CN106348316A - Preparation method of ammonium sulfate - Google Patents
Preparation method of ammonium sulfate Download PDFInfo
- Publication number
- CN106348316A CN106348316A CN201610716758.4A CN201610716758A CN106348316A CN 106348316 A CN106348316 A CN 106348316A CN 201610716758 A CN201610716758 A CN 201610716758A CN 106348316 A CN106348316 A CN 106348316A
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- Prior art keywords
- ardealite
- preparation
- ball milling
- ammonium carbonate
- ball
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
- C01C1/244—Preparation by double decomposition of ammonium salts with sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a preparation method of ammonium sulfate. The method comprises the following steps: enabling ardealite and ammonium carbonate to have solid-liquid phase reaction in a water phase under the ball-milling condition to obtain mixed liquid of a product; separating the ammonium carbonate out from the mixed liquid of the product. According to the preparation method of the ammonium sulfate, the ardealite and the ammonium carbonate are enabled to have the solid-liquid phase reaction in the water phase under the ball-milling condition, so that a higher conversion rate is obtained. Furthermore, ardealite solid is taken as a raw material, so that waste is changed into valuable, the production cost is lowered, and the environmental pollution caused by ardealite solid waste is avoided.
Description
Technical field
The present invention relates to the technical field of ammonium sulfate, more particularly, to a kind of preparation method of ammonium sulfate.
Background technology
Ammonium sulfate industrially has extensive purposes, be such as largely used to manufacture compound fertilizer, persulfuric acid money, dyeing auxiliaries,
Fireproof agent, white carbon etc..In recent years due to the development of biochemistry product, the production of many enzyme preparations, need to there is substantial amounts of sulfur
Sour ammonium makees salting-out agents.Additionally, ammonium sulfate is also the important source material producing potassium sulfate.With developing rapidly of China's industrial or agricultural.Sulfur
The market demand of sour ammonium is increasing year by year, and ammonium sulfate market is well sold and in short supply.
In prior art, the main method preparing ammonium sulfate is to be obtained by ammonia neutralisation of sulphuric acid, or by oven gas
Ammonia sulfuric acid absorption that by-product separates and be obtained.By ammonia be dissolved in the produced ammonia of water can not all ionize out ammonium from
Son, thus ammonia be difficult to all will be complete for sulfuric acid reaction, lead to conversion ratio limited.
Content of the invention
In view of this, the present invention provides a kind of preparation method of ammonium sulfate, and this preparation method has higher conversion ratio.
A kind of method preparing ammonium sulfate, comprises the following steps:
Be there is solid-liquid phase reaction under ball milling in aqueous phase in ardealite and ammonium carbonate, obtain product mixture；
Ammonium carbonate is isolated from product mixture.
The principle of above-mentioned solid-liquid phase reaction is caso4+(nh4)2co3=caco3+(nh4)2so4.The motive force of reaction is main
From caco3And caso4Poor solubility, at 25 DEG C, caco3And caso4Solubility product be respectively 8.1 × 10-9With 2.9 ×
10-5, due to caco3Solubility product compares caso4Much smaller, reaction can be smoothed out.Under room temperature, chemical equilibrium constant k=of this reaction
[so4 2-]/[so4 2-] [co3 2-]= ksp(caso4) / (ca co3)=3580, it follows that reaction motive force is very big, thus
The conversion ratio of reaction is higher.
Above-mentioned in aqueous phase reaction form can be ardealite and ammonium carbonate are positioned in water make the two or
Ammonium carbonate is made into aqueous solution, by the aqueous solution of this ammonium carbonate and ardealite haptoreaction.The consumption of water is preferred with 0.3～0.8,
Counted with the gross mass of ardealite and ammonium carbonate for 1, the consumption of such as water is 0.3,0.32,0.35,0.4,0.45,0.50,0.55,
0.60th, 0.70,0.75,0.78 or 0.8 etc., preferably 0.5 etc..
Ardealite is the industrial residue of discharge during Wet-process Phosphoric Acid Production, and its main component is calcium sulphate dihydrate.This
Bright employing trade waste ardealite is raw material, not only reduces production cost, also eliminate the process to ardealite simultaneously and
Causing and cost, can turn waste into wealth, it is to avoid the pollution to environment for the ardealite.
