CN1165130A - Method for preparing sulfonyl azophoska compound fertilizer - Google Patents
Method for preparing sulfonyl azophoska compound fertilizer Download PDFInfo
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- CN1165130A CN1165130A CN 97105751 CN97105751A CN1165130A CN 1165130 A CN1165130 A CN 1165130A CN 97105751 CN97105751 CN 97105751 CN 97105751 A CN97105751 A CN 97105751A CN 1165130 A CN1165130 A CN 1165130A
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- repone
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Abstract
A process for producing compound S-base N-P-K fertilizer includes such steps as low-temp. reaction of potassium chloride on sulfuric acid to generate potassium hydrogen sulfate, addition of diluted phosphoric acid resulted from reaction of phosphorus ore with sulfuric acid, neutralizing with ammonia gas prepared from natural gas or coal and granulating, and features less energy consumption, low corrosion to apparatus, short productive flow and less investment in apparatus. Said fertilizer mainly contains ammonium hydrogen phosphate, ammonium potassium sulfate and ammonium sulfate.
Description
The present invention relates to a kind of production method of sulfenyl nitrogen-phosphorus-potassium compound fertilizer material, more specifically, the present invention relates to a kind of is the production method of the described fertilizer of raw material production with sulfuric acid, Repone K, phosphoric acid and ammonia.
At present, the nitrogen-phosphorus-potassium compound fertilizer of producing no chlorine or low chlorine generally is with nitrogenous, phosphorated and potassic finished product fertilizers are made through mixing granulation, only in view of this, its technology is simple, invest little, but, by used finished product fertilizer, as vitriolate of tartar is at high temperature to be made by Repone K and sulfuric acid, urea is made by synthetic ammonia, ammonium phosphate concentrates the ammonia neutralization by Phosphoric Acid Concentration or slip and makes, like this, begin to produce the whole process of these composite fertilizers, produce sulfenyl nitrogen-phosphorus-potassium compound fertilizer energy consumption height from raw material, technical process is long, investment is big, the product cost height is conspicuous.
Therefore, some researchists once studied the method for producing NpK complex fertilizer with basic raw materials such as sulfuric acid, phosphoric acid, ammonia, so that shortened process reduces production costs, obtained the compound manure of high-content nutrient.For example Japanese patent application JP81092187 has proposed to react with molten state with Repone K and excess sulfuric acid heating, so that remove the hydrogenchloride of generation, neutralizes with ammonia then.Chinese patent application number a kind of method of not having chlorine composite fertilizer with Repone K as raw material production of 91109650.7 propositions, this method is to allow the mixing acid of Repone K and sulfuric acid or sulfuric acid and phosphoric acid react 0.5-2 hour at 70-120 ℃, feed the ammonia neutralization again, reach 6.5-7 until pH.Chinese patent application numbers 94111088 has proposed a kind of using Repone K has been changed into sal enixum, allocates phosphoric acid again into, with in the ammonia and the method for production Nitrogen, Phosphorus and Potassium, wherein needs potassium hydrogen sulfate solution is adjusted to more than 120 ℃.The applicant once proposed a kind of using Repone K was changed into sal enixum, allocated phosphoric acid again into, with in the ammonia and the method (Chinese patent application number 93111207.9) of producing potassium sulphate type ternary composite fertilizer.All these methods comprise that all Repone K and sulfuric acid reaction produce the step of sal enixum, are little thermopositive reaction owing to generate the reaction of sal enixum, so need the outside to provide heat that this reaction can be carried out under comparatively high temps.Usually as with steam, deep fat or high-temperature flue gas, provide the heat of this reaction by the reactor interlayer, this heating means heat transfer coefficient is lower, and dispels the heat in a large number to the outside, so greatly reduces thermo-efficiency.If can take rational and effective heat supply scheme, to improving thermo-efficiency, reduce production costs, reduce equipment corrosion, the control that improves technological process plays crucial effects.Yet above-mentioned these patent applications are not made any improvement or are proposed more effective more rational technical scheme this processing step, improve the practical application effect of this method.
Therefore, in order to overcome the defective that exists in the prior art, the objective of the invention is to propose a kind of production method of not having the sulfenyl nitrogen-phosphorus-potassium compound fertilizer of chlorine or low chlorine.
