CN101618974B - Method for preparing triple superphosphate fertilizer by using waste water generated in synthetic process of 2, 4, 6-trichloropyrimidine - Google Patents
Method for preparing triple superphosphate fertilizer by using waste water generated in synthetic process of 2, 4, 6-trichloropyrimidine Download PDFInfo
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- CN101618974B CN101618974B CN200910117390XA CN200910117390A CN101618974B CN 101618974 B CN101618974 B CN 101618974B CN 200910117390X A CN200910117390X A CN 200910117390XA CN 200910117390 A CN200910117390 A CN 200910117390A CN 101618974 B CN101618974 B CN 101618974B
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- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a method for preparing triple superphosphate fertilizer by using waste water generated in the synthetic process of 2, 4, 6-trichloropyrimidine, which comprises the following steps: separating out a catalyst in the waste water by a reduced pressure distillation method, and acquiring calcium phosphate in a deposition mode; then mixing the calcium phosphate and phosphorous acid in a certain proportion, stirring, still standing, depositing and separating out deposits; and drying for 2-3 hours through decompression at the constant temperature of 70+/-5 DEG C and under the vacuum degree of 60-80kPa to acquire the triple superphosphate fertilizer. The prepared finished product of the triple superphosphate fertilizer has high contents of phosphorus (total phosphorus, available phosphorus and water-soluble phosphorus) and low mass fractions of free acid and free water, and each technical index of the triple superphosphate fertilizer is superior to the requirement of high-class products in the Chemical Industry Standard of the People's Republic of China (GB 21634-2008). Meanwhile, the catalyst in a waste liquid is recovered, the phosphorus and the organic catalyst in the waste liquid can be recycled, and the method has good social meanings and high economic value.
Description
Technical field
The invention belongs to wastewater treatment and recovery and utilization technology field, relate to a kind of 2,4, the recovery utilisation technology of phosphorus and catalyzer in the waste water that produces in the 6-trichloropyrimidine building-up process, be specifically related to a kind ofly utilize 2,4, the waste water that produces in the 6-trichloropyrimidine building-up process prepares the method for triple superphosphate fertilizer.
Background technology
Triple superphosphate fertilizer is used widely in agriculture production as one of member of phosphate fertilizer family.In the double superhosphate phosphorus mainly consist of a water mono-calcium phosphate and small-amount free acid, but do not contain or seldom contain gypsum.Because the various impurity that bring in phosphorus ore and the phosphoric acid are so still contain the phosphoric acid salt of small amounts of iron, aluminium and magnesium in the product.Finished product gray or canescence powdery contain available phosphorus usually (with P
2O
5Meter) 42%～44%.Because the content of phosphorus is about 2 times of normal superphosphate in the triple superphosphate fertilizer, so the title of double superhosphate is arranged.
Double superhosphate can make base manure or topdress, seed manure, foliage top dressing, foliage spray and produce the raw material of compound fertilizer.Because of triple superphosphate fertilizer is the water soluble phosphorous fertilizer of high density, do not contain gypsum, the concentration height is convenient to transportation and storage, and is good in economic efficiency.Its amount of application can reduce with reference to normal superphosphate in right amount according to phosphorus pentoxide content as required.Double superhosphate belongs to the quick-acting phosphate fertilizer of subacidity, is the highest single water soluble phosphorous fertilizer of present widely used concentration, the fertilizer efficiency height, and adaptability is strong, has the effect of improvement alkaline soil.Main plant phosphoric and the calcium constituents etc. supplied with promote plant germination, root growth, plant development, branch, solid and ripe.Double superhosphate both can be used separately, also can mix use with other nutrient.If mix use with nitrogenous fertilizer, have certain nitrogen fixation.Because of double superhosphate sulfur acid calcium not, so to happiness sulphur crop, as potato, leguminous crop and crop in cruciferae etc., and use on the soil of a lack of sulfur, its effect is not as good as the calcium superphosphate of equivalent effective constituent.But to impeded drainage, the rice terrace that reductibility is strong, application effect is better.
