CN104229765B - A kind of production method preparing ammonium phosphate by-product Radix Paeoniae Rubra special fertilizer - Google Patents

Abstract

The present invention relates to the field of chemical technology, in particular to a production method for preparing ammonium phosphate by-product Radix Paeoniae Rubra special fertilizer, by analyzing the nutrient requirements in the growth process of Radix Radix Radix Radix Paeoniae Rubra, combined with the shortcomings in the preparation process of ammonium phosphate products for analysis and analysis. We understand that the combination of the preparation process of red peony special compound fertilizer and the preparation process of ammonium phosphate products makes the two processes complement each other, reduces the waste liquid discharge in the preparation process of ammonium phosphate products, and avoids the deep crystallization. The shortcomings of the low purity of the ammonium phosphate products from the past have improved the quality of the ammonium phosphate products; by adjusting and matching the nutrient elements in the waste liquid, the prepared special compound fertilizer for red peony can meet the nutritional needs of red peony and improve the quality of the ammonium phosphate product. The growth rate of Radix Paeoniae Rubra improves the yield and quality of Radix Paeoniae Rubra, reduces the soil compaction rate, improves the land utilization rate, and has significant environmental protection value and economic benefits.

Description

A production method for preparing ammonium phosphate by-product red peony special fertilizer

technical field

The invention relates to the technical field of chemical industry, in particular to a production method for preparing ammonium phosphate by-product red peony special fertilizer.

Background technique

Radix Paeoniae Rubra, also known as Muchishao, Chishaoyao, Red Chishao, Cao Chishao, is a plant of Ranunculaceae, a perennial herb, which has the effects of clearing heat and cooling blood, dissipating blood stasis and relieving pain. When people cultivate Radix Paeoniae Rubra, they usually use compound fertilizer and urea as the main fertilizers, and the effect is better; but the nutrients in the fertilizers are difficult to meet the needs of Radix Paeoniae Rubra, and because most growers are concerned about the growth law of Radix Paeoniae Rubra and the There is little understanding of nutritional requirements, and the fertilizers applied lack certain nutrients. According to the theory of short boards of wooden barrels, when a certain nutrient element is lacking, it will also affect the absorption of other nutrient elements, resulting in low yield of Radix Paeoniae Rubra and leaves. Withering, falling off, less flowering, few results, underdeveloped roots, slow growth and other problems; for this reason, some researchers have studied the special fertilizer for red peony root, such as "A Kind of Red Peony Chinese Herbal Nutritional Fertilizer" with the patent number 201010156942.0. A kind of raw material is potassium dihydrogen phosphate, potassium sulfate, insecticide, phenolic resin, livestock and poultry manure, pumpkin powder, bitter gourd powder, pine needle powder and other Chinese herbal medicine plant powder and straw powder, which are made into lumps through fermentation. Nutritional fertilizer, it can be seen that the preparation of special fertilizer for red peony root is relatively rare in the prior art, and some technical solutions are all formed by using traditional chemical fertilizers or farmyard manure, and according to the absorption of nitrogen, phosphorus and potassium fertilizers by crops From the perspective of the situation, the absorption rate of nitrogen fertilizer by crops is 20-46%, phosphorus fertilizer is 10-25%, and potassium fertilizer is about 46-60%. This will cause a large amount of nitrogen, phosphorus and potassium fertilizers to remain in the soil, causing soil pollution. Therefore, For the cultivation of Radix Paeoniae Rubra, it is urgent to improve this defect, so that the special fertilizer for Radix Paeoniae Rubra can meet the fertilizer requirements of Radix Paeoniae Rubra, reduce the nitrogen, phosphorus and potassium elements remaining in the soil, and improve the utilization rate of the compound fertilizer for Radix Paeoniae Rubra.

