JPS6046070B2 - Manufacturing method of chemical compound fertilizer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention applies to artificial or naturally occurring inorganic compound minerals containing iron, aluminum, calcium, magnesium, silica, etc. as main components, so-called organic materials such as animal and plant waste from cities, agriculture, forestry and fisheries, etc. The present invention relates to a method for producing chemical compound fertilizers using fertilizers, and in particular to saving heat energy used in production.

Examples of inorganic compound minerals whose main components are iron, aluminum, calcium, magnesium, and silica include coal ash discharged from coal-fired power plants, which are well known as man-made materials, and various slag discharged from the steel industry. There are also naturally occurring substances such as serpentinite, volcanic rock, potassium feldspar, ma,
I'm in charge of my job.

All of these coals are unused due to their low content of active ingredients; for example, only a portion of coal ash slag is used as a raw material for cement concrete and artificial aggregate for civil engineering and construction. Most of them are subject to disposal. As a result, it is currently difficult to secure a dumping site. In addition, cities, agriculture, forestry and fisheries industries also discharge large amounts of various organic substances from animals and plants, and these are also in the same situation as the mineral substances mentioned above. Therefore, in recent years, these unused resources have been converted into inexpensive chemical compound fertilizers to overcome the predicament in mining, industry, agriculture, forestry, and fisheries, etc., and at the same time, to lower the cost of agricultural products and to provide common fertilizers for mining, industry, etc. and agriculture. Ideas have been proposed to bring about the benefits of the invention, and some products, such as those made by the present inventor, have already been put into practical use. However, the conventional method requires a large amount of thermal energy during production because it uses a firing method, and it is not only disadvantageous in terms of resource conservation, but also increases in price, making it unsatisfactory. J Therefore, the present inventor conducted various research and proposed a chemical compound fertilizer characterized by the following wet manufacturing method, which does not require heat treatment like the baking method (for example, Japanese Patent Application No. 55-86097 (■ Japanese Patent Application Publication No. 5
7-11892), Japanese Patent Application No. 55-106753 (■ Japanese Patent Application Publication No. 57-38389), Japanese Patent Application No. 55-10675
No. 4 (see Japanese Unexamined Patent Publication No. 57-38390). In this method, a large amount of water is discharged together with gypsum in the process of making phosphoric acid by reacting sulfuric acid with phosphate rock on an inorganic compound mineral material such as the coal ash mentioned above, or a mixture thereof mixed with an organic material. By adding a low-concentration phosphoric acid mixture such as a phosphoric acid solution, even substances that are extremely stable under natural conditions are easily decomposed and phosphorylated to produce gel sols such as phosphates and silicon phosphates. Then, supplementary fertilizer ingredients such as chlorides such as potassium chloride and ammonium chloride, sulfates such as ammonium sulfate and calcium sulfate, magnesium, urea, etc. are mixed with this to take advantage of the self-condensing and solidifying granulation properties of the phosphate gel sol. The aim is to create a chemical compound fertilizer using waste, which is granulated and solidified to contain the necessary fertilizer components such as inorganic compounds, added phosphoric acid, and supplementary fertilizer components. In addition, when chloride is used as a supplementary fertilizer component in this method, as in the concurrent application, the hydrochloric acid can be separated by azeotropically drying the phosphate and silicophosphate gel sol by heating the resulting mixture of hydrochloric acid and hydrogen. It is possible to produce a chemical compound fertilizer with less chlorine content.
Furthermore, by mixing urea into the gel sol and then reacting it with acetaldehyde or the like, a highly slow-release chemical compound fertilizer can be produced. According to this method, the required thermal energy may be sufficient to promote granulation and solidification.

In addition, the fertilizer components are incorporated and solidified in the gel-sol, and the solidification of granulation using the gel-sol is different from the conventional mixing method, and the direct manufacturing method, which is the method used to make fertilizers using granulating materials. It's better than that. It also has low absorption and solubility. Therefore, it is less soluble and slow-acting compared to conventional products. This makes it more economical by reducing the loss of fertilizer components due to runoff, and at the same time reduces the number of times and labor required for fertilization, and there is less risk of water pollution or concentration disturbances! Fertilizers with various advantages can be provided. However, a drawback of this method is that the phosphoric acid mixture at a low concentration used for producing phosphate and silicophosphate gel sol requires a large volume, which is inconvenient for transportation.

