CN1944352A - Process for producing boron magnesium phospho-ammonium fertilizer using boron mud - Google Patents
Process for producing boron magnesium phospho-ammonium fertilizer using boron mud Download PDFInfo
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Abstract
The process of producing boron-magnesium-phosphorus-ammonium fertilizer with boron mud includes the following steps: air drying and stoving boron mud to water content below 2 %; adding sulfuric acid solution to boron mud at 60-90 deg.c via stirring to form sulfate slurry; heating the sulfate slurry to 80-95 deg.c, adding phosphoric acid via stirring to reaction for 20-40 min, cooling to room temperature and curing to obtain phosphorus compound; crushing the phosphorus compound, adding ammonium bicarbonate and borax and pelletizing the mixture; and drying to obtain the product. The soluble compound fertilizer is suitable for various kinds of soil and various kinds of crop.
Description
Technical Field
The invention belongs to the technical field of agricultural compound fertilizers, and particularly relates to a process method for producing a boron-magnesium-phosphorus-ammonium fertilizer by using boric sludge.
Background
Boron sludge is the residual impurity in the production of boron products, and because the boron sludge contains alkaline (insoluble) elements such as boron, magnesium, calcium and the like, the boron sludge is subjected to chemical analysis, and the boron sludge mainly comprises the following components: contains soluble free alkali 4-5 wt%, magnesium carbonate and magnesium oxide 25-30 wt%, calcium carbonate and calcium oxide 12-13 wt%, boron 5-6 wt%, insoluble phosphorus 12-14 wt% and small amount of Fe, Zn, Mn and other elements. If the water is not pretreated and is directly scattered in soil after being stacked and lost, the water flows to the soil to harm green plants to wither, flows to a water area to harm organisms in water to destroy the ecological balance of water quality, causes diseases and even death after being drunk by people and livestock, also affects farmland irrigation, is extremely serious in harm and is a great public nuisance for polluting the whole environment. More than eighty percent of borax production enterprises in China are concentrated in Liaoning province of old industrial base in northeast, a large amount of boron mud is generated in the borax production process, the accumulation of the boron mud only in Liaoning county reaches 600 million tons, and the accumulation speed of the boron mud is increased gradually at the speed of dozens of million tons every year. Therefore, the problem of boron mud pollution is the first problem to be solved urgently in the areas of borax production enterprises. At present, many scientific institutions and enterprises successfully test some technological methods for utilizing boron mud, and the effect is mostly not ideal. Or secondary pollution phenomenon exists; or boron mud is not used as a main production raw material, so that the capacity of solving the pollution source is limited; or the production process is complicated, the production cost is too high, or the application range of the product is narrow. So mass production has not been established.
Through the component analysis and research of the boron mud, the boron mud contains a small amount of soda ash introduced in the production process, and other components are water-insoluble and are difficult to absorb by plants. Only by neutralizing the excessive sodium carbonate, other components become water-soluble and structure-soluble coexisting substances, and the plant fertilizer can be used. According to the existing form of chemical components, the requirements can be completely met through chemical reaction, and the technology is mature.
Disclosure of Invention
The invention aims to provide a process method for producing boron-magnesium-phosphorus-ammonium fertilizer by using boron mud as a carrier and trace elements in the boron mud as effective components.