In order to realize the object of the invention, can be achieved through the following technical solutions:
1, a kind of production method of sulfenyl nitrogen-phosphorus-potassium compound fertilizer is characterized in that described production method is made up of following step:
(1) adopts interchanger that 92-98% (weight) sulfuric acid is heated to 80-160 ℃, or adopt the gas of heat that Repone K is heated to 200-500 ℃;
(2) allow hot sulfuric acid of described 92-98% (weight) and Repone K, or 92-98% (weight) sulfuric acid and described thermal chlorination potassium, or hot sulfuric acid of described 92-98% (weight) and described thermal chlorination potassium, be (0.8-2.0) by mole with the ratio of sulfuric acid and Repone K: 1 reacted 30-120 minute; Obtain potassium hydrogen sulfate solution and hydrogen chloride gas;
(3) above-mentioned potassium hydrogen sulfate solution with P
2O
5Weight is counted the phosphoric acid solution of 18-25, respectively with K
2O and P
2O
5The weight meter is according to K
2O and P
2O
5Weight ratio be to mix in 0.5: 1 to 2: 1, obtain a kind of mixed solution;
(4) feed gaseous ammonia in the above-mentioned mixed solution and neutralize, reach 5.4-10, obtain the slip of moisture 25-40% (weight) until the pH of its slip;
(5) above-mentioned slip being sent into the hot-wind inlet temperature is 200-550 ℃ spray granulation drier or ammoniation and granulation drying machine, carries out granulating and drying and obtains its product.
2,, it is characterized in that described 92-98% (weight) sulfuric acid is heated to 100-140 ℃ according to above-mentioned 1 described production method.
3, according to 1 described production method, the gas that it is characterized in that described heat is the hot flue gases of coal combustion, Sweet natural gas or other fuel.
4,, it is characterized in that Repone K is heated to 250-400 ℃ according to 1 described production method.
5,, it is characterized in that being (1.0-1.6): 1 by the ratio of mole sulfuric acid and Repone K according to 1 described production method.
6,, it is characterized in that described sulfuric acid and Repone K reaction 50-100 minute according to 1 described production method.
7,, it is characterized in that described potassium hydrogen sulfate solution and described phosphoric acid solution are respectively with K according to 1 described production method
2O and P
2O
5The weight meter, its K
2O and P
2O
5The weight ratio ratio be 0.6: 1 to 1.5: 1.
8,, it is characterized in that be 6.5-9.0 with the gaseous ammonia neutralization until the pH that reaches its slip according to 1 described production method.
9,, it is characterized in that described hydrogen chloride gas water absorption obtains hydrochloric acid according to 1 described production method.
Below with the invention will be further described.
The present invention produces sal enixum by Repone K with acid reaction under lower temperature to produce dilute phosphoric acid by Rock Phosphate (72Min BPL) and sulfuric acid reaction, described sal enixum is mixed with described dilute phosphoric acid, use the gaseous ammonia neutralization of producing again by Sweet natural gas or coal, obtain product of the present invention by granulation, determine through material phase analysis: main thing is ammonium hydrogen phosphate, potassium-ammonium sulfate, ammonium sulfate mutually, secondly is vitriolate of tartar, ammonium chloride urea double salt etc.
At present, Repone K and vitriolic reaction are to adopt room temperature sulfuric acid and Repone K to react in enamel reaction still or in the Reaktionsofen of silicon carbide lining, because this reaction is little thermopositive reaction, so adopt the indirect heating mode to provide heat usually to reactive system, as the heat of this reaction is provided by the reactor interlayer with steam, deep fat or high-temperature flue gas, this type of heating heat transfer coefficient is lower, and dispels the heat in a large number to the outside, therefore greatly reduces thermo-efficiency.
It is to adopt normally used metal or nonmetallic heat exchanger on the chemical industry that the present invention heats sulfuric acid, allow steam, oil bath or stack gas pass through interchanger, at this moment, the two-phase of interchanger is liquid gas phase or liquid liquid phase, the heat exchange efficiency height, and before control instruments being installed in the sulfuric acid inlet, like this, sulfuric acid is because of the heating temperature is not low, and is little to equipment corrosion, can prolong the equipment usage period, boost productivity.
At first, allow 92-98% (weight) sulfuric acid stream through under meter, again by interchanger, through steam, stack gas or oil bath heating, the sulfuric acid temperature reaches 80-160 ℃.Preferably 100-140 ℃, more preferably 110-130 ℃.
Perhaps can adopt high-temperature flue gas directly Repone K to be heated to 200-500 ℃.Preferably Repone K is heated to 250-400 ℃.More preferably Repone K is heated to 250-350 ℃.