Phosphorus is the integral part of nucleic acid and thuja acid, is to form protoplasma and nuclear main component, and almost many important organic compound all contain phosphorus in the plant materials.Phosphorus has important effect to plant nutrition, and phosphorus has the accelerating effect, is important to results and crop quality; Using of phosphate fertilizer can promote that crop and fruit is full; Phosphorus can improve the quality of many fruit, vegetables and food crop, and output improves.The content of phosphorus in plant materials is only second to nitrogen and potassium, and generally content is higher in seed.Phosphorus participates in photosynthesis, respiration, energy storage and transmission, cell fission, cell increase and some other process in plant materials.Phosphorus can promote the formation and the growth of early stage root system, improves the ability that plant adapts to external environmental condition, helps to strengthen the disease resistance of some plants and helps the anti-severe cold of spending winter of plant.
Calcium is one of component of cell walls, and the formation of plasma membrane, the activation of enzyme etc. are had good effect, can strengthen the resistibility of crop to disease and pest, a large amount of calcium of quick growth needs of crop.But the calcium in the soil exists with the form of Calucium Silicate powder (acid soil) and lime carbonate (neutrality and alkaline soil) mostly, the calcium oxide that in the production process of triple superphosphate fertilizer, adds, and acidity that can sweetening of the soil plays the effect of improving the soil.
The method of traditional mode of production double superhosphate is to be raw material with the Rock Phosphate (72Min BPL), reacts with phosphoric acid (phosphoric acid can make from wet method and Re Fa) and Rock Phosphate (72Min BPL), and it is mono-calcium phosphate and Lin Suanergai that chemical precipitation, defluorinate obtain primary product.This production method is owing to when impurity such as contained iron, aluminium, magnesium are too high in phosphorus ore and the phosphate raw material, can make the product bonding, and easily by soil fixing, movability is little, and crop is difficult to absorb.Iron in the phosphoric acid by wet process, aluminium ion concentration are too high, can make that hydrogen ion activity reduces in the phosphoric acid, thereby have reduced the ability of phosphorolytic cleavage phosphorus ore.In addition, defluorination process control is unstable, makes the fluorine content height in the finished product, and plant and environment are had bigger infringement and pollution, the difficult requirement that reaches the GB premium grads.
Pyrimidine and derivative thereof are the important synthetic medicine of a class and the intermediate of active fuel, are mainly used in synthesizing of anti-microbial infection medicine, hypnosis and downern and synthesizing of active fuel.2,4, the 6-trichloropyrimidine is as the intermediate of synthetic medicine and active fuel, and its demand is bigger.It with the barbituric acid raw material, with the phosphorus oxychloride is chlorizating agent, under the catalysis of QD catalyst compounded (N, N-Diethyl Aniline, N, accelerine, quinoline), Synthetic 2,4, contain a large amount of phosphorus (content of phosphorus is 3.52～3.72g/L, exists with the form of phosphoric acid) and catalyzer in the waste liquid that produces in the technology of 6-trichloropyrimidine, if with its direct discharging, can cause serious pollution to environment.If the phosphorus in the waste liquid is recycled, it is turned waste into wealth, then have good social effect and very high economic worth.
Summary of the invention
The purpose of this invention is to provide and a kind ofly utilize 2,4, the waste water that produces in the 6-trichloropyrimidine building-up process prepares the method for triple superphosphate fertilizer.
The present invention prepares the method for triple superphosphate fertilizer, comprises following two processing steps:
(1) recovery of catalyzer
Regulate pH to 8.5～10.5 of waste water, stir and make organic phase and inorganic layering mutually, and separate organic phase with mutually inorganic; Organic phase is cooled off with the distillation of water vapour distillation under vacuum, and the yellow oil that slips out in the liquid is catalyzer, recycles; The rate of recovery of catalyzer is 81～89%.Inorganicly be used to prepare triple superphosphate fertilizer mutually.
