CN1292367A - Production method of granular nitrogen-phosphorus composite fertilizer containing secondary element - Google Patents
Production method of granular nitrogen-phosphorus composite fertilizer containing secondary element Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G1/00—Mixtures of fertilisers belonging individually to different subclasses of C05
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B11/00—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes
- C05B11/04—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid
- C05B11/08—Fertilisers produced by wet-treating or leaching raw materials either with acids in such amounts and concentrations as to yield solutions followed by neutralisation, or with alkaline lyes using mineral acid using sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
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Abstract
The production method of granular nitrogen-phosphorous composite fertilizer and azophoska containing secondary elements includes the following steps: dissolving urea in sulfuric acid to obtain urea sulfate solution, then adding ground phosphate rock in the urea sulfate solution to make reaction to obtain fertilizer slurry, adding neutralizing ageng to make neutralization, then granulating to obtain nitrogen-phosphorous composite fertilizer. At the same time of adding neutralizing agent the basic fertilizer containing nitrogen, phosphorous and potassium can be added so as to obtain the invented azophoska. Said invention is short in production period, and has no three-waste discharge.
Description
The invention relates to a method for preparing granular nitrogen-phosphorus or nitrogen-phosphorus-potassium compound fertilizer containing secondary elements.
In the existing production technology of granular nitrogen-phosphorus-potassium compound fertilizer, the commonly used production technology is a granulation method, and the essence is that powdery, crystalline or fine granular base fertilizer is agglomerated into granules. The powder fertilizer is agglomerated and adhered into granule by means of wetting the surface of the powder with the solution produced by fertilizer salt, the added salt solution and water vapor, and through mutual friction, turning over and extrusion in the granulator and under proper liquid phase amount. At present, the main systems for producing the domestic medium and low concentration compound fertilizer comprise: ammonium chloride-calcium superphosphate-potassium chloride (potassium sulfate) system and urea-calcium superphosphate-potassium chloride (potassium sulfate) system, wherein the main source of phosphorus in the compound fertilizer is superphosphate product. The traditional common calcium production generally adopts a classical stacking aging method, and the production process is carried out by phosphorusThe method comprises three procedures of mixing reaction of mineral powder and sulfuric acid, solidification and cutting of reaction slurry and stacking and curing of fresh fertilizer, and has the advantages of simple production process and lower cost. The calcium superphosphate product contains effective P2O512-18 percent of water and 10-14 percent of water, and the product can be converted into the product only by curing for 10-20 days, and the physical properties of the product are not ideal. The raw material of the common calcium used as the compound fertilizer needs to be pretreated.
The Chinese patent of Zhengzhou industrial university discloses a production technology of a granular compound fertilizer by a one-step method of partially-acidified phosphorite, the patent number is 91122622.8, the grant notice number is CN1063674C, and the grant notice date is 1996, 10 months and 2 days. The technology introduces a one-step process for preparing granular compound fertilizer by using urea as nitrogen source, potassium chloride or potassium sulfate as potassium source, powdered rock phosphate as phosphorus source and sulfuric acid, phosphoric acid or mixed sulfuric-phosphoric acid as acidifying agent. The technology is characterized by low investment, no drying, no material return and low cost. However, citric acid solution is adopted for leaching phosphorus in citric acid soluble phosphorus detection of the product, and neutral ammonium citrate solution is adopted for leaching phosphorus in citric acid soluble phosphorus detection specified in the national compound fertilizer standard GB 15063-94. The former has higher effective phosphorus measurement data. The product inspection refers to the standard Q/ZGF 002-94 of the Zhengzhou industrial university enterprise for partially acidified phosphorite compound fertilizer.
