CN1016774B - Dry process for neutralizing potassium sulfate produced from potassium chloride and sulfuric acid - Google Patents
Dry process for neutralizing potassium sulfate produced from potassium chloride and sulfuric acidInfo
- Publication number
- CN1016774B CN1016774B CN 85104005 CN85104005A CN1016774B CN 1016774 B CN1016774 B CN 1016774B CN 85104005 CN85104005 CN 85104005 CN 85104005 A CN85104005 A CN 85104005A CN 1016774 B CN1016774 B CN 1016774B
- Authority
- CN
- China
- Prior art keywords
- vitriolate
- tartar
- sulfuric acid
- neutralizing agent
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Abstract
The present invention relates to dry technology used for neutralizing potassium sulfate which is generated by sulphuric acid and potassium chloride and contains unreacted sulphuric acid and corresponding compounds thereof. The method comprises: potassium sulfate containing unreacted sulphuric acid and corresponding compounds thereof is mixed with at least one powdery neutralizing agent, the powdery neutralizing agent is selected from a group of substances which comprise calcium hydroxide, calcium oxide, calcium carbonate, magnesium hydroxide, magnesium oxide and magnesium carbonate, the dosage is 0.5 to 2 of equivalent weight of unreacted sulphuric acid and corresponding compounds thereof, and water or water vapor is 0.03% to 1% of the weight of the potassium sulfate. Pulverization is carried out after extrusion and granulation are carried out to the mixture.
Description
The present invention relates to the dry process of a neutralisation of sulphuric acid potassium.Especially relate to a kind of like this in and technology, promptly a certain amount of neutralizing agent as calcium hydroxide and very a spot of water or water vapor with mixed mutually according to a vitriolate of tartar that improved method produced, just with generate by Repone K and sulfuric acid and contain unreacted vitriolic vitriolate of tartar and mix mutually, (following it will be called as the improved method vitriolate of tartar), at last, by extruder grain this mixture that is used for neutralizing.
In recent years, people had produced prose style free from parallelism blending fertilizer and had dropped into application, and these fertilizer are important source material with the granulo-fertilizer.As what it is well known that, prose style free from parallelism blending fertilizer is to be produced by the corresponding component of granular various fertilizer mixes, in order that make the corresponding component of fertilizer have the admixture of a definite proportioning and storage and use gained.Therefore, under the situation of potash fertilizer raw material, also require these corresponding components to be in graininess.The vitriolate of tartar that is used for the potash fertilizer raw material normally reacts with dry type by Repone K and sulfuric acid and obtains, and still, so the improved method vitriolate of tartar that obtains often contains the sulfuric acid of percentum, promptly unreacted sulfuric acid (following will the detailed description in detail).If this improved method vitriolate of tartar is a granulous, for example as the potash fertilizer that is used for prose style free from parallelism blending, this just can not in the particle of gained in the unreacted sulfuric acid that contains.So, the present inventor had put into practice a kind of technology already, in this technology, the improved method vitriolate of tartar be with as a kind of alkaline matter of neutralizing agent and quite a large amount of water (for example, for improved method vitriolate of tartar weight 5% to 8%) mix mutually, to improve neutralization, before granulation, just finish neutralization reaction, after this it is dry with moisture eliminator or corresponding apparatus neutral improved method vitriolate of tartar to be carried out the first time, and then makes its granulating.In addition, with regard to the improved method vitriolate of tartar,, be not developed into an effective granulation process method so far as yet also not as the corresponding component of other fertilizer.So just used the technology of extruder grain.According to such prior art, before the granulation of improved method vitriolate of tartar, require a neutralization procedure and drying step.
Therefore, if might make improved method vitriolate of tartar (still unneutralized product) be subjected to neutralizing effect and granulation simultaneously, this just might save above-mentioned neutralization procedure and drying step, thereby has saved the energy and simplified production process.