The purpose of the invention is realized by the following steps:
(1) pretreatment of boric sludge
Firstly, naturally drying the boron mud to reduce the water content to below 10 percent, and then drying the boron mud at the temperature of 100-150 ℃ to reduce the water content to below 2 percent, thus finishing the pretreatment of the boron mud for later use;
(2) chemical composition adjustment in boron sludge
Diluting 500kg of concentrated sulfuric acid to 30-60%, heating to 60-90 ℃, slowly adding the concentrated sulfuric acid into pretreated 1150-plus 1500kg of boric sludge under continuous stirring, and maintaining the reaction temperature of 60-90 ℃ until no bubbles are generated to generate sulfate slurry for later use;
the chemical reaction formula is
(3) Phosphating treatment
Heating the sulfate slurry to 80-95 ℃, adding 300kg of 80-85% phosphoric acid, reacting under continuous stirring, maintaining the reaction temperature of 80-95 ℃, cooling to normal temperature after reacting for 20-40 minutes, and curing to obtain a phosphating reactant, wherein the pH value of the reactant is 3-4.5;
(4) boron nitride controlled granulation
Crushing the phosphating reactant, adding 1150-1500kg of ammonium bicarbonate, fully mixing the materials, and granulating the mixture, wherein the pH value of the mixture is 6.5-7.5; and then drying by hot air at 40-80 ℃ to finish the powder making process, thus obtaining the finished base fertilizer.
The invention also includes: adding 350-400kg of borax while adding ammonium bicarbonate, fully mixing, and then granulating.
The invention has the advantages that:
1. the product has low cost of raw materials, and boron mud is waste. The sulfuric acid and phosphoric acid used may be waste, (spent sulfuric acid, phosphoric acid sources have been addressed). The price of ammonium bicarbonate is also low. In addition, due to the humic acid, the soil softening is changed, the hardening is not pulled, the stress resistance is strong, and the utilization rate is high.
2. The present invention uses waste slag (boron mud) from borax production to convert insoluble elements of boron, magnesium, calcium, zinc, etc. into soluble substances, and thus, the present invention replaces the compound with single component of magnesium, calcium, zinc, etc. and is supplemented with high-quality nitrogen, phosphorus, potassium and humic acid, so that the present invention is a soluble fertilizer with normal effect and suitable for various crops and various soils. Is characterized in that: not only is a soluble quick-acting fertilizer, but also can keep the normal effect, and has the advantages of high utilization rate, wide application range, considerable yield increase amplitude and the like. The formed humic acid phosphorus and ammonium play roles of promoting nitrogen and protecting phosphorus without loss, crops can be required and absorbed at any time, the temperature of a soil layer can be increased by 2-3 ℃, and the humic acid phosphorus and ammonium have the function of loosening the soil; the nitrogen is protected by phosphorus, so that the loss and volatilization are not easy, the fertilizer efficiency is long, and the utilization rate is high. Potassium, calcium, magnesium, boron, zinc, iron and sulfur are trace elements required by crops, and the yield increasing effect is more obvious when the fertilizer is applied in a proper amount at proper time.
3. As for the innovation of the technology, the boron mud has large moisture, after the processes of air drying and drying, most of hydroxide and carbonate in the boron mud are decomposed, the proportion of magnesium oxide in the boron mud can reach up to 70 percent, and the treatment can provide an operable basis for the following procedures so as to obtain a physical and chemical state substance capable of being granulated.
4. The utilization rate of raw materials is high, the synthetic process is scientific and reasonable, and the sulfuric acid is used as a neutralizer for neutralizing the alkalinity of the boric sludge and also generates a restricted solubility magnesium fertilizer which can be absorbed by crops. Phosphoric acid is also dual-purpose, namely, the phosphoric acid is used as a neutralizing agent and generates a phosphate fertilizer which can be absorbed by crops. The ammonium bicarbonate can be used for supplementing nitrogen fertilizer while neutralizing the pH value of the product in the later reaction period.
5. The product has wide application and strong practicability, and can be used as a base fertilizer in areas lacking boron and magnesium soil in the south, and large-area areas of fruits and economic crops such as rapes, cottons, oranges, bananas and the like, and can supplement a large amount of elements such as nitrogen fertilizer and phosphorus fertilizer at one time while supplementing the boron and magnesium fertilizer. Greatly reduces the application amount of the original nitrogen fertilizer and phosphate fertilizer. Reduces the investment cost for farmers
6. The product has good derivation and the proportion of available nutrients can be randomly blended according to soil rationality of different regions and fertilizer requirement characteristics of different crops. On the basis, the major, middle and trace elements can be mixed to achieve the best use effect.