The technology developed by research division of Paris mining institute of France for producing nitrogen-Phosphorus compound fertilizer by using the existing calcium production device is reported in Phosphorus&Potasicum (No. 191, 1994). The technology uses urea sulfate solution (urea: sulfuric acid: water = 3.6: 1, mol ratio) to replace sulfuric acid as decomposition liquid of phosphorite, and the powdery nitrogen-phosphorus compound fertilizer is prepared by three stages of mixing reaction of the decomposition liquid and the phosphorite, solidification and formation of slurry and curing of fresh fertilizer. The gross nutrient (N + P) can be prepared from the Morocco phosphorite2O5) Over 30% of nitrogen-phosphorus compound fertilizer containing 20.90% of N and effective P2O59.70 percent and 1.0 percent of water. The process basically has no fluorine escape, no waste water discharge and good operation environment, the water content of the obtained product is far lower than that of a common calcium product, and the available nutrients are obviously improved. The main components of the product are calcium sulfate tetra-urea and calcium sulfateThe fertilizer efficiency of the compound and monocalcium phosphate monohydrate is obviously improved compared with that of urea and calcium superphosphate which are equivalent in quantity and are simply mixed and applied. However, the technology is only suitable for phosphorite with higher reaction activity, such as Morocco phosphorite, jodan phosphorite and the like. The general reactivity of the phosphorite in China is low, and the problems that reaction slurry is not solidified for a long time, fresh fertilizer and cured material have poor physical properties and normal production cannot be realized when the technology is used are encountered.
The invention aims to provide a method for manufacturing a granular nitrogen-phosphorus compound fertilizer containing secondary elements. The method uses urea sulfate solution with certain concentration to decompose phosphate rock powder aiming at the characteristics of low reaction activity and poor slurry solidification performance after reaction of phosphate rock in China, and uses alkaline substances containing medium elements of calcium and magnesium as a neutralizing agent to neutralize and granulate the acidic reaction slurry; or adding basic fertilizers such as potassium salt (potassium chloride or potassium sulfate), monoammonium phosphate, diammonium phosphate and the like and return materials to perform slurry granulation, and drying and screening the granulated materials to obtain granular nitrogen-phosphorus or nitrogen-phosphorus-potassium compound fertilizers.
The method for manufacturing the granular nitrogen-phosphorus compound fertilizer containing the secondary elements is realized in the way. The manufacturing method comprises the following steps:
(1) dissolving urea in a sulfuric acid solution to generate a urea sulfate solution, wherein the temperature of the solution is kept at 70-80 ℃, the ratio of urea to sulfuric acid to water is (3.1-3.5) = (1): (5.5-6.5) (molar ratio),
(2) adding phosphate rock powder into a urea sulfate solution to react to prepare fertilizer slurry, wherein the ratio of the phosphate rock powder to the urea sulfate solution is phosphate rock powder to urea sulfate solution = 1: 3.06-3.19 (weight ratio), the reaction temperature is 70-75 ℃, the reaction time is 40-60 minutes,
(3) and neutralizing and granulating the fertilizer slurry by using a neutralizer, wherein the neutralizer is a calcium magnesium phosphate fertilizer, and finally preparing the granular nitrogen-phosphorus compound fertilizer.
In the process of granulating the fertilizer slurry, a neutralizer calcium magnesium phosphate fertilizer and a basic fertilizer containing nitrogen, phosphorus and potassium are added, and finally, the granular nitrogen-phosphorus-potassium compound fertilizer containing medium elements can be prepared.
The preparation method of the compound fertilizer comprises the step of mixing the fertilizer slurry and the neutralizer calcium magnesium phosphate fertilizer according to the weight ratio of the fertilizer slurry to the calcium magnesium phosphate fertilizer =1 to (0.18-0.3).
The fineness of the ground phosphate rock is-100 meshes and is more than 93 percent, and-200 meshes and is more than 78 percent.
In the method for manufacturing the compound fertilizer, the basic fertilizer containing nitrogen, phosphorus and potassium is monoammonium phosphate, diammonium phosphate, potassium chloride, potassium sulfate and the like.
The principle of the manufacturing method of the nitrogen-phosphorus compound fertilizer is as follows: first, urea is dissolved in a sulfuric acid solution to form a urea sulfate solution. The urea is weakly alkaline and can react with sulfuric acid to generate urea sulfate, and the chemical reaction formula is as follows:
the urea sulfate adduct has a high solubility in water and retains the acidity of the sulfuric acid in the adduct, which decreases with increasing proportion of urea in the adduct.
In production, metered concentrated sulfuric acid, water and granular urea are added into a dissolving tank with a stirrer, the granular urea is dissolved in a sulfuric acid solution to generate a urea sulfate solution, and the temperature of the solution is kept at 70-80 ℃. The solution composition is as follows: urea, sulfuric acid and water in a molar ratio of (3.1-3.5) to (1) to (5.5-6.5).