(2) preparation of triple superphosphate fertilizer
The inorganic calcium oxide that adds its quality 0.8～2.0% in mutually behind above-mentioned recovery catalyzer stirs calcium oxide is partly dissolved; The concentrated hydrochloric acid that adds waste liquid quality 8～12% again stirs, and calcium oxide is dissolved fully; Reconcile pH to 11.0～14.0, leave standstill, precipitation, and isolate precipitation, in 140～160 ℃ of oven dry down, obtain calcium phosphate; The rate of recovery of phosphorus is 99.77%～99.86% in the waste water.
Calcium phosphate is mixed with the mass ratio of phosphoric acid with 1: 1.0～1: 1.3 (preferred proportion is 1: 1.2～1: 1.25), stir, leave standstill, precipitation, and isolate precipitation, in 70 ± 5 ℃ constant temperature, vacuum tightness is drying under reduced pressure 2～3 hours under the condition of 60～80kPa, obtains triple superphosphate fertilizer.Productive rate 90.02%～93.60%.
The triple superphosphate fertilizer of the present invention's preparation carries out check and analysis according to " State Standard of the People's Republic of China " requirement (GB21634-2008), and total phosphorus is (with P
2O
5Meter) massfraction is 44.05%～47.25%, (GB is 〉=44.0); Available phosphorus is (with P
2O
5Meter) massfraction is 42.50%～46.14% (GB is 〉=42.0%); Water-soluble phosphorus is (with P
2O
5Meter) massfraction is 38.00～45.34% (GB is 〉=36.0%); Free acid is (with P
2O
5Meter) massfraction is 3.55%～3.85% (GB is≤7.0%); The massfraction of free-water is 2.93%～3.50% (GB is≤8.0%).Its every technical indicator all is better than the requirement of " State Standard of the People's Republic of China " (GB 21634-2008) premium grads.
The present invention compared with prior art has the following advantages:
1, the present invention is with 2; 4; the waste water that produces in the 6-trichloropyrimidine building-up process is raw material, reclaims by methods such as precipitations and makes triple super phosphate fertilizer, has realized 2; 4; the recycling of phosphorus in the waste liquid that produces in the 6-trichloropyrimidine production process (rate of recovery of phosphorus is 99.77%～99.86%) is turned waste into wealth it, has both protected environment; make full use of the phosphorus in the waste water again, had good social effect and very high economic worth.
2, the present invention has reclaimed QD catalyst compounded (rate of recovery of catalyzer is 81～89%) simultaneously in the recovery technology of phosphorus, makes catalyzer 2,4, can recycle in 6-trichloropyrimidine synthetic, effectively reduces synthetic cost.
3, in the triple superphosphate fertilizer finished product of the present invention's preparation, the content height of phosphorus (total phosphorus, available phosphorus, water-soluble phosphorus), the massfraction of free acid and free-water is low, and its every technical indicator all is better than the requirement of " People's Republic of China's chemical industry standard " (GB 21634-2008) premium grads.Foreign matter content is few in the triple superphosphate fertilizer finished product of producing, and helps the absorption of plant, to plant and not infringement and pollution of soil.
4, the method for the triple superphosphate fertilizer of the present invention's preparation, the technology simple operations is convenient, and cost is low, the productive rate height.
5, the present invention does not have waste gas, waste liquid, waste sludge discharge in preparation process, and the use of organic solvent-free meets the synthetic theory of Green Chemistry, environmental protection.