With 92-98% (weight) sulfuric acid heating or that do not heat and Repone K that do not heat or heating, count (0.8-2.0) with mole: 1 ratio adds in the reactive tank continuously equably.Described sulfuric acid preferably heating or that do not heat is (1.0-1.6) with the mol ratio of Repone K that do not heat or heating: 1, and sulfuric acid more preferably heating or that do not heat is (1.0-1.1) with the mol ratio of Repone K that do not heat or heating: 1.
This individual layer reactive tank is with acid-proof ceramic tile or any other acid resisting material lining, and the outer lagging material that applies need not heating installation or heater block heats reactive tank.
The reaction times of above-mentioned sulfuric acid and Repone K generally is 30-120 minute, preferably 50-100 minute, and more preferably 60-80 minute.
The sal enixum mixture that Repone K and sulfuric acid reaction obtain flows out from reactive tank continuously, deliver to concentration be that 18-25% is (with P
2O
5Meter) dilute phosphoric acid blended tempering tank, simultaneously, adopt normally used method to collect the hydrogen chloride gas that above-mentioned reaction produces from reactive tank top, and its gas is delivered to the absorption tower absorb, but absorption agent is selected the medium of water or other absorbing hydrogen chlorides, preferably water for use.If make water, then can obtain hydrochloric acid by-product.
Described dilute phosphoric acid is to adopt normally used phosphoric acid production method to produce, and promptly by Rock Phosphate (72Min BPL), through fragmentation, ball milling is to the 80-120 order, adds sulfuric acid and decomposes the 18-25% that obtains (with P
2O
5Meter) dilute phosphoric acid, the SO of liquid phase in extracting phosphoric acid groove
3Content is advisable with 2-5%.
Above-mentioned potassium hydrogen sulfate solution is according to K
2O and P
2O
5Weight ratio be 0.5-1 to 2: 1 adds and to be equipped with in the tempering tank of described dilute phosphoric acid solution, obtains a kind of mixed solution; Preferably the sal enixum mixture solution is according to K
2O and P
2O
5Weight ratio be to add in the described dilute phosphoric acid solution, in 0.6: 1 to 1.5: 1 more preferably according to K
2O and P
2O
5Weight ratio be to add in the described dilute phosphoric acid solution in 0.8: 1 to 1.2: 1.But the ratio of described sal enixum and described dilute phosphoric acid can be adjusted according to practical condition and fertilizer user's requirement.
With sal enixum in the tempering tank and dilute phosphoric acid mixed solution, with being pumped in the tubular reactor, feeding is neutralized by coal or Sweet natural gas, hydrogen and nitrogen synthetic gaseous ammonia.In it and degree can according in and the pH value of slip controlled, thereby usage quantity that can pilot-gas ammonia.In and the pH of slip generally be controlled at 5.4-10.Be preferably 6.5-9.0, more preferably 7.5-8.5.
Certainly, also can add described dilute phosphoric acid then, carry out neutralizing second time with gaseous ammonia again with in the described gaseous ammonia and described phosphoric acid hydrogen potassium solution.When implementing this mode, the pH value of the potassium hydrogen phosphate of use and the concentration of dilute phosphoric acid and control and the embodiment of other conditions and front are essentially identical.
The slip that obtains by above-mentioned neutralization procedure contains the water of 25-40%.This slip promptly obtains product of the present invention through dehydration.Can adopt general drying mode well known to those skilled in the art to carry out drying.Preferably this slip can be delivered to the spray granulating machine and carry out drying-granulating, or deliver to the ammoniation and granulation drying machine and carry out drying-granulating.In these cases, the temperature of hot-air mouth generally should be controlled at 200-550 ℃, preferably be controlled at 300-450 ℃, more preferably be controlled at 300-350 ℃.
Product by the inventive method production obtains shows through material phase analysis: main thing is ammonium hydrogen phosphate, potassium-ammonium sulfate [(NH mutually
4K)
2SO
4], ammonium sulfate, secondly be vitriolate of tartar, ammonium chloride urea double salt [NH
4CICO (NH
2)
2], and a spot of Fe (NH
4)
2H
2F (PO
4)
2, potassium primary phosphate etc.
Product by the inventive method production obtains shows through chemical analysis: when potassium hydrogen sulfate solution and phosphoric acid solution respectively with K
2O and P
2O
5The weight meter, K
2O and P
2O
5Weight ratio when being 1: 1 proportioning, be neutralized to pH with gas ammonia and equal 8.5, in described composite fertilizer gross weight, total nitrogen can reach 14-15%, total P
2O
5All be not less than 15% with general potassium amount, water-soluble attitude sulphur content works energetically 11%, and cl content is less than 2.6%.As above-mentioned K
2O and P
2O
5Weight ratio between 2: 1, carried out proportioning at 0.5: 1 when adjusting, be neutralized to PH with gas ammonia and equal 8.5, in described composite fertilizer gross weight, total nitrogen is roughly 10-15%, total P
2O
5Be roughly 10-20%, general potassium amount is roughly 8-20%.