At the same time, in the preparation process of ammonium phosphate products, one of wet-process phosphoric acid and hot-process phosphoric acid is usually used to prepare ammonium phosphate products. This process will affect the purity of ammonium phosphate products, making ammonium phosphate The purity of the product is low. Therefore, it is necessary to design an additional purification process for ammonium phosphate to purify the ammonium phosphate product, thereby increasing the preparation cost of the ammonium phosphate product. Therefore, some people react by using phosphoric acid and urea at a temperature lower than 80 degrees Celsius. To produce an intermediate such as urea phosphate, and then use the intermediate as a raw material to react with ammonia gas to produce ammonium phosphate products. This process requires cooling and cyclic crystallization of ammonium phosphate products, but often requires deep crystallization of ammonium phosphate products. Only in this way can a large amount of nitrogen and phosphorus nutrients in the waste liquid be discharged into the environment, thereby avoiding the waste of resources and reducing the production cost of ammonium phosphate products. However, due to the deep crystallization process, other products will also be crystallized out. , thereby affecting the purity of the ammonium phosphate product.

For this reason, through long-term hard research and exploration, the researcher combined the preparation process of red peony special compound fertilizer with the preparation process of ammonium phosphate, and complemented each other through the advantages and disadvantages of the two, and provided the preparation process for ammonium phosphate products and red peony. The preparation process of special compound fertilizer for peony provides a new idea.

Contents of the invention

In order to solve the above-mentioned technical problems in the prior art, the present invention provides a production method for preparing ammonium phosphate by-product Radix Paeoniae Rubra special fertilizer, which has the advantages of simple process, can reduce the discharge of waste liquid in the preparation process of ammonium phosphate products, and increase the production of phosphoric acid. The purity of the ammonium product meets the requirements of the rapid growth of Radix Paeoniae Rubra and improves the quality of Radix Radix Radix Paeoniae Alba.

Specifically, it is achieved through the following technical solutions:

A production method for preparing ammonium phosphate by-product red peony root special fertilizer, using phosphoric acid and urea to mix according to the molar ratio of (1.5-1.8): 1, stirring and reacting for 1-2.5 hours at a temperature of 90-110°C to obtain an intermediate Slurry; then feed ammonia gas into the intermediate slurry, and control the reaction temperature to 60-90°C, stir and react for 20-30 minutes, and control the end point pH value to 9.8-11.4 to obtain ammonium phosphate slurry; then add phosphoric acid The ammonium slurry is placed in a circulating cooling crystallizer for circulating cooling crystallization treatment, and the nitrogen and phosphorus elements in the solution are detected, analyzed and adjusted so that the molar ratio of the nitrogen and phosphorus elements in the solution is 1.1: (1.1-1.7), Stop crystallization and filter treatment, the filter cake is an ammonium phosphate product, add potassium components and medium and trace element compounds to the filtrate, and adjust the mol ratio of the nitrogen, phosphorus and potassium element components in the solution to be 1.1: (1.1-1.7): (1.3-1.5 ), the primary product of compound fertilizer is obtained; then the primary product of compound fertilizer is placed in a dryer, and the temperature is raised to 60-70°C at a heating rate of 10°C/min, and after drying for 1.5-2.5h, By adjusting the water content to 1.5-2.5%, the compound fertilizer special for red peony root can be prepared.

When the phosphoric acid and urea react to prepare the intermediate slurry, the stirring speed is 180-200r/min.

The stirring speed is 400-500 r/min when the stirring reaction is carried out for 20-30 minutes after the ammonia gas is introduced.

The circulating cooling crystallization treatment in the circulating cooling crystallizer is to lower the temperature to ≤30 °C at a cooling rate of 5 °C/min.

The potassium component is one of potassium hydroxide, potassium sulfate and potassium chloride.

The concentration of the potassium component is 30%.

The middle and trace element compound is calcium ion EDTA chelate, iron ion EDTA chelate, zinc ion EDTA chelate, selenium ion EDTA chelate, magnesium ion EDTA chelate, borax, humic acid, plant ash mixture.

The added amount of the middle and trace element compound is about 16% of the total weight of the solution.

Described compound state compound fertilizer, its composition contains following nitrogen, phosphorus and potassium compound state structural formula:

Wherein, the dotted line between the carbon atom and the oxygen atom indicates that there is a coordination bond between the C atom and the O atom.

When adding potassium components and trace element compounds, you can also add fermented and decomposed livestock and poultry manure, pumpkin powder, bitter gourd powder, straw powder, pine needle powder, Houttuynia cordata powder, dandelion powder, tangerine peel powder, fungicide, marsh Slag, biogas slurry and other organic or inorganic substances.

