5 hours;

3) After centrifugation or filtration dehydration, wash with water 2-3 times;

4) Add copper salt with a copper content equivalent to 2-10% of the ore weight, or its hydrous crystal salt, add water to make a slurry with a concentration of about 10%, and stir the ion exchange reaction time for not less than ten hours. Stir from time to time;

5) After centrifugation or filtration dehydration, wash 1-2 times and dehydrate again;

6) The product obtained in step 5) is naturally cooled and dried, or dried at a temperature lower than 90°C, and ground to a size of less than 300 mesh to obtain a powder with a water content of less than 10%, which is then used;

Or: add no more than 5% dispersant to the resulting product in step 5, add water and stir to make 10-30% ore slurry, and dry it with spray drying equipment. The temperature at the discharge port does not exceed 90°C, and the powder with a water content of less than 10% is obtained for use;

Or: add no more than 5% dispersant to the obtained product in step 5), add water and stir, and prepare a suspension for use.

The said sepiolite and palygorskite are both magnesium silicate minerals with layered chain structure, and they are produced in the form of clay, mudstone, shale or loose massive ore in nature.

Said copper salt is copper sulfate, copper chloride, copper nitrate.

The dispersant is one or more of sodium triphosphate, tetrasodium pyrophosphate and sodium lignosulfonate.

The advantages of the present invention are:

1) Using the cation exchange capacity of natural sepiolite and palygorskite to carry copper ions, the production cost is low;

2) The content of copper element in fungicides and fungicides is low, which reduces the environmental residues;

3) The slow-release ability of sepiolite and palygorskite makes the product bactericidal and fungicidal for a long time;

4) It is safe to use and has a wide range of applications.

Detailed ways

The raw materials used in the present invention are separated and purified natural sepiolite and palygorskite, wherein the palygorskite is sometimes called attapulgite. The purification technology of sepiolite and palygorskite is well known, and it includes steps such as crushing, beating to make a suspension, and classifying and collecting particles smaller than 2-5μ. This highly purified sepiolite and palygorskite are light green, light yellow clay minerals with layered chain crystal structure. Conventional mining equipment can be used in the separation and purification process.

The acid treatment of sepiolite and palygorskite can remove the carbonate impurities contained in the raw materials on the one hand; The lattice is activated, that is, the interlayer positions are open to foreign cations. Note that the used acid liquid must be neutralized before discharge to avoid polluting the environment.

The copper loading reaction is essentially an ion replacement reaction in which copper ions in the solution replace interlayer cations in sepiolite and palygorskite lattices. The copper salts used are copper sulfate, copper chloride, and copper nitrate. The requirements for the amount of copper salt used are not very strict. Generally speaking, the content of copper element in the copper salt is not less than 2.5% of the dry weight of sepiolite and palygorskite.

In the production process of the present invention, the requirements for the amount of water added in the relevant steps are not very strict. Under the premise that the equipment such as stirring, mixing and spray drying can operate normally, water should be reduced as much as possible to reduce production costs. Conventional equipment can be used for stirring and mixing, and the time limit for mixing is suitable for forming an apparently uniform slurry.

Dispersants suitable for use in the present invention are not critical. The recommended dispersant is one or more of sodium triphosphate, tetrasodium pyrophosphate and sodium lignosulfonate. The purpose of adding a dispersant is to reduce the viscosity of the slurry, making it possible to spray dry the high-concentration slurry, thereby reducing the drying energy consumption; in addition, the dispersant can increase the stability of the suspension and delay its precipitation.

The sepiolite and palygorskite after copper loading can be dried by conventional drying methods, and the drying temperature should not exceed 80°C; they can also be dried in the sun in a dry climate, and then ground to a particle size of no more than 300 mesh.

The slurry is preferably dried with spray drying equipment. The air inlet temperature of the spray dryer is controlled within the range of 120-250°C, and the outlet temperature does not exceed 90°C. The spray-dried product is a free-flowing solid powder. The spray drying equipment used in the present invention is conventional and well known in the art.

The preparation of the present invention has two types, solid powder with water content less than 10%, and suspension containing dispersant. The copper content of the solid powder preparation is generally between 2% and 3%. In the suspension, the content of copper-loaded sepiolite and palygorskite should be controlled between 10% and 20%.

The use concentration suggestion of preparation of the present invention in different application fields is as follows:

1) Used as an environmental disinfectant. The preparation of the invention is diluted with water, prepared into a suspension containing 0.05% to 0.15% of copper-loaded sepiolite and palygorskite, and evenly sprayed on walls, floors and surfaces to be disinfected.

2) Control bacterial and fungal diseases of crops. The preparation of the invention is formulated into a suspension containing 0.1-0.2% of copper-loaded sepiolite and palygorskite, and is evenly sprayed on plants to be protected. It can prevent bacterial and fungal diseases of food crops, oil crops, economic crops, vegetables, fruits, flowers, medicinal plants and various forest trees.