The boron-magnesium-phosphorus-ammonium fertilizer of the invention is characterized by also comprising the following components:
the present invention relates to a multi-element compound fertilizer, which is characterized by that the beneficial components in boron mud are reacted by sulfuric acid and phosphoric acid to make the reaction product be soluble compound fertilizer, then the soluble compound fertilizer is mixed with ammonium hydrogen carbonate, borax and water, granulated, dried and covered with slurry so as to obtain the invented product. The invention uses boric sludge to be treated by sulfuric acid and phosphoric acid, so that the component elements of the boric sludge are changed into the fertilizer which can be directly absorbed by plants, thereby fundamentally replacing single fertilizer, and the fertilizer is suitable for various plants and various soils.
The invention also has the advantages of simple and safe whole conversion process, no waste liquid discharge and no secondary pollution phenomenon.
The main properties and effects of the essential nutrients for general crops are summarized as follows:
① N, nitrogen is the main element constituting protein which is the basic substance in cell biomass composition, N is the main component of chlorophyll, enzyme (biocatalyst), nucleic acid, vitamin, biological fiber, etc.;
② P, phosphorus is a constituent of nucleic acids and nucleotides, which is a major component of protoplasm and cell nucleus, and nucleotides and derivatives thereof are participants in organic substance conversion and energy conversion in crops;
③ K, potassium can regulate the colloid state of protoplasm and improve the intensity of photosynthesis, has close relation with the transportation formed by saccharides in crops, and has good influence on the nitrogen metabolism of the crops;
④ Ca, calcium has certain effect on metabolism of carbohydrate and nitrogen-containing substances in crops, and can eliminate toxic action of ions (such as ammonium, hydrogen, aluminum, and sodium) on crops, and calcium is mainly in the form of calcium pectate and exists in the middle layer of cell wall, and can enhance resistance of crops to diseases and insect pests;
⑤ Mg,magnesium is a component of chlorophyll and phytate (storage form of phosphoric acid), and can promote the activation of phosphatase and glucose convertase, and is extremely beneficial to the conversion of monosaccharide, thus playing an important role in carbohydrate metabolism;
⑥ B, boron has certain effects on the growth of root, stem and other organs, the development of young meristems and the flowering and fructification of crops, can accelerate the transportation of carbohydrates in crops, promote the metabolism of nitrogen elements in crops, enhance the photosynthesis of crops, improve the supply and distribution of organic matters in crops, enhance the activity of rhizobia of bean crops, improve the nitrogen fixation capacity and improve the disease resistance of crops;
Detailed Description
The present invention will be further illustrated by the following examples, which are merely exemplary of the present invention and are not intended to limit the scope of the invention. The scope of the claims shall be governed by the claims.
Example 1
(1) Pretreatment of boric sludge
Naturally drying the newly-obtained boric sludge to reduce the water content to below 10%, and then drying at the temperature of 120-150 ℃ to reduce the water content to below 2%, thus finishing the pretreatment of the boric sludge for later use.
(2) Chemical composition adjustment in boron sludge
Diluting 500kg of 92.5% sulfuric acid to 30%, heating to 75-85 ℃, slowly adding 1250kg of pretreated boric sludge under continuous stirring, maintaining the reaction temperature of 75-85 ℃ until no bubbles are generated, and converting most calcium carbonate into calcium sulfate in about 15 minutes to generate sulfate slurry for later use.
The chemical reaction formula is
(3) Phosphating treatment
Heating the slurry treated by the sulfuric acid to 80-95 ℃, adding 300kg of 85% phosphoric acid, reacting under continuous stirring, maintaining the reaction temperature at 80-95 ℃, reacting for 30 minutes, cooling and curing to obtain a phosphating reactant, wherein the pH value of the reactant is 3.2-3.5.