Compared with the prior art, the technical effect of the technical solution of the present invention is reflected in:

1. Through the analysis of the nutritional requirements in the growth process of Radix Paeoniae Rubra and the shortcomings in the preparation process of ammonium phosphate products, the preparation process of compound fertilizer for Radix Paeoniae Rubra and the preparation process of ammonium phosphate products are combined, The two processes complement each other, reduce the discharge of waste liquid in the ammonium phosphate product preparation process, avoid the disadvantage of low purity of the ammonium phosphate product caused by deep crystallization, and improve the quality of the ammonium phosphate product.

2. By adjusting and matching the nutrient elements in the waste liquid, the prepared special compound fertilizer for red peony can meet the nutritional needs of red peony, increase the growth rate of red peony, improve the yield and quality of red peony, and at the same time, avoid the Improper matching of elements leads to excessive residual elements in the soil, which reduces the soil compaction rate and improves the land utilization rate, which has significant environmental protection value and economic benefits.

3. Through the control of technical parameters in the production process of compound fertilizers, that is, temperature, raw material concentration and ratio control, after the reaction of phosphoric acid and urea, urea phosphate products are produced. Urea phosphate products themselves have strong acidity, while phosphoric acid and urea Urea is a compounded double salt formed by coordinating bonds, which is also used as a fertilizer for crops in traditional technology, and the absorption rate of the compounded double salt by crops is higher than that of urea, ammonium carbonate, and ammonium nitrate. It is a compound fertilizer with excellent absorption rate of mono- and binary fertilizers. However, in the presence of phosphoric acid, complex decomposition and polymerization reactions will occur at a temperature of 80-250°C. , so that urea phosphate forms (H ₂ PO ₄ )- and (H ₂ NCONH ₃ ) ⁺ two ions, (H ₂ NCONH ₃ ) ⁺ ions are close to phosphoric acid, and form at a temperature of 80-160°C The intermediate ion and dihydrogen phosphate form a coordination bond between C and O. This intermediate ion can chelate with the middle element compound to form a multi-element intermediate ion, which can then continue to interact with other negatively charged compounds or ions Form a chelate, increase the element content in the double salt, and then adjust the nutrient content in the double salt where the ion exists. At the same time, the chelate can be hydrolyzed and absorbed by the crops, which can effectively provide fertilizer for the crops for a long time At the same time, combined with the determination of the element content in the solution where the ion exists, the content of each element when the double salt is formed is adjusted, and the compound fertilizer containing the compound state double salt structure is obtained by drying, which improves the quality of the special fertilizer for red peony root.

detailed description

The technical solutions of the present invention will be further limited below in conjunction with specific embodiments, but the scope of protection is not limited to the descriptions made.

Principle description:

The present invention studies and discusses the mechanism of the reaction between phosphoric acid and carbonamide, and combines the prior art literature to understand that phosphoric acid and carbonamide react to form urea phosphate, and its molecular formula is: CO(NH ₂ ) ₂ .H ₃ PO ₄ , In a higher temperature environment, the chemical bond between H and O in phosphoric acid will be broken, and hydrogen ions will combine with urea to form an ion state with a positive charge, making urea phosphate form an ion double salt that attracts positive and negative charges. , and its mechanism structure reaction is as follows: CO(NH ₂ ) ₂ .H ₃ PO ₄ →(H ₂ PO ₄ )-.(H ₂ NCONH ₃ ) ⁺

Furthermore, in the presence of phosphoric acid in the presence of phosphoric acid, the (H ₂ NCONH ₃ ) ⁺ positive ion in the double salt of urea phosphate ion is close to phosphoric acid to form the intermediate ion of the C→O coordination bond, which is (CO ₅ PN ₂ H ₈ ) ⁺ , so that the urea phosphate intermediate contains a large amount of (H ₂ PO ₄ )- and (CO ₅ PN ₂ H ₈ ) ⁺ ions. Ions form ammonium phosphate crystals and are separated out, and the content of nitrogen and phosphorus elements in the filtrate is detected and analyzed, and potassium, magnesium, iron and other medium and trace elements are added according to the needs of red peony root to adjust the nutritional structure in the filtrate. Make the nutrient structure layer meet the requirement of Radix Paeoniae Rubra, and then dry to prepare the special chemical compound fertilizer for Radix Paeoniae Rubra containing N, P, K and other elements.