The production method of sulfenyl nitrogen-phosphorus-potassium compound fertilizer of the present invention has many positive effects with respect to prior art.
1, can significantly reduce the energy expenditure of production process.Compare with existing production method, because the present invention produces and has adopted interchanger in the sal enixum, improved thermo-efficiency, so producing the energy of sal enixum use can reduce more than 70%, as adopt the reactor production per kilogram sal enixum of common strap clamp layer to need about 216 kilocalories of heats, need about 50 kilocalories of heats and adopt method of the present invention to produce the per kilogram sal enixum.
In addition, compare with adopting prior art to produce to produce described composite fertilizer again behind the various finished product fertilizers, adopt production method energy needed of the present invention can reduce by 7 * 10
5More than the kilocalorie/ton.
2, because the present invention produces and adopted interchanger in the sal enixum, use the sulfuric acid temperature low, thus equipment corrosion reduced, like this, the security that can enhance productivity and produce.
3, because the production that present method will be produced raw produce such as sal enixum, phosphoric acid, ammonia is combined into one, so shortened Production Flow Chart greatly, reduced facility investment, compared with usual method, facility investment can reduce more than 40%.Can adopt canalization to carry owing to produce, simple to operate, safety, the product of producing is stable, nitrogen, phosphorus, potassium ratio are easily adjusted in the product, and environmental pollution is little, in addition owing to reduced the transportation of finished product fertilizer material, thereby reduced the circulation of finished product fertilizer material on market, therefore, can reduce production costs greatly, improve the economic benefit of producing.Product of the present invention reduces about 500 yuan than usual method production cost is per ton.
For the present invention being described better rather than limiting its protection domain, list following embodiment:
One, embodiment 1
The preparation of sulfenyl nitrogen-phosphorus-potassium compound fertilizer of the present invention, its step is as follows:
1, with P
2O
5Count the preparation of 20% dilute phosphoric acid:
Allow and contain P
2O
5The Rock Phosphate (72Min BPL) of 29.2% (weight) is milled to 100 orders, and the rock phosphate powder of sieving rate 90% is in being metered into reactive tank.According to this Rock Phosphate (72Min BPL) P
2O
5Cubage, for 92% (weight) sulfuric acid of 103% of theoretical amount reacts with ground phosphate rock through being metered into reactive tank, it is 6 hours that temperature of reaction is controlled at 75 ℃, reaction times, SO in the control liquid phase
3Concentration be 4% (weight), the slip liquid-solid ratio is 2.4: 1, after reaction finishes the phosphoric acid material pulp in the reactive tank is delivered to filter through shurry pump and filters, through three washings, its filtrate is dilute phosphoric acid again, its concentration is with P
2O
5The dilute phosphoric acid of meter 20%.
2, gaseous ammonia is synthetic:
The ammonia that this embodiment adopts Linyi, Shandong chemical general factory to produce.Adopt coal synthesis gas ammonia, the technological process of production of its ammonia is the normally used technical process of present China synthetic ammonia.
3, the production of sal enixum:
(1) adopts the 5m that produces by Lanzhou chemical machinery research institute of the Ministry of Chemical Industry
2Interchanger is heated to 130 ℃ with 98% (weight) sulfuric acid; The structure of its interchanger is a shell and tube.
(2) allowing described hot sulfuric acid of 98% (weight) and Repone K, is to react 60 minute at 1: 1 by mole with the ratio of sulfuric acid and Repone K; Obtain 90-95% (weight) potassium hydrogen sulfate solution, simultaneously hydrogen chloride gas is extracted out and delivered to the absorption tower and absorb and obtain hydrochloric acid;
4, add described dilute phosphoric acid
According to K
2O and P
2O
5Weight ratio be 1: 1, add with P toward above-mentioned potassium hydrogen sulfate solution
2O
5Weight is counted 20% described dilute phosphoric acid, obtains a kind of mixed solution;
5, feed described gaseous ammonia in the above-mentioned mixed solution and neutralize, reach 8.0, obtain the slip of moisture 29% (weight) until the pH of its slip;
6, allowing above-mentioned slip send into the hot-air mouth temperature is that 350 ℃ spray granulation drier carries out granulating and drying and obtains its product.