In addition, because the chemical activation energy is small, the reaction takes time and the production process takes time, and there is the disadvantage that drying and solidification requires a small amount of thermal energy compared to the conventional calcination method. be. The present invention aims to provide a method for producing a chemical compound fertilizer that eliminates the above-mentioned difficulties, and the details thereof will be explained below with reference to the drawings.

The present invention is a highly concentrated phosphoric acid solution obtained by heating and dehydrating a phosphoric acid raw material such as super phosphoric acid, that is, an orthophosphoric acid solution, and is
When a high-concentration phosphoric acid solution of 76% P2O5 was produced in A.A., it was named super phosphoric acid, and is generally referred to as pure orthophosphoric acid (
Phosphoric acid (P2O5) concentration of 100% H3PO4) 72.4
Superphosphoric acid, which contains more than 2% phosphoric acid and is considered to be a fluid phosphoric acid solution that is a mixture of orthophosphoric acid and polyphosphoric acid in which both coexist to a certain extent, or condensed phosphoric acid, condensed phosphates, that is, generally orthophosphoric acid or its We focused on the fact that phosphates, which are made by polymerizing two or more phosphorus molecules by heating and dehydrating salt, have a much smaller volume than a phosphoric acid mixture and store abundant chemical active energy. By using it for the phosphorylation of materials, it is easy to transport the phosphoric acid raw material, and the heat generated by hydrolysis is actively generated, promoting the phosphorylation of inorganic compound minerals, etc., shortening the reaction time, and We came up with the idea that the actively generated phosphorylation reaction heat compensates for the temperature drop due to endothermic absorption of mixed chlorides, keeps the gel sol warm, and has a large effect on self-solidification heat formation, which greatly helps in saving thermal energy. It has been done.

Next, the present invention will be explained using the manufacturing process diagram shown in FIG. As shown in the figure, the raw materials are inorganic compound mineral substance 1, organic substance 2,
After weighing 4, 5, and 6 of super phosphoric acid 3 and super phosphoric acid 3, respectively, they are fed into a mixing reactor and mixed to form super phosphoric acid 3.
An active phosphorylation reaction is caused to form a slurry7. When the generation of hydrogen starts, chloride and other supplementary fertilizer components 8 are weighed 9 and mixed uniformly 10, acidity is adjusted 11 as necessary, and the mixture is heated using a dry granulation reaction heat forming machine. and is granulated and solidified 12 using the heat of the phosphorylation reaction. In addition, the phosphate, silicophosphate Kelsol, which is formed by mixing chloride into the mixture slurry 7 in the mixing reactor, contains hydrochloric acid and becomes a fertilizer with a high content of hydrochloric acid roots. , silicophosphate gel sol, hydrochloric acid,
By adding a step of azeotropic drying 13 of a mixed product such as hydrogen to separate hydrochloric acid 14, and sending it to a drying granulation reaction maturing machine for granulation and solidification 12, it is possible to create a fertilizer with a low content of chlorine radicals. can.

In addition, 15 urea is weighed 15 to 7 products from which hydrochloric acid has been separated, phosphates from which hydrochloric acid has not been separated, and silicophosphate gel sol.
6 and mix uniformly to make a kneaded material or granular material 17,
For example, an aldehyde-based compound 18 that undergoes a polycondensation reaction with urea.
Weigh 19 and mix or contact 2 in liquid or gaseous form.
By adding a step of making the gel sol 0 and then sending it to a dry granulation reaction maturing machine for granulation and solidification 12, it is possible to slow down the reluctance due to the physical action of the gel sol's self-coagulating property, and to add the chemical effect of the urea polycondensate. It is also possible to create a fertilizer that has slow-release properties in large amounts of moisture, such as in paddy fields, by adding weight to slow-release properties due to physical stability. Next, the present invention will be specifically explained with reference to Examples. Example 1 Coal ash
307k9 super phosphoric acid 102
kg Potassium chloride 142k9 Organic liquid (alcohol waste liquid) 312k9 Urea
217kg acetaldehyde
It was produced using 100k9 by the following manufacturing process operations to obtain a yield of 1000k9.

Coal ash is mixed with alcohol waste, potassium chloride, and phosphoric anhydride.

Then, phosphoric anhydride generates phosphoric acid while being hydrolyzed, and at the same time phosphorylates organic substances in coal ash and alcohol waste liquid, generating heat and generating gel sol mainly composed of phosphates and silicon phosphates. Thereafter, the mixture is left to stand for a suitable period of time or kept under stirring, and urea is added and mixed before and after the start of self-coagulation. Next, acetaldehyde is mixed with this to produce a urea polycondensate, which is then dried and granulated to solidify. As described above, acetaldehyde may be in liquid form, but if gaseous acetaldehyde is used and brought into contact with the granulated product, the urea on the outer circumferential side of the granulated fertilizer will be polycondensed.