The urea sulfate solution can be used for decomposing the ground phosphate rock because of strong acidity. During the acid mine reaction, urea and calcium sulfate form a stable adduct, tetra urea calcium sulfate. The tricalcium phosphate in the ground phosphate rock is mostly converted into monocalcium phosphate and dicalcium phosphate which can be absorbed by plants. In the presence of sulfurWhile the urea acid decomposes the powdered rock phosphate, some impurities such as carbonate (RCO) in the powdered rock phosphate3) Iron oxide (Fe)2O3) Alumina (Al)2O3) Etc. also participate in the reaction to consume sulfuric acid. In order to make the reaction of decomposing the powdered rock phosphate by the urea sulfate proceed completely,the process contemplates the use of an excess of urea sulfate solution, so that the slurry will contain a certain amount of free phosphoric acid and sulfuric acid. The chemical reaction formula for the reaction of urea sulfate and powderedrock phosphate can be simply expressed as:
in the formula: a + b = 1.
In the process of preparing the fertilizer slurry by decomposing the phosphate rock powder by the urea sulfate solution, the proportion of the phosphate rock powder to the urea sulfate solution is that the phosphate rock powder to the urea sulfate solution is =1 to (3.06-3.19) (weight ratio), the reaction temperature is 70-75 ℃, the reaction time is 40-60 minutes, the fineness of the phosphate rock powder is-100 meshes and is more than 93%, and the fineness of-200 meshes and is more than 78%.
By adopting the manufacturing method of the compound fertilizer, excessive sulfuric acid is used in the manufacturing process of the fertilizer slurry, so that the content of free acid in the slurry is high, and a neutralizer is required to be used during slurry returning granulation. In consideration of the fact that the available nutrients in the fertilizer are not reduced too much after the neutralizing agent is used, and the calcium-magnesia phosphate fertilizer is rich in medium elements such as calcium and magnesium, the calcium-magnesia phosphate fertilizer is selected as the neutralizing agent. But the effective P in calcium magnesium phosphate fertilizer2O5All are citrate soluble, and the neutralized product should ensure the water solubility P in the fertilizer2O5And effective P2O5The ratio of the fertilizer to the fertilizer meets the requirements of the national compound fertilizer standard.
The reacted slurry is conveyed to a spray pipe arranged in a rotary drum granulator by a slurry pump, and is atomized into fine liquid drops by a spray head and sprayed onto a continuously stirred bed layer. The neutralizer calcium magnesium phosphate fertilizer or the granulating raw material such as potassium chloride, potassium sulfate, monoammonium phosphate, diammonium phosphate and the like and the return material are respectively conveyed into a granulator after being metered, the granulating temperature is 50-70 ℃, and the granulating water content is 3.5-6.5% (weight percentage). The addition amount of the neutralizer calcium magnesium phosphate fertilizer is that the weight ratio of the fertilizer slurry to the calcium magnesium phosphate fertilizer is that =1 to (0.18-0.3). The granulated fertilizer particles overflow from the outlet end of the granulator to the inlet end of the rotary dryer, and hot furnace gas for drying is provided by burning coal gas or heavy oil or coal. And (3) feeding the dried material into a vibrating screen from a discharge box of the dryer for classification, crushing large particles by a crusher, mixing the large particles with fine powder, returning the mixture to a granulator, and packaging the qualified particles as a product.
Compared with the prior art, the invention has the following advantages:
1. the invention aims at two phosphate fertilizer varieties of common calcium and calcium magnesium phosphate fertilizer and the largest nitrogen fertilizer variety of urea in China, produces granular compound fertilizer products by one-step method through organic combination, and accords with the development direction of compound fertilizers in China.
2. The invention improves the traditional ordinary calcium production process and the Urea Superphosphate (USP) production process, starts from the basic conditions of low reaction activity and poor curing performance of phosphate rock in China, eliminates the curing period of 6-9 days in ordinary calcium production and the procedure of preparing granular fertilizer by secondary processing of powdery fertilizer, shortens the production period, improves the labor productivity and reduces the investment cost.