Yet, we have found that, if the improved method vitriolate of tartar only mixes mutually with neutralizing agent, and then be again direct granulation or granulation and pulverizing, in to generated granular or process that powdered improved method vitriolate of tartar is stored, neutralization reaction has just begun gradually: a part of water that constitutes the vitriolate of tartar crystal water can be owing to the high temperature that produces in the neutralization reaction is released so; The existence of this water-content has further promoted neutralization reaction, and with so-called caking phenomenon, i.e. the mutual bonding phenomenon of particulate state vitriolate of tartar.So the product of caking yes can not be as prose style free from parallelism blending.
Inventor of the present invention just in and a required dry process of improved method vitriolate of tartar done deep research, just might save neutralization procedure and drying step according to this method, and when after neutralization is reflected at granulation and porphyrization, proceeding, do not produce caking phenomenon.The result, we are surprised to find, if a spot of water or water vapor are mixed mutually (and in the traditional dry neutralization procedure before granulation of water at this moment or water vapor amount ratio employed water or water vapor much less) with the improved method vitriolate of tartar that contains unreacted sulfuric acid and respective compound thereof, at this moment, thermogenesis when neutralization reaction is mixed just takes place hardly, and the flowability of improved method vitriolate of tartar powder also is without prejudice; Thereby this just might carry out this mixing at short notice, carries out granulation and pulverizing easily equably as early as possible.In addition, in the process of granulation and pulverising step, the neutralization reaction under the above-mentioned situation will be carrying out than higher speed, and when pulverising step was finished, this neutralization reaction had also been finished basically; So in granular product, just can not find caking, and, can be in store thereafter yet through the powder-like product that porphyrization obtains.
The present invention and previous technology are different significantly, the purpose of this invention is to provide one and are used for and the novel dry process of improved method vitriolate of tartar, and (annotate: the powder that equally also produces it) be prerequisite with the particle that produces the improved method vitriolate of tartar.The purpose of another aspect of the present invention is the technology that an extruder grain will be provided for the improved method vitriolate of tartar, and this technology does not promptly need neutralization procedure not need drying step yet.
The present invention has following main composition (1) and as (2)～(4) of embodiment:
(1) at the dry process of the vitriolate of tartar that generated by dry-chlorinated potassium and sulfuric acid of being used for neutralizing, its improvements comprise:
The vitriolate of tartar that contains unreacted sulfuric acid and respective compound thereof is mixed mutually with at least a powdered neutralizing agent, this powdered neutralizing agent is selected from one group of material that includes calcium hydroxide, calcium oxide, lime carbonate, magnesium hydroxide, magnesium oxide and magnesiumcarbonate, and its consumption is equivalent to normal 0.5 to 2 times of unreacted sulfuric acid and respective compound, water or water vapor consumption are 0.03% to 1% of this vitriolate of tartar weight, make this mixture stand extruder grain earlier, and then carry out pulverization process.
(2) according to the technology of above-mentioned (1) bar, it is 50 orders or less than 50 purpose powder-like products greater than the granular product of 50 orders (Tyler standard sieve) and its granularity that the above-mentioned product of having pulverized is screened into its granularity.
(3) according to the technology of above-mentioned (1) bar, described mixing is to carry out 1 minute to 1 hour under 0 ℃ to 200 ℃ temperature.
(4) according to the technology of above-mentioned (1) bar, described extruder grain is undertaken by roller press, extrusion machine or tabletting machine.
The detailed description of most preferred embodiment
Formation of the present invention and effect thereof will be described in detail below.
Employed improved method vitriolate of tartar obtains by making the reaction of sulfuric acid and Repone K among the present invention, the ratio of reactant is roughly 1 mole sulfuric acid to 2 moles Repone K, reaction process is carried out under anhydrous condition, can be divided into two steps altogether, previous step is carried out (Lie equation (1) as follows) under about 100 ℃ temperature, then a step is carried out (Lie equation (2) as follows) between about 300～400 ℃:
Because this two-step reaction all is inhomogeneous reaction, so they can not proceed to 100%, and the reaction product in second step contains a spot of H
2SO
4, KCl and KHSO
4Especially KCl and KHSO
4, the content of each (even comprises H in many cases
2SO
4Situation with the 2KCl reaction) is about 1～5 weight %.