Embodiment
Embodiment 1
(1) recovery of catalyzer
Get 2,4, the waste water 500mL that produces in the 6-trichloropyrimidine building-up process adds 40mL distilled water in the beaker of 1000mL, to the NaOH solution 15.5mL that wherein adds mass concentration 20%, transfers pH to 8.50.Solution is divided into two-layer, and the upper strata is a khaki color emulsion, and lower floor is a colourless liquid.The khaki color emulsion that separates and collect the upper strata with separating funnel; Add the 40mL water washing in the khaki color emulsion of collecting, stir, leave standstill, separate with separating funnel, subnatant is used to prepare triple superphosphate fertilizer with last time gained subnatant merging.Add 40mL distilled water in the yellow emulsion of topsoil (organic phase), distill out organic phase with the water vapour distillation under vacuum then, cooling 60min, slipping out liquid is divided into two-layer, the upper strata yellow oil is catalyzer, separate, collect with separating funnel, and to record its volume be 2.90mL that the rate of recovery of calculating catalyzer is 85.29%; Lower floor's colourless liquid merges with front gained subnatant, is used to prepare triple superphosphate fertilizer.
(2) preparation of triple superphosphate fertilizer
Pipette lower floor's mixed solution that the above-mentioned separation of 500mL obtains in the beaker of 1000mL, add the 5.0403g calcium oxide, stir calcium oxide is partly dissolved; Add industrial concentrated hydrochloric acid 50.0mL again, stir, calcium oxide is dissolved fully; The NaOH solution 180.0mL that drips mass concentration 20% then reconciles pH to 13.6, leaves standstill, and precipitation is washed and isolated to precipitation with filtrate, in 156 ℃ of oven dry down, obtains 9.2870g calcium phosphate.The rate of recovery of phosphorus is 99.86% in the waste liquid.Mother liquor stays to do and prepares triple superphosphate fertilizer once more.
Take by weighing calcium phosphate 4.6332g, mix, stir, leave standstill, precipitation, centrifugation with the phosphoric acid 3.41mL (mass ratio of calcium phosphate, phosphoric acid is 1: 1.260) of 1.712g/mL; With filtrate washing and isolate precipitation, place the freeze-day with constant temperature instrument, at 70 ℃, vacuum tightness is that drying under reduced pressure took out after 3 hours under the 70.0kPa, weighs after placing moisture eliminator to cool off 60min then, obtains triple superphosphate fertilizer 9.6118g, productive rate 91.60%.Filtrate staying done and prepared the triple super phosphate fertilizer use once more.
The triple superphosphate fertilizer of present embodiment preparation carries out check and analysis according to " State Standard of the People's Republic of China " requirement (GB21634-2008), and total phosphorus is (with P
2O
5Meter) massfraction is 46.25%, (GB is 〉=44.0); Available phosphorus is (with P
2O
5Meter) massfraction is 45.14% (GB is 〉=42.0%); Water-soluble phosphorus is (with P
2O
5Meter) massfraction is 44.04% (GB is 〉=36.0%); Free acid is (with P
2O
5Meter) massfraction is 3.55% (GB is≤7.0%); The massfraction of free-water is 2.93% (GB is≤8.0%).Its every technical indicator all is better than " State Standard of the People's Republic of China " (GB21634-2008) requirement of premium grads.
Embodiment 2
(1) recovery of catalyzer
Get 2,4, the waste water 500mL that produces in the 6-trichloropyrimidine building-up process adds 40mL distilled water in the beaker of 1000mL, to the NaOH solution 15.0mL that wherein adds mass concentration 20%, transfers pH to 8.00.Solution is divided into two-layer, and the upper strata is a khaki color emulsion, and lower floor is a colourless liquid.Separate and collect khaki color emulsion with separating funnel; Add the 40mL water washing in khaki color emulsion, stir, leave standstill, separate with separating funnel, subnatant is used to prepare triple superphosphate fertilizer with last time gained subnatant merging.Add 40mL distilled water in the yellow emulsion of topsoil (organic phase), distill out organic phase with the water vapour distillation under vacuum then, cooling 60min, slipping out liquid is divided into two-layer, the upper strata yellow oil is catalyzer, separate, collect with separating funnel, and to record its volume be 2.80mL that the rate of recovery of calculating catalyzer is 82.35%; Lower floor's colourless liquid merges with front gained subnatant, is used to prepare triple superphosphate fertilizer.