(4) Boron nitride controlled granulation
And crushing the phosphating reactant, adding 1250kg of ammonium bicarbonate, and fully mixing until the pH value is 6.9-7.1, thus obtaining the base fertilizer. Adding 375kg of borax for fully mixing according to the requirement, and then granulating; drying by hot air at 60 ℃ to finish the powder making process, thus obtaining the finished product of the special fertilizer.
Four, boron magnesium phosphor ammonium fertilizer process manufacturing weight part ratio
0.4 portion of 92.5 percent sulfuric acid
(II) 85% phosphoric acid 0.25 part
1 part of (III) boron mud (after treatment)
Ammonium bicarbonate 1 part
(V) 0.3 part of borax
Fifthly, the component proportion of the finished product boron-magnesium-phosphorus-ammonium fertilizer
Nitrogen (% N) 5.8
Phosphorus (P)2O5) % 5.1
8.1% of magnesium (Mg)
Boron (B)% 1.1
The results of rape tests using the above products are detailed in Table 1
TABLE 1
In addition, compared with the conventional fertilizer, the invention is applied to the tobacco producing area, and shows that the stem circumference is increased by 0.05-0.13cm, the leaf number is increased by 0.5, the pitch is shortened by 0.23-0.27cm, the waist leaf is increased by 1-2cm, and the width is increased by 1-1.6 cm. The dry smoke rate is increased by 1.1-1.3%, and the yield per mu is increased by 3.3-8.8%. The first-class smoke proportion is improved by 36.9-55.9%.
Example 2
100 kg of the base fertilizer is taken, 70 kg of urea and 30 kg of potassium sulfate are added and mixed. The obtained compound fertilizer has the proportion of nitrogen, phosphorus, potassium, magnesium and boron of 4: 1: 2: 0.5: 0.1, and is a special fertilizer for fruit trees and vegetables in the vegetative growth period. The product is characterized by quick effect. Emphasizes the supply of nitrogen and balances phosphorus, potassium and trace elements.
Example 3
100 kg of the base fertilizer is taken, 85 kg of potassium sulfate and 15 kg of potassium hydrogen are added and mixed. The compound fertilizer with the ratio of nitrogen, phosphorus, potassium, magnesium and boron of 1: 1.2: 3.1: 0.5: 1 can be obtained, the demand of potassium during fruit expansion can be met, the sweetness of the fruit is increased, and the coloring is improved. Meanwhile, the synergistic effect of high potassium and magnesium can strengthen the physique of crops and increase the cold resistance, drought resistance and disease resistance.
Example 4
100 kg of the base fertilizer is taken, and 50kg of potassium sulfate, 10 kg of ferrous sulfate, 10 kg of zinc sulfate, 10 kg of calcium silicate powder, 10 kg of ammonium molybdate and 10 kg of manganese sulfate are added. Can obtain a compound full-element fertilizer containing large, medium and trace elements, and can balance the nutrients necessary for crops.
Claims (4)
1. A process method for producing a boron-magnesium-phosphorus-ammonium fertilizer by using boric sludge is characterized by comprising the following steps:
(1) pretreatment of boric sludge
Firstly, naturally drying the boron mud to reduce the water content to below 10 percent, and then drying the boron mud at the temperature of 100-150 ℃ to reduce the water content to below 2 percent, thus finishing the pretreatment of the boron mud for later use;
(2) chemical composition adjustment in boron sludge
Diluting 500kg of concentrated sulfuric acid to 30-60%, heating to 60-90 ℃, slowly adding the concentrated sulfuric acid into pretreated 1150-plus 1500kg of boric sludge under continuous stirring, and maintaining the reaction temperature of 60-90 ℃ until no bubbles are generated to generate sulfate slurry for later use;
the chemical reaction formula is
(3) Phosphating treatment
Heating the sulfate slurry to 80-95 ℃, adding 300kg of 80-85% phosphoric acid, reacting under continuous stirring, maintaining the reaction temperature of 80-95 ℃, cooling to normal temperature after reacting for 20-40 minutes, and curing to obtain a phosphating reactant, wherein the pH value of the reactant is 3-4.5;
(4) boron nitride controlled granulation
Crushing the phosphating reactant, adding 1150-1500kg of ammonium bicarbonate, fully mixing the materials, and granulating the mixture, wherein the pH value of the mixture is 6.5-7.5; and then drying by hot air at 40-80 ℃ to finish the powder making process, thus obtaining the finished base fertilizer.