Its specific reaction principle will be further explained by the following reaction structural formula and reaction mechanism:

Reaction formula one:

CO(NH ₂ ) ₂ +H ₃ PO ₄ →CO(NH ₂ ) _{2.H 3} PO ₄

Reaction two:

Reaction three:

Wherein, the dotted line between the carbon atom and the oxygen atom indicates that there is a coordination bond between the C atom and the O atom.

Reaction four:

After the crystalline ammonium phosphate product comes out, potassium and other elements are added to the filtrate, which will react with the dihydrogen phosphate, hydrogen phosphate and other elements remaining in the filtrate. The intermediate ion is reacted to generate compound fertilizer special for red peony root in the form of double salt.

Noun description:

Ureaphosphate (UP), CAS No. 4861-19-2, molecular formula CH ₇ N ₂ O ₅ P, can be expressed as CO(NH ₂ ) ₂ ·H ₃ PO ₄ :

It is a fine chemical product widely used in animal husbandry, industry, agriculture and other fields. Its solid is white crystal or crystalline powder, soluble in water and alcohol, insoluble in ether, toluene and carbon tetrachloride, and its aqueous solution is It is acidic and starts to decompose when melting to release carbon dioxide and ammonia.

Embodiment: The present invention will be further elaborated below with specific operation examples.

Example 1

A production method for preparing ammonium phosphate by-product Radix Paeoniae Rubra, which uses phosphoric acid and urea to mix at a molar ratio of 1.5:1, and stirs and reacts for 1 hour at a temperature of 90°C to obtain an intermediate slurry; Ammonia gas was passed into the medium, and the reaction temperature was controlled at 60°C. After stirring for 20 minutes, the pH value of the end point was controlled to be 9.8 to obtain ammonium phosphate slurry; then the ammonium phosphate slurry was placed in a circulating cooling crystallizer for circulating cooling crystallization treatment , and the nitrogen and phosphorus elements in the solution are detected, analyzed and adjusted so that the molar ratio of the nitrogen and phosphorus elements in the solution is 1.1:1.1, stop crystallization and filter, the filter cake is an ammonium phosphate product, and potassium components are added to the filtrate and medium and trace element compounds, and adjust the molar ratio of nitrogen, phosphorus, and potassium elements in the solution to 1.1:1.1:1.3 to obtain the first product of compound fertilizer; then place the first product of compound fertilizer in a dryer, and use The heating rate is 10°C/min, and the temperature is raised to 60°C. After drying for 1.5 hours, the moisture content is adjusted to 1.5%, and the special compound fertilizer for Radix Paeoniae Rubra can be obtained.

When the phosphoric acid and urea react to prepare the intermediate slurry, the stirring speed is 180r/min.

The stirring speed is 400 r/min when the stirring reaction is carried out for 20 minutes after the ammonia gas is introduced.

The circulating cooling crystallization process in the circulating cooling crystallizer is to lower the temperature to 30 °C at a cooling rate of 5 °C/min.

The potassium component is potassium hydroxide.

The concentration of the potassium component is 30%.

The described trace element compound is 0.6% calcium ion EDTA chelate, 0.03% iron ion EDTA chelate, 0.05% zinc ion EDTA chelate, 0.02% selenium ion EDTA chelate, 0.04% magnesium ion EDTA chelate compound, 0.02% borax, 4.3% humic acid, 6.5% plant ash.