(2) preparation of triple superphosphate fertilizer
Pipette subnatant mixed solution that the above-mentioned separation of 500mL obtains in the beaker of 1000mL, add the 5.0352g calcium oxide, stir calcium oxide is partly dissolved; Add industrial concentrated hydrochloric acid 48.0mL again, stir, calcium oxide is dissolved fully; Drip the NaOH solution 170.0mL of mass concentration 20% then, reconcile pH to 12.9, leave standstill, precipitation is washed and isolated to precipitation with filtrate, in 160 ℃ of oven dry down, obtains 9.2859g calcium phosphate.The rate of recovery of phosphorus is 99.84% in the waste liquid.Filtrate staying done and prepared the triple super phosphate fertilizer use once more.
Take by weighing the calcium phosphate 4.6332g of above-mentioned preparation, mix with the phosphoric acid 3.30mL of 1.712g/mL (mass ratio of calcium phosphate, phosphoric acid is 1: 1.258), stir, leave standstill, precipitation, centrifugation; With filtrate washing and isolate precipitation, place the freeze-day with constant temperature instrument, at 65 ℃, vacuum tightness is that drying under reduced pressure took out after 2 hours under the 64.0kPa, weighs after placing moisture eliminator to cool off 40min then, obtains triple superphosphate fertilizer 9.4460g.Productive rate 90.02%.Filtrate staying done and prepared the triple super phosphate fertilizer use once more.
The triple superphosphate fertilizer of present embodiment preparation carries out check and analysis according to " State Standard of the People's Republic of China " requirement (GB21634-2008), and total phosphorus is (with P
2O
5Meter) massfraction is 44.05%, (GB is 〉=44.0); Available phosphorus is (with P
2O
5Meter) massfraction is 42.02% (GB is 〉=42.0%); Water-soluble phosphorus is (with P
2O
5Meter) massfraction is 38.00% (GB is 〉=36.0%); Free acid is (with P
2O
5Meter) massfraction is 3.85% (GB is≤7.0%); The massfraction of free-water is 3.50% (GB is≤8.0%).Its every technical indicator all is better than " State Standard of the People's Republic of China " (GB21634-2008) requirement of premium grads.
Embodiment 3
(1) recovery of catalyzer
Get 2,4, the waste water 500mL that produces in the 6-trichloropyrimidine building-up process adds 40mL distilled water in the beaker of 1000mL, to the NaOH solution 15.2mL that wherein adds mass concentration 20%, transfers pH to 8.40.Solution is divided into two-layer, and the upper strata is a khaki color emulsion, and lower floor is a colourless liquid.Separate and collect khaki color emulsion with separating funnel; Add the 40mL water washing in khaki color emulsion, stir, leave standstill, separate with separating funnel, subnatant is used to prepare triple superphosphate fertilizer with last time gained subnatant merging.Add 40mL distilled water in the yellow emulsion of topsoil (organic phase), distillate organic phase with water vapour underpressure distillation steaming method then, cooling 60min, slipping out liquid is divided into two-layer, the upper strata yellow oil is catalyzer, separate, collect with separating funnel, and to record its volume be 2.82mL that the rate of recovery of calculating catalyzer is: 82.94%; Lower floor's colourless liquid merges with front gained subnatant, is used to prepare triple superphosphate fertilizer.
(2) preparation of triple superphosphate fertilizer
Pipette subnatant mixed solution that the above-mentioned separation of 500mL obtains in the beaker of 1000mL, add the 5.0000g calcium oxide, stir calcium oxide is partly dissolved; Add concentrated hydrochloric acid 47.0mL again, stir, calcium oxide is dissolved fully; Drip the NaOH solution 175.0mL of mass concentration 20% then, reconcile pH to 13.5, leave standstill, precipitation is washed and isolated to precipitation with filtrate, in 158 ℃ of oven dry down, obtains 9.2842g calcium phosphate.The rate of recovery of phosphorus is 99.83% in the waste liquid.Filtrate staying done and prepared the triple super phosphate fertilizer use once more.