Its product is determined through material phase analysis, mainly is ammonium hydrogen phosphate, ammonium sulfate, potassium-ammonium sulfate in the product, a spot of vitriolate of tartar etc.Its nitrogen, phosphorus, potassium, sulphur content are not 15% with described product gross weight score substantially; 15%; 15%; 11%.
Calculate after measured, product of the present invention per ton all consumes total energy from ore processing beginning meter and is about 9 * 10
5Kilocalorie.
Embodiment 2
The preparation of sulfenyl nitrogen-phosphorus-potassium compound fertilizer of the present invention, its step is as follows:
1, with P
2O
5Count the preparation of 22% dilute phosphoric acid;
Allow and contain P
2O
5The Rock Phosphate (72Min BPL) of 29.2% (weight) is milled to 100 orders, and its rock phosphate powder is in being metered into reactive tank.According to this rock phosphate powder P
2O
5Cubage, for 92% (weight) sulfuric acid of 104% of theoretical amount reacts with ground phosphate rock through being metered into reactive tank, it is 6 hours that temperature of reaction is controlled at 76 ℃, reaction times, SO in the control liquid phase
3Concentration is 4.5% (weight), and the slip liquid-solid ratio is 2.4: 1, after reaction finishes the phosphoric acid material pulp in the reactive tank is delivered to filter through shurry pump and filters, and through three washings, its filtrate is dilute phosphoric acid again, and its concentration is with P
2O
5The dilute phosphoric acid of meter 22%.
2, gaseous ammonia is synthetic:
The ammonia that this embodiment adopts Linyi, Shandong chemical general factory to produce.Adopt coal synthesis gas ammonia, the technological process of production of its ammonia is the normally used technical process of present China synthetic ammonia.
3, the production of sal enixum:
(1) adopts the 5m that produces by Lanzhou chemical machinery research institute of the Ministry of Chemical Industry
2Interchanger is heated to 100 ℃ with 96% (weight) sulfuric acid; The structure of its interchanger is a shell and tube;
(2) allowing described hot sulfuric acid of 96% (weight) and Repone K, is to react 90 minute at 1.2: 1 by mole with the ratio of sulfuric acid and Repone K; Obtain 85% (weight) potassium hydrogen sulfate solution, simultaneously hydrogen chloride gas is extracted out and delivered to the absorption tower and absorb and obtain hydrochloric acid;
4, add described dilute phosphoric acid
According to K
2O and P
2O
5Weight ratio be 0.8: 1, add with P toward above-mentioned potassium hydrogen sulfate solution
2O
5Weight is counted 22% described dilute phosphoric acid, obtains a kind of mixed solution;
5, feed described gaseous ammonia in the above-mentioned mixed solution and neutralize, reach 6.5, obtain the slip of moisture 34% (weight) until the pH of its slip;
6, allowing above-mentioned slip send into the hot-air mouth temperature is that 320 ℃ spray granulation drier carries out granulating and drying and obtains its product.
Its product is determined through material phase analysis, mainly is ammonium hydrogen phosphate, ammonium sulfate, potassium-ammonium sulfate in the product, a spot of vitriolate of tartar etc.Its nitrogen, phosphorus, potassium, sulphur content are not 14% with described product gross weight score substantially; 16%; 13.5%; 10%.
Calculate after measured, product consumed energy of the present invention per ton is 9.0 * 10
5Kilocalorie.
Embodiment 3
The preparation condition of this embodiment is identical with the condition of embodiment 1, the 5m that just adopts 350 ℃ of stack gas heating Repone K and adopt Lanzhou chemical machinery research institute of the Ministry of Chemical Industry to produce
2Interchanger adds normal temperature sulfuric acid, makes the temperature of its Repone K reach 280 ℃, and the vitriolic temperature reaches 100 ℃.
Its product is determined through material phase analysis, mainly is ammonium hydrogen phosphate, ammonium sulfate, potassium-ammonium sulfate in the product, a spot of vitriolate of tartar etc.Its nitrogen, phosphorus, potassium, sulphur content are not 15.0% with described product gross weight score; 15.0%; 15.0%; 11%.
Calculate after measured, product consumed energy of the present invention per ton is 1.1 * 10
6Kilocalorie.
Embodiment 4
The preparation condition of this embodiment is identical with the condition of embodiment 1, just adopts 380 ℃ of stack gases heating Repone K, makes the temperature of its Repone K reach 360 ℃ and the 5m that adopts Lanzhou chemical machinery research institute of the Ministry of Chemical Industry to produce
2Interchanger heating normal temperature sulfuric acid makes the vitriolic temperature reach 80 ℃.