Example 2

A production method for preparing ammonium phosphate by-product Radix Paeoniae Rubra special fertilizer, using phosphoric acid and urea to mix according to the molar ratio of 1.8:1, stirring and reacting at a temperature of 110°C for 2.5 hours to obtain an intermediate slurry; Ammonia gas is introduced into the slurry, and the reaction temperature is controlled at 90°C. After stirring for 30 minutes, the pH value at the end point is controlled to be 11.4 to obtain ammonium phosphate slurry; then the ammonium phosphate slurry is placed in a circulating cooling crystallizer for circulating cooling crystallization treatment, and detect, analyze and adjust the nitrogen and phosphorus elements in the solution so that the molar ratio of the nitrogen and phosphorus elements in the solution is 1.1:1.7, then stop the crystallization and filter the treatment, the filter cake is an ammonium phosphate product, and add potassium to the filtrate Components and trace element compounds, and adjust the molar ratio of nitrogen, phosphorus and potassium elements in the solution to 1.1:1.7:1.5 to obtain the primary product of compound fertilizer; then place the primary product of compound fertilizer in the dryer, The temperature is raised to 70° C. at a heating rate of 10° C./min, and after drying for 2.5 hours, the moisture content is adjusted to 2.5 percent to obtain a special compound fertilizer for red peony root.

When the phosphoric acid and urea react to prepare the intermediate slurry, the stirring speed is 200r/min.

The stirring speed is 500 r/min when the stirring reaction is carried out for 30 minutes after the ammonia gas is introduced.

The circulating cooling crystallization treatment in the circulating cooling crystallizer is to lower the temperature to 20 °C at a cooling rate of 5 °C/min.

The potassium component is potassium sulfate.

The concentration of the potassium component is 30%.

The medium and trace element compound is 0.2% calcium ion EDTA chelate, 0.05% iron ion EDTA chelate, 0.03% zinc ion EDTA chelate, 0.04% selenium ion EDTA chelate, 0.01% magnesium ion EDTA chelate compound, 0.05% borax, 3.7% humic acid, 5.4% plant ash.

Example 3

A production method for preparing ammonium phosphate by-product red peony root special fertilizer, using phosphoric acid and urea to mix according to the molar ratio of 1.65:1, stirring and reacting for 2 hours at a temperature of 100°C to obtain an intermediate slurry; Ammonia gas was passed into the medium, and the reaction temperature was controlled at 75°C. After stirring for 25 minutes, the pH value of the end point was controlled to be 10.3 to obtain ammonium phosphate slurry; then the ammonium phosphate slurry was placed in a circulating cooling crystallizer for circulating cooling crystallization treatment , and detect, analyze and adjust the nitrogen and phosphorus elements in the solution, so that the molar ratio of the nitrogen and phosphorus elements in the solution is 1.1:1.4, stop the crystallization and filter, the filter cake is ammonium phosphate product, and add potassium to the filtrate and medium and trace element compounds, and adjust the molar ratio of nitrogen, phosphorus and potassium elements in the solution to 1.1:1.4:1.4 to obtain the first product of compound fertilizer; then place the first product of compound fertilizer in a dryer and use The heating rate is 10°C/min, and the temperature is raised to 65°C. After drying for 2 hours, the moisture content is adjusted to 2%, and the special compound fertilizer for red peony root can be prepared.

When the phosphoric acid and urea react to prepare the intermediate slurry, the stirring speed is 190r/min.

The stirring speed is 450 r/min when the stirring reaction is carried out for 25 minutes after the introduction of ammonia gas.

The circulating cooling crystallization treatment in the circulating cooling crystallizer is to lower the temperature to 25 °C at a cooling rate of 5 °C/min.

The potassium component is potassium chloride.

The concentration of the potassium component is 30%.

The described trace element compound is 0.3% calcium ion EDTA chelate, 0.02% iron ion EDTA chelate, 0.02% zinc ion EDTA chelate, 0.03% selenium ion EDTA chelate, 0.06% magnesium ion EDTA chelate compound, 0.05% borax, 2.6% humic acid, 7.8% plant ash.

Experimental example: the technical effect and product characteristics of the technical solution of the present invention will be further described in conjunction with specific examples below.

Test example The effect of the special compound fertilizer of Radix Paeoniae Rubra of the present invention on the growth situation of Radix Paeoniae Rubra

Experimental group: the Paeoniae Rubra special compound fertilizer that adopts embodiment 1, embodiment 2, embodiment 3 to make is carried out Radix Paeoniae Rubra according to traditional planting technology of Radix Paeoniae Rubra, and adds 160kg of compound fertilizers of the present invention per mu.