Above-mentioned unreacted sulfuric acid and corresponding compounds are except above-mentioned H
2SO
4And KHSO
4In addition, also comprise the potassium pyrosulfate that generates according to following equation (3).Potassium pyrosulfate is by KHSO
4Thermolysis generate, as shown in the following equation:
Potassium pyrosulfate and water reaction revert back to KHSO again
4So the respective compound here is meant KHSO
4And potassium pyrosulfate.
As for employed neutralizing agent among the present invention, those neutralizing agents can be used under the temperature from 0 ℃ to 200 ℃, are to react with contained unreacted sulfuric acid and corresponding compounds in the vitriolate of tartar that is not neutralized as yet.Use the reaction product (vitriol) that is caused behind these neutralizing agents that the vitriolate of tartar that as fertilizer sources reacts component is not produced injurious effects.The object lesson of neutralizing agent is at least a compound that chooses from the compound of one group of calcium or magnesium, and the compound of these calcium or magnesium comprises calcium hydroxide, calcium oxide, lime carbonate, magnesium hydroxide, magnesium oxide and magnesiumcarbonate.As for their shape, have is that (this sieve mesh means taylor criteria screen cloth system to 100 purpose powders by granularity for example, this is applicable to existing sieve mesh), it is ideal comparatively, 20 purpose granular products then are that we are undesirable, the amount of employed neutralizing agent is normal 0.5 to 2 times of the unreacted sulfuric acid that contained in the predetermined improved method vitriolate of tartar and respective compound, and preferably between 0.8 to 1.5 times.For example be less than 0.5 equivalent, the acidity of this vitriolate of tartar will very high (being that the pH value will be low) after the neutralization reaction so; So this product just is not suitable for prose style free from parallelism blended fertilizer.For example surpass normal 2 times, so, stayed the corresponding component (K of fertilizer in the vitriolate of tartar after the neutralization reaction
2O) concentration will reduce to a certain extent, and that this is us is undesirable.
Employed water or water vapor are 0.03% to 1% of improved method vitriolate of tartar weight in neutralization reaction of the present invention, but preferably 0.05% to 0.5%.The improved method vitriolate of tartar, the hybrid mode of neutralizing agent and water or water vapor has no particular limits, but the mixture of three kinds of raw materials will be at the same time or is sent in succession in the mixing tank of open or sealing, and under 0～200 ℃ temperature, carry out fusion, and preferably under 15～110 ℃ temperature, continue 1 minute to 1 hour, better is 5 minutes to 30 minutes, the temperature of employed water vapor always is not limited in more than 100 ℃ or 100 ℃, but the pressure in airtight mixing tank remains on for example decompression of 100mmHg (reduced pressure) following time, just might use the water vapor that is lower than 100 ℃ (for example 90 ℃).The raw material of blending as powder in the time of a weak point so, just has no particular limits mixing tank whenever possible.Ribbon blender for example, the V-type mixing tank, jar type mixing tank that agitator is housed etc. all can be used.
In the fusion process, the there has just begun the reaction between a part of unreacted sulfuric acid and the neutralizing agent, but because the time of fusion is shorter than the needed time of subsequent step of extruder grain and crushing process greatly, for example be 1/5～1/100 of these subsequent step required times, so, because of the rising of temperature in the caused mixing tank of neutralization reaction heat just so not remarkable.This blending step not only can be carried out off and on but also can be carried out continuously.
Resulting admixture (improved method vitriolate of tartar, neutralizing agent and water) is sent to as going in the extruder grain step of the key step of technology of the present invention and the pulverising step.Because this adulterant is a kind of flour with good fluidity, so this feeding step can realize reposefully.
The improved method vitriolate of tartar can not adopt dish type tablets press or plunger tablets press to wait to carry out granulation, and the situation of the raw material of this corresponding component with other fertilizer or compound manure is different, so granulation process is to realize by means of compression molding machine.This class compression molding machine has roller press, compression tablets press, extrusion machine, tabletting machine or the like.It is very short need adopting the hold-time of the above-mentioned admixture that roller press for example processes, and is about 20 seconds to 1 minute; Therefore, the just molded and porphyrization subsequently of sulfuric acid that is not neutralized as yet and the neutralization reaction between the neutralizing agent in the admixture, similarly also in the later treating processes of porphyrization (for example screening), proceed down in fact in granulation, being molded to the timed interval of pulverizing and sieving from granulation is 30 minutes to 5 hours, but preferably at 1 hour to 3 hours.