Take by weighing the calcium phosphate 4.6332g of above-mentioned preparation, mix with the phosphoric acid 3.35mL of 1.712g/mL (mass ratio of calcium phosphate, phosphoric acid is 1: 1.2585), stir, leave standstill, precipitation, centrifugation; Precipitation places the freeze-day with constant temperature instrument, in 71 ℃, takes out behind the drying under reduced pressure 2.5h under the vacuum tightness 66.0kPa, weigh after placing moisture eliminator cooling 45min, triple superphosphate fertilizer 9.4963g, productive rate is 90.50%.Filtrate staying done and prepared the triple super phosphate fertilizer use once more.
The triple superphosphate fertilizer of present embodiment preparation carries out check and analysis according to " State Standard of the People's Republic of China " requirement (GB21634-2008), and total phosphorus is (with P
2O
5Meter) massfraction is 45.15%, (GB is 〉=44.0); Available phosphorus is (with P
2O
5Meter) massfraction is 43.63% (GB is 〉=42.0%); Water-soluble phosphorus is (with P
2O
5Meter) massfraction is 41.10% (GB is 〉=36.0%); Free acid is (with P
2O
5Meter) massfraction is 3.70% (GB is≤7.0%); The massfraction of free-water is 3.13% (GB is≤8.0%); Its every technical indicator all is better than " State Standard of the People's Republic of China " (GB21634-2008) requirement of premium grads.
Embodiment 4
(1) recovery of catalyzer
Get 2,4, the waste water 500mL that produces in the 6-trichloropyrimidine building-up process adds 40mL distilled water in the beaker of 1000mL, to the NaOH solution 15.1mL that wherein adds mass concentration 20%, transfers pH to 8.20.Solution is divided into two-layer, and the upper strata is a khaki color emulsion, and lower floor is a colourless liquid.Separate and collect khaki color emulsion with separating funnel; Add the 40mL water washing in khaki color emulsion, stir, leave standstill, separate with separating funnel, subnatant is used to prepare triple superphosphate fertilizer with last time gained subnatant merging.Add 40mL distilled water in the yellow emulsion of topsoil (organic phase), distill out organic phase with the water vapour distillation under vacuum then, cooling 60min, slipping out liquid is divided into two-layer, the upper strata yellow oil is catalyzer, separate, collect with separating funnel, and to record its volume be 2.84mL that the rate of recovery of calculating catalyzer is 83.53%; Lower floor's colourless liquid merges with front gained subnatant, is used to prepare triple superphosphate fertilizer.
(2) preparation of triple superphosphate fertilizer
Pipette subnatant mixed solution that the above-mentioned separation of 500mL obtains in the beaker of 1000mL, add the 5.0013g calcium oxide, stir calcium oxide is partly dissolved; Add concentrated hydrochloric acid 46.0mL again, stir, calcium oxide is dissolved fully; Drip the NaOH solution 172.0mL of mass concentration 20% then, reconcile pH to 13.2, leave standstill, precipitation is washed and isolated to precipitation with filtrate, in 159 ℃ of oven dry down, obtains 9.2814g calcium phosphate.The rate of recovery of phosphorus is 99.80% in the waste liquid.Filtrate staying done and prepared the triple super phosphate fertilizer use once more.
Take by weighing the calcium phosphate 4.6332g of above-mentioned preparation, mix with the phosphoric acid 3.40mL of 1.712g/mL (mass ratio of calcium phosphate and phosphoric acid is 1: 1.2590), stir, leave standstill, precipitation, centrifugation; Precipitation places the freeze-day with constant temperature instrument, at 74 ℃, takes out behind the drying under reduced pressure 2.2h under the vacuum tightness 68.0kPa, weigh after placing moisture eliminator cooling 50min, triple superphosphate fertilizer 9.5520g, productive rate is 91.03%.Filtrate staying done and prepared the triple super phosphate fertilizer use once more.