Its product is determined through material phase analysis, main ammonium hydrogen phosphate, ammonium sulfate, potassium-ammonium sulfate in the product, a spot of vitriolate of tartar etc.Its nitrogen, phosphorus, potassium, sulphur content are not 15.0% with described product gross weight score substantially; 15.0%; 15.0%; 11%.
Calculate after measured, the clear energy consumption of product of the present invention per ton is 1.05 * 10
6Kilocalorie.
Embodiment 5
The preparation of sulfenyl nitrogen-phosphorus-potassium compound fertilizer of the present invention, its step is as follows:
1, with P
2O
5The Rock Phosphate (72Min BPL) of 29.2% (weight) is milled to 80 orders, and its rock phosphate powder is in being metered into reactive tank.According to this rock phosphate powder P
2O
5Cubage, for 92% (weight) sulfuric acid of 104% of theoretical amount reacts with ground phosphate rock through being metered into reactive tank, temperature of reaction is controlled at 76 ℃, and the reaction times is 6 hours, SO in the control liquid phase
3Concentration is 4.0% (weight), and the slip liquid-solid ratio is 2.2: 1, after reaction finishes the phosphoric acid material pulp in the reactive tank is delivered to filter through shurry pump and filters, and through three washings, its filtrate is dilute phosphoric acid again, and its concentration is with P
2O
5The dilute phosphoric acid of meter 22%.
2, gaseous ammonia is synthetic:
The ammonia that this embodiment adopts Linyi, Shandong chemical general factory to produce.Adopt coal synthesis gas ammonia, the technological process of production of its ammonia is the normally used technical process of present China synthetic ammonia.
3, the production of sal enixum:
(1) adopts the 5m that produces by Lanzhou chemical machinery research institute of the Ministry of Chemical Industry
2Interchanger is heated to 140 ℃ with 96% (weight) sulfuric acid; The structure of its interchanger is a shell and tube.
(2) allowing described hot sulfuric acid of 96% (weight) and Repone K, is to react 60 minute at 1.8: 1 by mole with the ratio of sulfuric acid and Repone K; Obtain 60% (weight) potassium hydrogen sulfate solution, simultaneously hydrogen chloride gas is extracted out and delivered to the absorption tower and absorb and obtain hydrochloric acid;
4, add described dilute phosphoric acid
According to K
2O and P
2O
5Weight ratio be 0.8: 1, add with P toward above-mentioned potassium hydrogen sulfate solution
2O
5Weight is counted 22% described dilute phosphoric acid, obtains a kind of mixed solution;
5, feed described gaseous ammonia in the above-mentioned mixed solution and neutralize, reach 7.0, obtain the slip of moisture 36% (weight) until the pH of its slip;
6, allowing above-mentioned slip send into the hot-air mouth temperature is that 400 ℃ spray granulation drier carries out granulating and drying and obtains its product.
Its product is determined through material phase analysis, mainly is ammonium hydrogen phosphate, ammonium sulfate, potassium-ammonium sulfate in the product, a spot of vitriolate of tartar etc.Its nitrogen, phosphorus, potassium, sulphur content are not 13.5% with described product gross weight score; 15%; 10%; 13%.
Calculate after measured, product consumed energy of the present invention per ton is 9.1 * 10
5Kilocalorie.
Embodiment 6
The preparation of sulfenyl nitrogen-phosphorus-potassium compound fertilizer of the present invention, its step is as follows:
1, with P
2O
5Count the preparation of 20% dilute phosphoric acid:
Allow and contain P
2O
5The Rock Phosphate (72Min BPL) of 29.2% (weight) is milled to 80 orders, and its rock phosphate powder is in being metered into reactive tank.According to this rock phosphate powder cubage, for 92% (weight) sulfuric acid of 104% of theoretical amount reacts with ground phosphate rock through being metered into reactive tank, it is 6 hours that temperature of reaction is controlled at 76 ℃, reaction times, SO in the control liquid phase
3Concentration is 4.0% (repetition), and slip liquid-solid ratio 2.3: 1 is delivered to filter with the phosphoric acid material pulp in the reactive tank through shurry pump after reaction finishes and filtered, and through three washings, its filtrate is dilute phosphoric acid again, and its concentration is with P
2O
5The dilute phosphoric acid of meter 20%.