3. In the invention, because the alkaline urea is introduced in the reaction process and the operation is carried out under a proper temperature condition, the fluorine contained in the phosphorite basically does not escape, and the three wastes are not discharged, so that the operation environment is greatly improved, and the method is a clean production process which meets the modern environmental protection requirement.
4. The granular nitrogen-phosphorus or nitrogen-phosphorus-potassium compound fertilizer with the total nutrient of more than 25% obtained by the invention has better physical properties, and the product quality meets the requirements of the national compound fertilizer standard GB 15063-94. The fertilizer contains reasonable water-soluble phosphorus/citrate-soluble phosphorus ratio, has the characteristics of quick fertilizer availability and farmyard manure durability, meets the large demand of crops on phosphorus in certain growth periods, ensures that the phosphorus is continuously and stably obtained in the whole growth period of the crops, and improves the utilization rate of the phosphate fertilizer. The nitrogen in the product is in the form of calcium sulfate tetra-urea, so that the leaching and volatilization loss of urea are avoided, and a fertilizer efficiency test proves that the product can effectively improve the utilization rate of urea. In addition, the product is rich in medium elements such as calcium, magnesium and sulfur required by crop growth, and is beneficial to plant growth and maintenance of balance of soil nutrients.
The following are specific examples of the present invention. The examples are intended to further illustrate the invention, but not to limit it. The percentages in the examples of the invention are percentages by weight.
Example 1:
granular urea 2.41 kg/hr, sulfuric acid (93% H)2SO4) 1.28 kg/h, 1.20 kg/h of water were added uniformly to a jacketed stirred reactor, and the particulate urea was dissolved in the sulfuric acid solution as a clear urea sulfate solution at a temperature of 70 ℃ for 10 minutes. The solution overflows into a mixing reactor with stirring and jacket heat preservation and contains P2O533.85% Kaiyang ground phosphate rock (-100 mesh 93.6%, -200 mesh 79.7%) was added uniformly to the mixing reactor in an amount of 1.58 kg/h for 40 minutes at a reaction slurry temperature of 70 ℃. The chemical composition of the slurry for sampling analysis is as follows: full P2O58.34% of water-soluble P2O56.18%, effective P2O57.35 percent, 17.13 percent of total N, 15.22 percent of free moisture and 88.13 percent of phosphorite decomposition rate. The slurry is uniformly conveyed by a rubber tube pump, is sprayed out through a spray pipe and is dispersed into fine liquid drops, and is mixed with a neutralizer and a return material in a rotary drum granulator for granulation, wherein the addition amount of the neutralizer, namely the calcium magnesium phosphate fertilizer, is 1.17 kg/h, the temperature of the granulated material in the granulator is 65-70 ℃, the moisture of the granulated material is 5.5-6.5%, and the multiple of the return material is 2.43 times. After the granulated material is dried by a rotary dryer, the percentage of qualified dried material particles (-4.75 + 1.0 mm) is 80.2%. The chemical analysis result of the nitrogen-phosphorus compound fertilizer product is as follows: total N16.59%, water soluble P2O54.25%, effective P2O59.13%, water content 3.37%, water-soluble P2O5Effective P2O546.55 percent of total nutrient (N + P)2O5) 25.72 percent, and the content of medium elements is as follows: CaO18.42%, MgO3.21%, S7.75%, compression strength of granules 12.02N/granule.