The triple superphosphate fertilizer of present embodiment preparation carries out check and analysis according to " State Standard of the People's Republic of China " requirement (GB21634-2008), and total phosphorus is (with P
2O
5Meter) massfraction is 45.96%, (GB is 〉=44.0); Available phosphorus is (with P
2O
5Meter) massfraction is 44.87% (GB is 〉=42.0%); Water-soluble phosphorus is (with P
2O
5Meter) massfraction is 43.07% (GB is 〉=36.0%); Free acid is (with P
2O
5Meter) massfraction is 3.62% (GB is≤7.0%); The massfraction of free-water is 3.02% (GB is≤8.0%); Its every technical indicator all is better than " State Standard of the People's Republic of China " (GB21634-2008) requirement of premium grads.
Embodiment 5
(1) recovery of catalyzer
Get 2,4, the waste water 500mL that produces in the 6-trichloropyrimidine building-up process adds 40mL distilled water in the beaker of 1000mL, to the NaOH solution 15.3mL that wherein adds mass concentration 20%, transfers pH to 8.45.Solution is divided into two-layer, and the upper strata is a khaki color emulsion, and lower floor is a colourless liquid.Separate and collect khaki color emulsion with separating funnel; Add the 40mL water washing in khaki color emulsion, stir, leave standstill, separate with separating funnel, subnatant is used to prepare triple superphosphate fertilizer with last time gained subnatant merging.Add 40mL distilled water in the yellow emulsion of topsoil (organic phase), distill out organic phase with the water vapour distillation under vacuum then, cooling 60min, slipping out liquid is divided into two-layer, the upper strata yellow oil is catalyzer, separate, collect with separating funnel, and to record its volume be 2.88mL that the rate of recovery of calculating catalyzer is: 84.71%.Lower floor's colourless liquid merges with front gained subnatant, is used to prepare triple superphosphate fertilizer.
(2) preparation of triple superphosphate fertilizer
Pipette subnatant mixed solution that the above-mentioned separation of 500mL obtains in the beaker of 1000mL, add the 5.0005g calcium oxide, stir calcium oxide is partly dissolved; Add concentrated hydrochloric acid 47.0mL again, stir, calcium oxide is dissolved fully; Drip the NaOH solution 178.0mL of mass concentration 20% then, reconcile pH to 13.4, leave standstill, precipitation with the filtrate washing and isolate precipitation, is deposited in 157 ℃ of oven dry down, obtains 9.2861g calcium phosphate.The rate of recovery of phosphorus is 99.85% in the waste liquid.Filtrate staying done and prepared the triple super phosphate fertilizer use once more.
Take by weighing the calcium phosphate 4.6332g of above-mentioned preparation, mix with the phosphoric acid 3.38mL of 1.712g/mL (mass ratio of calcium phosphate and phosphoric acid is 1: 1.2595), stir, leave standstill, precipitation, centrifugation; Precipitation places the freeze-day with constant temperature instrument, at 75 ℃, takes out behind the drying under reduced pressure 2.7h under the vacuum tightness 65.0kPa, weigh after placing moisture eliminator cooling 55min then, triple superphosphate fertilizer 9.5278g, productive rate is 90.80%.Mother liquor stays to do and prepares the fertilizer use once more.
The triple superphosphate fertilizer of present embodiment preparation carries out check and analysis according to " State Standard of the People's Republic of China " requirement (GB21634-2008), and total phosphorus is (with P
2O
5Meter) massfraction is 44.87%, (GB is 〉=44.0); Available phosphorus is (with P
2O
5Meter) massfraction is 42.93% (GB is 〉=42.0%); Water-soluble phosphorus is (with P
2O
5Meter) massfraction is 38.99% (GB is 〉=36.0%); Free acid is (with P
2O
5Meter) massfraction is 3.80% (GB is≤7.0%); The massfraction of free-water is 3.41% (GB is≤8.0%); Its every technical indicator all is better than " State Standard of the People's Republic of China " (GB21634-2008) requirement of premium grads.