2, gaseous ammonia is synthetic:
The ammonia that this embodiment adopts Linyi, Shandong chemical general factory to produce.Adopt coal synthesis gas ammonia, the technological process of production of its ammonia is the normally used technical process of present China synthetic ammonia.
3, the production of sal enixum:
(1) adopts the 5m that produces by Lanzhou chemical machinery research institute of the Ministry of Chemical Industry
2Interchanger is heated to 120 ℃ with 92% (weight) sulfuric acid; The structure of its interchanger is a shell and tube;
(2) allowing described hot sulfuric acid of 92% (weight) and Repone K, is to react 110 minute at 1.0: 1.0 by mole with the ratio of sulfuric acid and Repone K; Obtain 95% (weight) potassium hydrogen sulfate solution, simultaneously hydrogen chloride gas is extracted out and delivered to the absorption tower and absorb and obtain hydrochloric acid;
4, add described dilute phosphoric acid
According to K
2O and P
2O
5Weight ratio be 1: 1, add with P toward above-mentioned potassium hydrogen sulfate solution
2O
5Weight is counted 20% described dilute phosphoric acid, obtains a kind of mixed solution;
5, feed described gaseous ammonia in the above-mentioned mixed solution and neutralize, reach 7.5, obtain the slip of moisture 36% (weight) until the pH of its slip;
6, allowing above-mentioned slip send into the hot-air mouth temperature is that 450 ℃ spray granulation drier carries out granulating and drying and obtains its product.
Its product is determined through material phase analysis, mainly is ammonium hydrogen phosphate, ammonium sulfate, potassium-ammonium sulfate in the product, a spot of vitriolate of tartar etc.Its nitrogen, phosphorus, potassium, sulphur content are not 14% with described product gross weight score; 15%; 15%; 11%.
Calculate after measured, product consumed energy of the present invention per ton is 9.05 * 10
5Kilocalorie.
Embodiment 7
The preparation condition of this embodiment is identical with the condition of embodiment 5, just adopts 350 ℃ of stack gases heating Repone K, makes the temperature of its Repone K reach 280 ℃ and the 5m that adopts Lanzhou chemical machinery research institute of the Ministry of Chemical Industry to produce
2Interchanger heating normal temperature sulfuric acid makes the vitriolic temperature reach 100 ℃.
Its product is determined through material phase analysis, mainly is ammonium hydrogen phosphate, ammonium sulfate, potassium-ammonium sulfate in the product, a spot of vitriolate of tartar etc.Its nitrogen, phosphorus, potassium, sulphur content are not 13.5% with described product gross weight score; 15%; 10%; 13%.
Calculate after measured, product consumed energy of the present invention per ton is 1.0 * 10
6Kilocalorie.
Embodiment 8
The preparation condition of this embodiment is identical with the condition of embodiment 5, just adopts 380 ℃ of stack gases heating Repone K, makes the temperature of its Repone K reach 360 ℃ and the 5m that adopts Lanzhou chemical machinery research institute of the Ministry of Chemical Industry to produce
2Interchanger heating normal temperature sulfuric acid makes the vitriolic temperature reach 80 ℃.
Its product is determined through material phase analysis, mainly is ammonium hydrogen phosphate, ammonium sulfate, potassium-ammonium sulfate in the product, a spot of vitriolate of tartar etc.Its nitrogen, phosphorus, potassium, sulphur content are not 13.5% with described product gross weight score; 15%; 10%; 13%.
Calculate after measured, product consumed energy of the present invention per ton is 1.05 * 10
6Kilocalorie.
Claims (9)
1, a kind of production method of sulfenyl nitrogen-phosphorus-potassium compound fertilizer, comprising by Rock Phosphate (72Min BPL) production with P
2O
5Weight counts the dilute phosphoric acid of 18-25%, by coal or gas production gaseous ammonia, produce potassium hydrogen sulfate solution with Repone K, described sal enixum is mixed with described dilute phosphoric acid and with described ammonia neutral step, it is characterized in that described potassium hydrogen sulfate solution production stage is by sulfuric acid:
(1) adopts interchanger that 92%-98% (weight) sulfuric acid is heated to 80-160 ℃, or adopt the gas of heat that Repone K is heated to 200-500 ℃;
(2) allow hot sulfuric acid of described 92%-98% (weight) and Repone K, or 92-98% (weight) sulfuric acid and described thermal chlorination potassium, or hot sulfuric acid of described 92-98% (weight) and described thermal chlorination potassium, be (0.8-2.0) by mole with the ratio of sulfuric acid and Repone K: 1 reacted 30-120 minute; Obtain potassium hydrogen sulfate solution and hydrogen chloride gas; Its feature also is:
(3) according to K
2O and P
2O
5Weight ratio be 0.5: 1 to 2: 1, with above-mentioned potassium hydrogen sulfate solution with P
2O
5Weight is counted the described dilute phosphoric acid mixing of 18-25%, obtains a kind of mixed solution; With described neutralization procedure be:
(4) feed described gaseous ammonia in the above-mentioned mixed solution and neutralize, reach 5.4-10, obtain the slip of moisture 25-40% (weight) until the pH of its slip;
At last, (5) allow above-mentioned slip send into the hot-wind inlet temperature is 200-550 ℃ spray granulation drier or ammoniation and granulation drying machine, carries out granulating and drying and obtains its product.