Example 2:
granular urea 2.49 kg/hr, sulfuric acid (93%H2SO4) 1.24 kg/h and 1.26 kg/h of water were added uniformly to a jacketed stirred reactor, and the particulate urea was dissolved in the sulfuric acid solution as a clear urea sulfate solution at 80 ℃ for 10 minutes. The solution overflows into a mixing reactor with stirring and jacket heat preservation and contains P2O533.85% Kaiyang ground phosphate rock (-100 mesh 93.6%, -200 mesh 79.7%) was added uniformly to the mixing reactor in an amount of 1.56 kg/h, reaction time 60 minutes, reaction slurry temperature 75 ℃. The chemical composition of the slurry for sampling analysis is as follows: full P2O58.10% of water-soluble P2O56.23%, effective P2O57.41 percent, 17.50 percent of total N, 16.61 percent of free moisture and 91.48 percent of phosphorite decomposition rate. MaterialThe slurry is uniformly conveyed by a rubber tube pump, is sprayed out through a spray pipe and is dispersed into fine liquid drops, and is mixed with a neutralizer and a return material in a rotary drum granulator for granulation, wherein the addition amount of the neutralizer, namely the calcium magnesium phosphate fertilizer, is 1.33 kg/h, the temperature of the granulated material in the granulator is 69-73 ℃, the moisture of the granulated material is 3.0-4.5%, and the multiple of the return material is 2.04 times. After the granulated material is dried by a rotary dryer, the percentage of qualified dried material particles (-4.75 + 1.0 mm) is 82.5%. The chemical analysis result of the nitrogen-phosphorus compound fertilizer product is as follows: total N16.80%, water soluble P2O53.61%, effective P2O58.99%, water content 2.01%, water soluble P2O5Effective P2O540.16%, total nutrient (N + P)2O5) 25.79 percent, and the content of the medium elements is as follows: CaO18.31%, MgO3.43%, S7.20%, compression strength of particles 18.55N/particle.
Example 3:
granular urea 3.00 kg/hr, sulfuric acid (93% H)2SO4) 1.52 kg/h, 1.56 kg/h of water were added uniformly to a jacketed stirred reactor, and the particulate urea was dissolved in the sulfuric acid solution as a clear urea sulfate solution at 75 ℃ for 10 minutes. The solution overflows into a mixing device with stirring and jacket heat preservationIn the reactor, containing P2O533.85% Kaiyang ground phosphate rock (-100 mesh 93.6%, -200 mesh 79.7%) was added uniformly in an amount of 2.01 kg/h to the mixing reactor for 40 minutes at a reaction slurry temperature of 70 ℃. The chemical composition of the slurry for sampling analysis is as follows: full P2O58.46% of water-soluble P2O56.32%, effective P2O57.61 percent, 17.15 percent of total N, 16.38 percent of free moisture and 89.95 percent of phosphorite decomposition rate. The prepared fertilizer slurry is uniformly delivered into a rotary drum granulator by a rubber tube pump at the flow rate of 8.09 kg/h, and the calcium magnesium phosphate fertilizer (containing P)2O512.53%) at 2.38 kg/h, monoammonium phosphate (N11.5%; effective P2O540%, granularity<1.0 mm 98.6%,<0.45 mm 81.1%,<1.80 kg/h, potassium chloride (K)2O60%,<1.9 mm 95.05%,<0.45 mm 42.0%) 2.69 kg/h, respectively metering and uniformly adding into a granulator, mixing and granulating the slurry with a neutralizer, a base fertilizer and a return material, wherein the temperature of the granulated material is 60-67 ℃, themoisture of the granulated material is 3.5-4.0%, and the multiple of the return material is 1.44, after the granulated material is dried by a dryer, the qualified particle percentage (-4.75 + 1.0 mm) of the dried material is 84.5%, the specification of the product nitrogen-phosphorus-potassium compound fertilizer is 12-12-12,the chemical analysis results are: total N12.12%, effective P2O512．92％，K212.27% of O, 2.49% of water and water-soluble P2O5Effective P20559.29 percent of total nutrient (N + P)2O5+K2O) is 37.31 percent, and the content of the medium elements is: CaO14.53%, MgO3.05%, S7.97%, compression strength of particles 10.32N/particle.