During this period of time, neutralization reaction is completely basically.Although water-content is very low and time neutralization reaction is short, its reason just is that probably the extruder grain effect has increased the pack density of admixture.Its result, the rate travel of water and sulfuric acid and respective compound thereof just becomes and is much higher than the rate travel of these materials in the mealy blend in this admixture.Owing to during this period of time produced neutralization reaction heat, a part of water will be from the surface evaporation of agglomerate and another part water has just constituted this a kind of crystal water the salt.
So pulverized by for example pulverizer through over-molded and material extruder grain.Resulting comminuting matter is divided into for example about 50 purpose granulated products with sieve and passes through the powder-like product of 50 meshes, for example be necessary, this a kind of powdered product in back can remake processing treatment or adopt tabletting machine to handle with roller press, thereby obtains a kind of granular product.Certainly, be not for prose style free from parallelism blending fertilizer, but for compound manure, powder-like product can be used same as before.
The kind of institute's use pulverizer and sieve and operational condition can be identical with traditional method.The condition that the material of extruder grain or the material pulverized are carried out processing treatment is a room temperature to 30 ℃, for the time 5 minutes～1 hour (hold-time that refers to the material feeding).Granulated product that is generated or powder-like product (neutral improved method vitriolate of tartar) are stored within the bunker usually, in the bag that can take out or pack in case of necessity.
According in the dry method of the present invention and technology,,, neutralising arrangement and being used to just do not needed so operating the power of this device because neutralization procedure is unnecessary yet.Might save the device that is used for dry neutralized product in addition and be used to operate the heat energy of this device.Moreover, be the adulterant that contains micro-moisture because send to the neutral adulterant, and keep under the neutralization reaction, be sent to roller press after, very successfully form agglomerate, the yield of the granular product after pulverizing is also higher.
Moreover, when the granular product of gained and powder-like product are stored, neither produce heat and also do not form caking; Therefore this just might have no obstacle ground these products uses in prose style free from parallelism blended fertilizer or be used for granulation process again.
To come below that present invention is described by embodiment.
Example
(press H containing 2.8% weight percent
2SO
4Calculating) unreacted vitriolic improved method vitriolate of tartar (100 tons) and corresponding compounds thereof are with white lime (Ca(OH that contains 90% or 90% above weight percent)
2) in 2.3% this ratio of above-mentioned vitriolate of tartar weight (100 tons), at room temperature mix with mixing tank.In mixing process, for 0.2% water of vitriolate of tartar weight mixes with the above-mentioned material of blended with spray method by sprinkling equipment again, thereby the resulting mixture of having made neutralizing treatment at room temperature pushes by roller press and obtains the flaky material of book.
This material is at room temperature pulverized by pulverizer, and the comminuting matter of gained by shaking sieve, is separated into granular product and powder-like product successively.
Above-mentioned granular product (50 tons) and powder-like product (50 tons) are placed on a bunker (3m * 4m * 10m height) respectively and are allowed to condition at hides one more than week under the room temperature, during this period of time, promptly can not cause that the bunker temperature rises, produce caking in the time of can not taking out of afterwards yet because of neutralization reaction heat.
After storage for some time, granular product and powder-like product are filled into respectively in the pocket of 30Kg again in being allowed to condition at bunker, and these packed things are stacked as the height of 3m and allow it deposit more than 6 months in a cell.The packed thing of sample is taken out from these packed thing groups, examine its caking situation in each section stacking height then, yet, no matter be granular product, powder-like product or any general stacking height are not all found caking phenomenon.