Term " ball milling " refers to the percussion of abrasive body (as steel ball, cobblestone etc.) and abrasive body and ball with falling
Grind the abrasive action of inwall and by crushing material and mix.In the present invention, ball milling can adopt dry ball milling or wet ball grinding.This
It is preferably dry ball milling, to avoid the impact adding to ammonium sulfate purity of solvent in bright.In the present invention, ball milling can excite solid phase
The mechanism of reaction is according to collision theory, only to there occurs effective collision between anakmetomeres, chemical reaction could occur, and anti-
Speed is answered to depend on the effective collision number of times of anakmetomeres.Sufficiently grinding not only makes reaction composition granule attenuate, contact area increases
Greatly, interior energy raises, reactivity increases, and also provides the required heat of reaction.Under ball action, ardealite and carbonic acid
Hydrogen is sufficiently disperseed by powder and is mixed, and increased granule contact probability, thus increased the collision frequency of reactant, with
When high-speed impact between abrading-ball and abrading-ball, abrading-ball and grinding jar and friction so that powder such as is impacted, sheared and is compressed at the work
With energy substantially increases, and anakmetomeres sum increases, and occurs the probability of effective collision to greatly increase, and therefore reaction generates sulphuric acid
By speed also greatly speed up.
In order to reduce the activation energy needed for solid-liquid phase reaction, can be by the way of high-energy ball milling.High-energy ball milling method is to pass through
The rotation of ball mill or vibration make the method that hard sphere carries out strong shock, grinding and stirring to raw material.Its cardinal principle is divided into
Following step: (1) crystal grain refinement.By mechanical milling process and impact several times and pulverize so that the starting powder put into by
Gradual change is little, and until Nano grade, in subsequent powder atom, surface produces a series of bond fission, and lattice produces defect, then defect
Constantly magnify, define in ball grinder a series of increase in time unordered.This destruction to original chemical state makes
System itself is exchanged with each other ion to seek new balance, thus bond energy of arranging in pairs or groups.Surface or the motion spreading to inside
The different material put into can be promoted mutually to invade other side and to form new steady statue, immediately chemical reaction occur, form noval chemical compound.
(2) localized bumps point heats up.The moment of collision can produce very big energy at collision, and the temperature of this moment raises and also can promote
Produce chemical action in this place, the bulk temperature in ball grinder is typically not over 70 DEG C, but the temperature of localized bumps point
But 70 DEG C to be far above.The ultra-high temperature of indivedual points of impingement can help the defect producing to be diffused；Heterogeneity is helped to invade
Other side；Help reconfigure between atom；Bond energy is helped to reorganize.Scientist is had to find the wink in effect for the mechanochemical process
Between namely 10-8～10-9In the range of s, locally can produce high temperature, highest can reach 1000k, and the high pressure of generation is
Height can reach 1 ~ 10 gpa.Such as planetary mills grinding zro2For 24 hours, distortion of lattice reached 6 × 10-3～10 × 10-3.
(3) lattice relaxation and structure crack.The continuous action of mechanical force can allow the lattice relaxation that itself exists in raw material, and intracell is former
The part electronics of son starts to enliven, and subsequently inspires high-energy electron and plasma area, original complete structure is broken
And crack.The high-energy inspiring 10 ev for ball mill is feasible, but this energy is heated to 1000 at typical condition
More than degree all it is extremely difficult to, so being possible to carry out the reaction that normal conditions heat chemistry can not be carried out by mechanical force.
The rotating speed of above-mentioned ball milling be preferably 500～800 rpm, such as 500 rpm, 520 rpm, 550 rpm, 600
Rpm, 700 rpm, 750 rpm or 800 rpm etc..Rotating speed decides the energy that ball milling can be provided by, and such as rotating speed is less than this scope,
Then it is unable to reach the required activation energy of reaction；If rotating speed exceedes this scope, also will not significantly bring the raising of conversion ratio.
In order to reach preferable conversion ratio and reducing energy consumption, with 1～5 preferably, for example ratio of grinding media to material is the ratio of grinding media to material of above-mentioned ball milling
1st, 1.2,1.5,2,2.5,3,4,4.5 or 5 etc..Herein, ratio of grinding media to material refers to the ratio of abrasive body and inventory.Permissible as abrasive body
Using zirconium pearl etc..