2, production method according to claim 1 is characterized in that described 92-98% (weight) sulfuric acid is heated to 100-140 ℃.
3, production method according to claim 1, the gas that it is characterized in that described heat are the hot flue gases of coal combustion, Sweet natural gas or other fuel.
4, production method according to claim 1 is characterized in that Repone K is heated to 250-400 ℃.
5, production method according to claim 1 is characterized in that being (1.0-1.6) by the ratio of mole sulfuric acid and Repone K: 1.
6, production method according to claim 1 is characterized in that described sulfuric acid and Repone K reaction 50-100 minute.
7, production method according to claim 1 is characterized in that described potassium hydrogen sulfate solution and described phosphoric acid solution are respectively with K
2O and P
2O
5The weight meter, its K
2O and P
2O
5Weight ratio be 0.6: 1 to 1.5: 1.
8, production method according to claim 1 is characterized in that be 6.5-9.0 with the gaseous ammonia neutralization until the pH that reaches its slip.
9, production method according to claim 1 is characterized in that described hydrogen chloride gas water absorption obtains hydrochloric acid.
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| CN97105751A CN1045947C (en) | 1997-03-26 | 1997-03-26 | Method for preparing sulfonyl azophoska compound fertilizer |
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|---|---|---|---|
| CN97105751A CN1045947C (en) | 1997-03-26 | 1997-03-26 | Method for preparing sulfonyl azophoska compound fertilizer |
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| CN1045947C CN1045947C (en) | 1999-10-27 |
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| CN1301236C (en) * | 2005-02-02 | 2007-02-21 | 高苏茂 | Method for producing sulfo composite fertilizer by using ammonified potassium bisulfate solution and its corresponding device |
| CN101445406B (en) * | 2008-12-18 | 2011-03-02 | 聊城鲁西化工第四化肥厂 | Spray granulation production method for chlorine-based compound fertilizer |
| CN101337847B (en) * | 2008-08-08 | 2011-09-21 | 贵州西洋肥业有限公司 | Method for preparing high-nitrogen sulfonyl azophoska compound fertilizer |
| CN102584408A (en) * | 2012-03-23 | 2012-07-18 | 河北冀衡赛瑞化工有限公司 | Method for producing nitro-sulfur-based composite fertilizer by full-liquid phase high tower granulation |
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| CN105236448A (en) * | 2015-10-14 | 2016-01-13 | 四川蓥峰实业有限公司 | New process for production of potassium sulfate and co-production of compound fertilizer |
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| CN105502321A (en) * | 2015-12-30 | 2016-04-20 | 川恒生态科技有限公司 | Production method of acidic potassium thiophosphate |
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| JPS5692187A (en) * | 1979-12-24 | 1981-07-25 | Central Glass Co Ltd | Manufacture of nonnchlorine furtilizer |
| CN1039222C (en) * | 1991-10-07 | 1998-07-22 | 大连化学工业公司 | Chloroless compound fertilizer using potassium chloride as raw material |
| CN1115749A (en) * | 1994-07-26 | 1996-01-31 | 湖南省郴州地区化肥厂 | Prodn process of ternary compound fertilizer with KCl |
| CN1128247A (en) * | 1995-10-12 | 1996-08-07 | 湖南省郴州化肥总厂 | Continuous production method of potassium sulphate type ternary granulated complex fertilizer by using potassium chloride |
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| CN101928165B (en) * | 2009-06-26 | 2012-09-05 | 朱德浩 | Method and device for preparing monopotassium phosphate and potassium ammonium phosphate by multistage steam injection |
| CN102992818A (en) * | 2011-09-15 | 2013-03-27 | 山东博丰利众化工有限公司 | Low chlorine potassium sulfate compound fertilizer production method |
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