3) Used as an animal feed additive. The solid powder preparation is used, and the dosage of 0.8-4 kg per ton of feed is used to add the preparation of the present invention into the feed and stir evenly. It can effectively prevent and treat animal digestive tract diseases caused by various pathogenic bacteria.

4) In neutral and weakly acidic water-based paints and water-based cosmetics, the preparation of the present invention is added at a concentration of 0.02% to 0.2%, and the product has obvious antibacterial and antifungal effects. In weakly alkaline water-based paints, the recommended concentration is 0.1% to 0.5%.

5) Used as antibacterial and antifungal additives for paper and textiles. For neutral and weakly acidic media, the recommended dosage is 0.05% to 0.2%; for weakly alkaline media, the recommended dosage is 0.1% to 0.3%.

6) Used as an antibacterial and antifungal additive for plastic materials and hydrophobic coatings. Use solid powder preparation, the recommended dosage is 0.5% to 5%. Before use, one of the coupling agents of silane, titanate and aluminate should be selected to coat the surface of the preparation of the present invention. Surface coating techniques are well known commercially.

Embodiment 1: Preparation of granular copper-loaded palygorskite fungicide and fungicide

1.1 Palygorskite lump ore in a certain place has a purity of about 90% after separation and purification, and the main impurities are carbonates. Weigh 100g of purified ore, add 900ml of water, and stir evenly to make a suspension.

1.2 Add 40 ml of industrial hydrochloric acid, and keep stirring during this period. After half an hour, the measured pH value is 2.0, and continue stirring for about 3 hours.

1.3 Centrifuge the sediment, pour off the supernatant. Add 900ml of water, stir evenly, centrifuge to precipitate, and pour off the supernatant. Repeat 1-2 times. Reconstitute the suspension to a volume of one liter.

1.4 Add 9 grams of CuSO ₄ ·5H ₂ O, stir well, and conduct ion exchange reaction for 10 hours, stirring from time to time.

1.5 Centrifuge the sediment, pour off the supernatant. Add 900ml of water, stir evenly, centrifuge to precipitate, and pour off the supernatant.

1.6 Centrifuge the sediment, pour off the supernatant. Add 900ml of water, stir evenly, centrifuge to precipitate, and pour off the supernatant.

1.7 Add 5 grams of sodium triphosphate, add 300 ml of water, stir well to make the mixture even, and spray dry under the condition that the inlet air temperature does not exceed 250°C to obtain a powder with a water content of less than 10%, which is ready for use.

The copper-loaded sepiolite, palygorskite fungicide and fungicide prepared by the above steps have a copper element content of 2.1%.

Example 2: Preparation of Suspended Liquid Copper-loaded Sepiolite Bactericide and Fungicide

2.1 Sepiolite shale in a certain place, after separation and purification, the sepiolite content is about 90%, and the impurities are mainly other clay minerals. Weigh 100g of purified ore, add 900ml of water, and stir evenly to make a suspension.

2.2 Add 20 ml of industrial sulfuric acid, and keep stirring during the period. After half an hour, the measured pH value is 2.0, and continue stirring for about 3 hours.

2.3 Centrifuge the sediment, pour off the supernatant. Add 900ml of water, stir evenly, centrifuge to precipitate, and pour off the supernatant. Repeat 1-2 times. Reconstitute the suspension to a volume of one liter.

2.4 Add 6 grams of CuCl ₂ , stir well, ion exchange reaction for 10 hours, stirring from time to time.

2.5 Centrifuge the sediment, pour off the supernatant. Add 900ml of water, stir evenly, centrifuge to precipitate, and pour off the supernatant.

2.6 Add 5 grams of tetrasodium pyrophosphate, add 400 ml of water, stir well to make the mixture even, and set aside.

Embodiment 3: the antibacterial performance of copper-loaded palygorskite

3.1 Strains

Escherichia coli, Staphylococcus aureus (provided by Zhejiang Institute of Microbiology)

3.2 Microbial culture experiment

Bacteria overnight culture: Bacteria were cultured overnight (about 12 hours) under aerobic conditions at a temperature of 37°C. The culture medium was washed twice by centrifugation (10,000 rpm), rinsed with distilled water to make a suspension, and the bacterial content was 10 ⁴ / ml～10 ⁵ /ml.

Add 0, 1, 2.5, 5, 10 and 20 mg of copper-loaded palygorskite prepared according to the method of Example 1 into 100 ml of distilled water, vibrate to mix evenly, then vibrate and cultivate for 24 hours at a temperature of 37°C.

Growth analysis: After 0, 2, 4, 6 and 24 hours respectively, take 0.1ml of the solution from the above mixture, dilute to a certain concentration, and culture on the plate for 24 hours at a temperature of 37°C. Plate counts were then performed. Each sample was counted in three parallel cultures, and the average value was taken.