2. The process method for producing the boron-magnesium-phosphorus-ammonium fertilizer by using the boric sludge as claimed in claim 1, which is characterized in that: adding 350-400kg of borax while adding ammonium bicarbonate, fully mixing, and then granulating.
3. The process method for producing the boron-magnesium-phosphorus-ammonium fertilizer by using the boric sludge as claimed in claim 1, which is characterized in that: (1) pretreatment of boric sludge
Firstly, naturally drying the boric sludge to reduce the water content to below 10 percent, and then drying the boric sludge at the temperature of 120-150 ℃ to reduce the water content to below 2 percent, thus finishing the pretreatment of the boric sludge for later use;
(2) chemical composition adjustment in boron sludge
Diluting 500kg of 92.5% concentrated sulfuric acid to 30%, heating to 75-85 ℃, slowly adding the diluted concentrated sulfuric acid to1250kg of pretreated boric sludge under continuous stirring, and maintaining the reaction temperature of 75-85 ℃ until no bubbles are generated to generate sulfate slurry for later use;
the chemical reaction formula is
(3) Phosphating treatment
Heating the sulfate slurry to 80-95 ℃, adding 300kg of 85% phosphoric acid, reacting under continuous stirring, maintaining the reaction temperature of 80-95 ℃, cooling to normal temperature after reacting for 30 minutes, and curing to obtain a phosphating reactant, wherein the pH value of the reactant is 3.2-3.5;
(4) boron nitride controlled granulation
Crushing the phosphating reactant, adding 1250kg of ammonium bicarbonate, fully mixing the materials, and granulating the mixture, wherein the pH value of the mixture is 6.9-7.1; then drying by hot air at 60 ℃ to finish the powdering process, thus obtaining the finished product.
4. The process method for producing the boron-magnesium-phosphorus-ammonium fertilizer by using the boric sludge as claimed in claim 3, which is characterized in that: then 375kg of borax was added for thorough mixing while adding ammonium bicarbonate, and then granulation was performed.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105418201A (en) * | 2016-01-08 | 2016-03-23 | 金玛(宽甸)肥业有限公司 | Drying-free preparing technology adopting particle boric magnesium fertilizer acid method |
CN108911797A (en) * | 2018-08-17 | 2018-11-30 | 营口菱镁化工集团有限公司 | A kind of ascharite fertilizer and preparation method thereof |
CN110078538A (en) * | 2019-04-16 | 2019-08-02 | 大连地拓环境科技有限公司 | A kind of comprehensive utilization tailing prepares silico-calcium potassium magnesium slow-release fertilizer and preparation method thereof |
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CN1136170C (en) * | 2000-08-29 | 2004-01-28 | 罗景泉 | High-effective multi-element complex mixed fertilizer |
CN1216832C (en) * | 2002-08-23 | 2005-08-31 | 丹东鑫阳矿业有限公司 | Method for producing borium and magnesium fertilizer by using boric sludge |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105418201A (en) * | 2016-01-08 | 2016-03-23 | 金玛(宽甸)肥业有限公司 | Drying-free preparing technology adopting particle boric magnesium fertilizer acid method |
CN108911797A (en) * | 2018-08-17 | 2018-11-30 | 营口菱镁化工集团有限公司 | A kind of ascharite fertilizer and preparation method thereof |
CN110078538A (en) * | 2019-04-16 | 2019-08-02 | 大连地拓环境科技有限公司 | A kind of comprehensive utilization tailing prepares silico-calcium potassium magnesium slow-release fertilizer and preparation method thereof |
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