Example 4:
granular urea 2.71 kg/hr, sulfuric acid (93% H)2SO4) 1.49 kg/h, 1.38 kg/h of water were added uniformly to a jacketed stirred reactor, and the particulate urea was dissolved in the sulfuric acid solution as a clear urea sulfate solution at 75 ℃ for 10 minutes. The solution overflows into a stirrer,In a jacketed insulated mixing reactor, containing P2O533.85% Kaiyang ground phosphate rock (-100 mesh 93.6%, -200 mesh 79.7%) was added uniformly to the mixing reactor in an amount of 1.82 kg/h for 40 minutes at a reaction slurry temperature of 70 ℃. The chemical composition of the slurry for sampling analysis is as follows: full P2O58.35% of water-soluble P2O56.29%, effective P2O57.52 percent, 16.90 percent of total N, 15.71 percent of free moisture and 90.06 percent of phosphorite decomposition rate. The prepared fertilizer slurry is uniformly delivered into a rotary drum granulator by a rubber tube pump at the flow rate of 7.44 kg/h, and a neutralizer calcium magnesium phosphate fertilizer (containing P)2O512.53%) at 1.53 kg/h, powdered monoammonium phosphate (N11.5%; effective P2O540.0 percent, granularity less than 1.0 mm 98.6 percent and less than 0.45 mm 81.1 percent, 1.66 kg/h, potassium sulfate (K)2O50%,<1.0 mm 97.0%,<0.45 mm 86.5%) 2.99 kg/h, respectively and uniformly adding into a granulator after metering, mixing and granulating the slurry with a neutralizer, a base fertilizer and a return material, wherein the temperature of the granulated material is 54-58, the moisture of the granulated material is 4.5-5.0%, and the multiple of the return material is 1.43 times, after the granulated material is dried by a dryer, the qualified particle percentage (-4.75 + 1.0 mm) of the dried material is 79.8%, the specification of the product nitrogen-phosphorus-potassium compound fertilizer is 12-11-13, and the chemical analysis result is that: total N12.30%, effective P2O510．89％，P2O513.00%, water content 1.89%, water-soluble P2O5Effective P2O561.89%, total nutrient (N + P)2O5+K2O) is 36.19 percent, and the content of medium elements is as follows: CaO13.56%, MgO2.45%, S8.51%, compression strength of granule 18.13N/granule.
Claims (5)
1. A method for preparing granular nitrogen-phosphorus compound fertilizer containing secondary elements is characterized by comprising the following steps:
(1) dissolving urea in a sulfuric acid solution to generate a urea sulfate solution, wherein the temperature of the solution is kept at 70-80 ℃, the ratio of urea to sulfuric acid to water is (3.1-3.5) = (1): (5.5-6.5) (molar ratio),
(2) adding phosphate rock powder into a urea sulfate solution to react to prepare fertilizer slurry, wherein the ratio of the phosphate rock powder to the urea sulfate solution is phosphate rock powder to urea sulfate solution = 1: 3.06-3.19 (weight ratio), the reaction temperature is 70-75 ℃, the reaction time is 40-60 minutes,
(3) and neutralizing and granulating the fertilizer slurry by using a neutralizer, wherein the neutralizer is a calcium magnesium phosphate fertilizer, and finally preparing the granular nitrogen-phosphorus compound fertilizer.
2. The method for producing a compound fertilizer according to claim 1, characterized in that: in the process of granulating the fertilizer slurry, a neutralizer calcium magnesium phosphate fertilizer and a basic fertilizer containing nitrogen, phosphorus and potassium are added, and finally the granular nitrogen-phosphorus-potassium compound fertilizer containing medium elements can be prepared.
3. The method for producing a compound fertilizer according to claim 1 or 2, wherein the ratio of the fertilizer slurry to the calcium-magnesia phosphate fertilizer as the neutralizer is 1: 0.18 to 0.3 (by weight).
4. The method for producing a compound fertilizer according to claim 1, characterized in that: the fineness of the ground phosphate rock is-100 meshes larger than 93 percent, and-200 meshes larger than 78 percent.
5. The method for manufacturing a compound fertilizer according to claim 2, characterized in that: the basic fertilizer containing nitrogen, phosphorus and potassium is monoammonium phosphate, diammonium phosphate, potassium chloride and potassium sulfate.
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| CN100348550C (en) * | 2004-02-06 | 2007-11-14 | 河北天人化工股份有限公司 | Production method of urocomposite fertilizer |
| CN102358726A (en) * | 2011-07-11 | 2012-02-22 | 熊建超 | Urea sulfate and preparation method thereof |
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| CN102731214B (en) * | 2012-07-12 | 2014-05-07 | 个旧市绿保复合肥有限责任公司 | Production process of sugarcane slow release fertilizer |
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| CN113597406A (en) * | 2018-12-21 | 2021-11-02 | 涡龙设备与工艺公司 | Method for recovering phosphorus |
| CN109593003A (en) * | 2019-01-31 | 2019-04-09 | 云南云天化以化磷业研究技术有限公司 | A kind of production method improving the water-soluble phosphorus content of citrate acid soluble phosphatic fertilizer |
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