It is also possible to use crotonaldehyde instead of acetaldehyde. Example ■Coal ash, slag mixture
307k9 organic matter (crushed fish and shellfish)
322k9 chloride, potassium sulfate salt 144
k9 condensed phosphoric acid 115k9 urea
217kg isobutyraldehyde 100k9 Mix condensed phosphoric acid with organic matter and dehydrate and phosphorylate the organic matter.

Coal ash and slag mixture are then mixed with this to produce phosphate, silicophosphate organic compound Kelsol. Next, potassium salt and urea are added and mixed uniformly, and then isobutyraldehyde is mixed. This makes urea phosphoric acid poorly soluble, solidifies it with a polycondensate, confines water-soluble substances such as potassium salt, and slows down the elution rate. The fertilizing effect can be promoted by using fibrous woody organic matter treated with phosphoric acid or alkali.
As is clear from the above explanation, in the present invention, in producing a gel sol such as phosphate, silicophosphate, etc., which has self-condensation and solidification properties with an inorganic compound mineral material such as coal ash,
This product uses concentrated condensed phosphoric acids such as super phosphoric acid, condensed phosphoric acid, and condensed phosphate salts, which have a much smaller volume than conventional phosphoric acid mixtures and are rich in chemical activation energy, and have the following excellent effects: This is demonstrated by the experimental examples shown in FIGS. 2 and 3.

Figures 2 and 3 show alcoholic dairy fermentation waste liquid (50% moisture) and plankton (90% moisture), which have high water content as organic substances, respectively, and 60% phosphoric acid solution or concentrated condensed phosphoric acid, fine coal ash, and salt. This figure shows the chemical compounding reaction temperature when compound and salt are sequentially mixed, and the temperature and time elapsed for changes in physical properties from the end of mixing until commercialization.

This sample product was designed to contain 10% of each of N, P2O5, K2O, and organic matter. In this way, in case B (in the case of the present invention) where concentrated condensed phosphoric acid is mixed with organic matter with a high water content, 6
In the case of a mixture of 0% phosphorus and acid solution, a temperature increase of about 30° C. is clearly seen compared to A, but this is due to heat generation from dissolution of phosphoric acid. Next, when pulverized coal ash is mixed, the phosphating reaction of B is faster than that of A, and the temperature rise is also large, about 30'C. A decrease in temperature was observed in both A and B due to heat transfer, dissolution endotherm, and heat radiation due to ammonium chloride and salt addition. After that, gel formation, viscosity generation, coagulation start, coagulation end, and solidification were extremely slow reaction processes in A, but B was faster and even solidified into a product quickly, resulting in a difference of 5 powders in the end. occured. In addition, when using concentrated condensed phosphoric acid, it was dried and matured to the point that it could be applied by air drying, but when using phosphoric acid solution, heating, drying with ventilation, and aging were necessary. As is clear from the above experimental examples, according to the present invention, since concentrated condensed phosphoric acids having a large amount of heat of solution and chemical activation energy are used, active phosphate reactions and chemical compounding reactions occur from beginning to end, resulting in external interference. The reaction time is shortened by promoting phosphorylation of inorganic compound minerals without the need for replenishment of thermal energy, and at the same time, the self-solidifying ability is increased, so the time for commercialization is also shortened.

Furthermore, condensed phosphoric acids are solidified powders that are lighter in weight than conventionally used phosphoric acid mixtures by the amount of water they contain, and their volume is small and easy to handle, making transportation easy and inexpensive. It exhibits excellent effects that cannot be obtained with conventional methods.

[Brief explanation of the drawing]

FIG. 1 is a process diagram showing the manufacturing method of the present invention, and FIGS. 2 and 3 are illustrations of experimental examples of the present invention, respectively.

Claims (1)

[Claims] 1. Supplementary fertilizer ingredients such as potassium salts and nitrogen salts are added to the mixed slurry product of inorganic compound minerals whose main components are iron, aluminum, calcium, magnesium, silica, etc., or a mixture of these with organic substances, and phosphoric acid raw materials. A method for producing a chemical compound fertilizer made by mixing the above, wherein concentrated phosphoric acid or a phosphate such as super phosphoric acid, condensed phosphoric acid, or condensed phosphate is used as the phosphoric acid raw material.