Claims (2)
1. utilize 2,4, the waste water that produces in the 6-trichloropyrimidine building-up process prepares the method for triple superphosphate fertilizer, comprises following two processing steps:
(1) recovery of catalyzer
Regulate pH to 8.0～8.5 of waste water, stir and make organic phase and inorganic layering mutually, and separate organic phase with mutually inorganic; Organic phase is cooled off with the distillation of water vapour distillation under vacuum, and the yellow oil that slips out in the liquid is catalyzer, recycles; Inorganicly be used to prepare triple superphosphate fertilizer mutually;
(2) preparation of triple superphosphate fertilizer
The inorganic calcium oxide that adds its quality 0.8～2.0% in mutually behind above-mentioned recovery catalyzer stirs calcium oxide is partly dissolved; The concentrated hydrochloric acid that adds waste liquid quality 8～12% again stirs, and calcium oxide is dissolved fully; Reconcile pH to 11.0～14.0, leave standstill, precipitation, and isolate precipitation, in 140～160 ℃ of oven dry down, obtain calcium phosphate;
Calcium phosphate is mixed with the mass ratio of phosphoric acid with 1: 1.0～1: 1.3, stir, leave standstill, precipitation, and isolate precipitation, in 70 ± 5 ℃ constant temperature, vacuum tightness is drying under reduced pressure 2～3 hours under the condition of 60～80kPa, obtains triple superphosphate fertilizer.
2. utilize 2,4 according to claim 1, the waste water that produces in the 6-trichloropyrimidine building-up process prepares the method for triple superphosphate fertilizer, it is characterized in that: calcium phosphate mixes with the mass ratio of phosphoric acid with 1: 1.2～1: 1.25 in the described step (2).
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| CN102583867B (en) * | 2012-03-20 | 2013-12-18 | 石家庄杰克化工有限公司 | Method for treating waste water in chloro pyrimidine combining process |
| CN102633382B (en) * | 2012-04-10 | 2014-12-10 | 重庆紫光化工股份有限公司 | 4,6-dichloropyrimidine waste water treatment and resource recovery method |
| CN110759537B (en) * | 2019-11-18 | 2022-04-19 | 中铁轨道交通装备有限公司 | Hydrogen fuel cell wastewater treatment control system and method |
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|---|---|---|---|---|
| CN85102768B (en) * | 1985-04-01 | 1987-11-04 | 湖北省化学研究所 | Production of phosphoric acid and phosphate by hydrochloric acid hydrolysis of phosphorus rock |
| CN1371862A (en) * | 2001-02-28 | 2002-10-02 | 四川大学 | Method for producing calcium hydrogen phosphate fodder |
| CN1724342A (en) * | 2005-07-05 | 2006-01-25 | 宜昌市仁和矿业有限责任公司 | Process for mfg. industrial phosphoric acid by low-grade phosphorus deposit in hydrogen chloride decomposition |
| CN101456545A (en) * | 2008-12-25 | 2009-06-17 | 四川大学 | Method for producing triple superphosphate and co-producing calcium chloride by middle-low grade phosphate rock |
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2009
- 2009-07-22 CN CN200910117390XA patent/CN101618974B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102768B (en) * | 1985-04-01 | 1987-11-04 | 湖北省化学研究所 | Production of phosphoric acid and phosphate by hydrochloric acid hydrolysis of phosphorus rock |
| CN1371862A (en) * | 2001-02-28 | 2002-10-02 | 四川大学 | Method for producing calcium hydrogen phosphate fodder |
| CN1724342A (en) * | 2005-07-05 | 2006-01-25 | 宜昌市仁和矿业有限责任公司 | Process for mfg. industrial phosphoric acid by low-grade phosphorus deposit in hydrogen chloride decomposition |
| CN101456545A (en) * | 2008-12-25 | 2009-06-17 | 四川大学 | Method for producing triple superphosphate and co-producing calcium chloride by middle-low grade phosphate rock |
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