Comparative example
Carry out the foregoing description repeatedly, just do not repeat mixing by the water of spray method, its result, the starting temperature of the powder-like product in 30 ℃ of bunkers just increased to 80 ℃ later in one day, also generate water vapor simultaneously, and when taking out of this product after the week, just found significant caking phenomenon.On the other hand, the starting temperature that is retained in the particulate state vitriolate of tartar in the bunker increased about 10 ℃ in one day later on, but progressively reduced later on, when taking out of after a week, did not find special caking phenomenon.
In addition, as for another kind caking situation, promptly the bag at 30Kg is filled, and when banking up into the 3m height and allowing it deposit more than 6 months, has found the part caking phenomenon.
Claims (3)
1, a kind of dry process of the vitriolate of tartar that generates by dry-chlorinated potassium and sulfuric acid of being used to neutralize, comprise: the vitriolate of tartar that contains unreacted sulfuric acid and respective compound is mixed mutually with at least a powdered neutralizing agent, this powdered neutralizing agent is selected from one group of material that includes calcium hydroxide, calcium oxide, lime carbonate, magnesium hydroxide, magnesium oxide and magnesiumcarbonate, it is characterized in that:
(a) neutralizing agent and unreacted sulfuric acid, KHSO
4And the mol ratio of potassium pyrosulfate is 0.5-2;
(b) water or water vapor are mixed mutually with vitriolate of tartar with the ratio of the 0.03-1% of vitriolate of tartar weight; This mixture of heating reaches 1 minute to 1 hour under 0-200 ℃ temperature.
(c) make this mixture stand the extruder grain effect, and then carry out pulverization process.
2,, it is characterized in that it is 50 orders or littler powder-like product greater than the granular product of 50 orders (Tyler standard sieve) and its granularity that the above-mentioned product of having pulverized is screened into its granularity according to the technology of claim 1.
3, according to the technology of claim 1, it is characterized in that described extruder grain be by roller press, the compression tablets press, extrusion machine or tabletting machine approach realize.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85104005 CN1016774B (en) | 1984-02-28 | 1985-05-21 | Dry process for neutralizing potassium sulfate produced from potassium chloride and sulfuric acid |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59036943A JPS60180913A (en) | 1984-02-28 | 1984-02-28 | Method for neutralizing modified potassium sulfate by dry process |
| CN 85104005 CN1016774B (en) | 1984-02-28 | 1985-05-21 | Dry process for neutralizing potassium sulfate produced from potassium chloride and sulfuric acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85104005A CN85104005A (en) | 1986-11-19 |
| CN1016774B true CN1016774B (en) | 1992-05-27 |
Family
ID=25741684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85104005 Expired CN1016774B (en) | 1984-02-28 | 1985-05-21 | Dry process for neutralizing potassium sulfate produced from potassium chloride and sulfuric acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1016774B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045760C (en) * | 1995-12-25 | 1999-10-20 | 夏纪华 | Raw stock and method for producing sodium metasilicate pentahydrate, anhydrous quick-dissolving sodium metasilicate 4A molecular sieve and potassium sulfate |
| CN102249766A (en) * | 2010-05-18 | 2011-11-23 | 国投新疆罗布泊钾盐有限责任公司 | Manufacture method of particle potash fertilizer |
| CN104843743B (en) * | 2015-05-29 | 2017-04-12 | 湖北三宁化工股份有限公司 | Method for producing potassium sulfate employing potassium hydrogen sulfate and calcium oxide |
| CN104909389B (en) * | 2015-05-29 | 2016-09-07 | 湖北三宁化工股份有限公司 | A kind of method preparing coproduction of potassium sulfate potassium hydroxide |
| CN105294270B (en) * | 2015-11-11 | 2018-10-09 | 河北萌帮水溶肥料有限公司 | A kind of granular potassium sulfate and preparation method thereof |
| CN106220278B (en) * | 2016-07-27 | 2019-10-25 | 中化云龙有限公司 | It is a kind of improve potassium sulfate compound fertilizer granule strength additive and high-strength complex Hefei particle preparation method |
-
1985
- 1985-05-21 CN CN 85104005 patent/CN1016774B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85104005A (en) | 1986-11-19 |
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