3.3 Bactericidal effect (see Table 1 and Table 2)

The first row of Table 1 and Table 2 is the weight of copper-loaded palygorskite added per 100 ml (10 ⁴ to 10 ⁵ bacteria/ml) of distilled water, and the first column is the incubation time after adding copper-loaded palygorskite , and the rest are the statistical results of plate culture counts (the average value of three parallel samples).

Table 1: Counting results of Escherichia coli in the culture medium (unit/ml) 0mg 1mg 2.5mg 5mg 10mg 20mg 0h 9.2×10 ⁴ 8.35×10 ⁴ 8.35×10 ⁴ 8.35×10 ⁴ 8.35×10 ⁴ 8.35×10 ⁴ 2 hours 9.4×10 ⁴ 5.6×10 ⁴ 3.6×10 ⁴ 2.5×10 ⁴ 6.3×10 ³ 0 4h 8.9×10 ⁴ 1.9×10 ⁴ 8.7×10 ³ 4.7×10 ² 1.5×10 ² 0 6 hours 8.4×10 ⁴ 7.5×10 ² 5.1×10 ² 0 0 0 24h 8.3×10 ⁴ 0 0 0 0 0

Table 2: Counting results of Staphylococcus aureus in the culture medium (unit/ml) 0mg 1mg 2.5mg 5mg 10mg 20mg 0h 1.19×10 ⁵ 1.19×10 ⁵ 1.19×10 ⁵ 1.19×10 ⁵ 1.19×10 ⁵ 1.19×10 ⁵ 2 hours 9.6×10 ⁴ 9.1×10 ⁴ 5.8×10 ⁴ 9.3×10 ³ 8.5×10 ² 0 4h 9.4×10 ⁴ 1.7×10 ⁴ 6.2×10 ³ 3.8×10 ² 0 0 6 hours 6.5×10 ⁴ 8.6×10 ² 4.8×10 ² 0 0 0 24h 6.1×10 ⁴ 0 0 0 0 0

The experimental results show that the copper-loaded palygorskite has a strong ability to kill both Gram-negative bacteria (Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus). When 20mg of copper-loaded sepiolite and palygorskite (concentration: 200mg/L) are used in 100ml of water, these two types of bacteria can be completely killed within 2 hours.

The invention provides a bactericide, a fungicide and a preparation method thereof, which take copper-loaded sepiolite and palygorskite as active components. The invention involves rich sources of raw materials, simple preparation process, low production cost and easy popularization and implementation. The bactericide and fungicide prepared based on the present invention can be widely used in disinfection and antibacterial treatment of environment, public facilities and daily necessities, feed additives for prevention and control of animal digestive tract infectious diseases, and in industries such as plastics, paper, cosmetics and textiles. Preparation of antibacterial fillers, antibacterial coatings and antibacterial films, etc.

Claims (4)

1. a copper-loaded sepiolite, palygorskite bactericide is characterized in that it is a kind of sepiolite, palygorskite that contains commutative copper ion, and by weight percentage, the content of copper in sepiolite, palygorskite is 0.5～6.5%.

2. the preparation method of a copper-loaded sepiolite, palygorskite bactericide is characterized in that its step is as follows:

1) through separating natural sepiolite, the palygorskite of purifying, adds the ore pulp that water is modulated into concentration 8-12%;

2) slowly add technical hydrochloric acid or industrial sulphuric acid, do not stop to stir, the pH value stabilization that makes ore pulp continued stir about 3-5 hour at 2.0-3.0;

3) behind the centrifugal or filtering means dehydration, water cleans 2-3 time;

4) add the mantoquita that copper content is equivalent to ore weight 2-10%, or its water-containing crystal salt, add the ore pulp that water is made concentration about 10% again, the back ion-exchange reactions time that stirs is no less than ten hours, during stir frequently;

5) behind the centrifugal or filtering means dehydration, clean 1-2 time, and dehydration again;

6) the step 5) gains are cool naturally shines dryly, or dries being lower than under 90 ℃ of temperature, is ground to less than 300 orders, obtains water content less than 10% powder, stand-by;

Perhaps: the step 5) gains add maximum 5% dispersant, adding water stirs, make the ore pulp of 10-30%, carry out drying with spray drying device, the spray dryer EAT should be controlled at 120～250 ℃ of scopes, the discharging opening temperature is no more than 90 ℃, obtains water content less than 10% powder, and is stand-by;

Perhaps: the adding of step 5) gains is no more than 5% dispersant, adds water and stirs, and it is stand-by to make suspension.

3. a kind of copper-loaded sepiolite according to claim 1, palygorskite bactericide, it is characterized in that, said sepiolite and palygorskite are the magnesium silicate mineral with layer chain structure, and they are clay, mud stone, shale or loose massive ore in natural output form.

4. the preparation method of a kind of copper-loaded sepiolite according to claim 2, palygorskite bactericide is characterized in that said mantoquita is copper sulphate, copper chloride, copper nitrate.