Control group: "A Nutrient Fertilizer for Chinese Herbal Medicine of Radix Paeoniae Alba" with patent number 201010156942.0 was used to plant Radix Paeoniae Rubra according to the traditional planting technology of Radix Paeoniae Rubra, and 160 kg of nutritional fertilizer was added per mu.

Note: The same amount of farmyard manure was used as base fertilizer in the above experimental group and control group.

Observe the growth situation of Radix Paeoniae Rubra after 10 days of fertilization, observe continuously for 1 month, and record as shown in Table 1 below:

Table 1:

It can be seen from the data in the table that the special fertilizer for Radix Paeoniae Rubra of the present invention can rapidly increase the growth rate of Radix Radix Radix Radix Paeoniae Alba, and has a longer fertilizer effect persistence.

It must be pointed out here that the above examples and test examples are limited to further explanation and understanding of the technical effects that the technical solution of the present invention can achieve, and are not limited to further limitations of the technical solution of the present invention. Improvements made on this basis without prominent substantive features and non-significant progress all belong to the protection category of the present invention.

Claims (7)

1. a kind of production method of preparing ammonium phosphate by-product Radix Paeoniae Rubra special fertilizer, it is characterized in that, adopt phosphoric acid and urea to be (1.5-1.8): 1 mixes according to mol ratio, be 90-110 ℃ at temperature, stirring reaction 1- After 2.5 hours, the intermediate slurry was obtained; then ammonia gas was introduced into the intermediate slurry, and the reaction temperature was controlled at 60-90°C. After stirring for 20-30 minutes, the pH value of the end point was controlled to be 9.8-11.4, and ammonium phosphate was obtained. slurry; then ammonium phosphate slurry is placed in a circulating cooling crystallizer to carry out circulating cooling crystallization treatment, and the nitrogen and phosphorus elements in the solution are detected, analyzed and adjusted so that the mol ratio of the nitrogen and phosphorus elements in the solution is 1.1:( 1.1-1.7) after, stop crystallization and filter processing, filter cake is ammonium phosphate product, adds potassium component and middle and trace element compound in filtrate, and the mol ratio of adjusting the nitrogen, phosphorus and potassium element composition in the solution is 1.1:(1.1-1.7 ): (1.3-1.5), the primary product of compound fertilizer is obtained; then the primary product of compound fertilizer is placed in the dryer, and the temperature is raised to 60-70°C at a heating rate of 10°C/min, and dried After 1.5-2.5 hours, adjust the water content to 1.5-2.5%, and then the special compound fertilizer for red peony root can be prepared. 2. the production method of preparing ammonium phosphate by-product red peony root special fertilizer as claimed in claim 1, is characterized in that, when described phosphoric acid and urea react to prepare intermediate slurry, stirring speed is 180-200r/min. 3. the production method of the special fertilizer for preparing ammonium phosphate by-product Radix Paeoniae Rubra as claimed in claim 1, is characterized in that, the stirring speed when carrying out stirring reaction 20-30min after described feeding ammonia is 400-500r/min . 4. the production method of the special fertilizer for preparing ammonium phosphate by-product Radix Paeoniae Rubra as claimed in claim 1, is characterized in that, in the described circulating cooling crystallizer, carrying out the circulating cooling crystallization process is that the temperature adopts cooling rate as 5 ℃/min Cool down to ≤30°C. 5. the production method of preparing ammonium phosphate by-product red peony special fertilizer as claimed in claim 1, is characterized in that, described potassium component is the one in potassium hydroxide, potassium sulfate, potassium chloride. 6. the production method of preparing ammonium phosphate by-product red peony root special fertilizer as claimed in claim 1, is characterized in that, described trace element compound is calcium ion EDTA chelate, iron ion EDTA chelate, zinc ion A mixture of EDTA chelate, selenium ion EDTA chelate, magnesium ion EDTA chelate, borax, humic acid, plant ash. 7. the production method of preparing ammonium phosphate by-product red peony root special fertilizer as claimed in claim 1, is characterized in that, described compound state compound fertilizer, contains following nitrogen phosphorus potassium compound state structural formula in its composition: Wherein, the dotted line between the carbon atom and the oxygen atom indicates that there is a coordination bond between the C atom and the O atom.