In order to reach preferable conversion ratio and reducing energy consumption, the time of ball milling is 10～20min, and the time of such as ball milling is
10min, 11min, 12min, 15min, 18min, 19min or 20min etc..
Temperature as ball milling is preferred with 10～40 DEG C, the temperature of such as ball milling can for 10 DEG C, 12 DEG C, 15 DEG C, 20 DEG C,
25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C etc..If temperature is too low, it is unable to reach the required activation energy of reaction, if temperature is too low, causes
The decomposition of ammonium carbonate solid and reduce the conversion ratio of reaction.
In order to reach preferable conversion ratio, the amount of substance ratio of ardealite solid and ammonium carbonate can be 0.9～1.1:1.Example
If the amount of substance of the two can be 0.90,0.92,0.95,1,1.05,1.07,1.08,1.09 or 1.1 etc..It is worth explaining,
Here the amount of substance of ardealite solid refers to the calcium sulphate dihydrate in ardealite solid for counting.
Isolate ammonium carbonate and carbon for example can be filtered out from product mixture using conventional method from product mixture
Sour calcium solid, gained filtrate is carried out concentrating, crystallizes.
Above-mentioned part of not addressing is it is adaptable to prior art.
As used herein, above-mentioned term:
" mass parts " refer to represent the basic measurement unit of the mass ratio relation of multiple components, and 1 part can represent arbitrary unit matter
Amount, such as can be expressed as 1g, may also indicate that 2.689g etc..If we say that the mass parts of a component are a part, the mass parts of b component
For b part then it represents that mass ratio a:b of the quality of a component and b component.Or ground, represents that the quality of a component is ak, b component
Quality for bk(k be Arbitrary Digit, represent multiplying factor).Can not misread, and unlike mass fraction, all components
Mass parts sum is not limited to 100 parts of restriction.
" one ", " a kind of " and " described " are used interchangeably and refer to one or more.
"and/or" be used for representing one of illustrated situation or both of which it may happen that, for example, a and/or b includes (a
And b) and (a or b).
In addition, included all numerical value (for example, 1 to 10 bag being comprised in the range of this herein by the scope that end points is stated
Include 1.4,1.9,2.33,5.75,9.98 etc.).
In addition, the statement of herein " at least one " include one and above all numbers (for example, at least 2, at least
4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100 etc.).
The present invention prepares in the method for ammonium sulfate, and just to carry out solid-liquid in aqueous phase under ball milling contrary for ardealite and ammonium carbonate
Should, thus there is higher conversion ratio.In addition, with ardealite solid as raw material, can turning waste into wealth, reduce production cost,
Avoid the discarded pollution to environment of ardealite solid.
Specific embodiment
To further illustrate technical scheme with reference to embodiment.
Embodiment 1
Proportioning raw material.Weigh amount of substance than the ardealite powder (purity is 90.27%) for 0.9:1 and the (analysis of ammonium carbonate crystal
Pure), and 0.3(counts with the gross mass of ardealite and ammonium carbonate for 1) deionized water.
Mill ball and above-mentioned raw materials are added high energy ball mill (U.S. spex sampleprep 8000m according to ball milling than 1
Type).Set the rotating speed of high energy ball mill as 500 rpm, the time of ball milling is 20min at 40 DEG C.After question response terminates, to anti-
Answer product mixture to be filtered, filtration is carried out concentrating under reduced pressure, be evaporated under reduced pressure to separate out ammonia sulfate crystal.
Embodiment 2
Proportioning raw material.Weigh amount of substance than the ardealite powder (purity is 90.27%) for 1.1:1 and the (analysis of ammonium carbonate crystal
Pure) and 0.8(counted with the gross mass of ardealite and ammonium carbonate for 1) deionized water.
Mill ball and above-mentioned raw materials are added high energy ball mill (U.S. spex sampleprep 8000m according to ball milling than 1
Type).Set the rotating speed of high energy ball mill as 800 rpm, the time of ball milling is 10min at 40 DEG C.After question response terminates, to anti-
Answer product mixture to be filtered, filtration is carried out concentrating under reduced pressure, be evaporated under reduced pressure to separate out ammonia sulfate crystal.
Embodiment 3
Proportioning raw material.Weigh amount of substance than the ardealite powder (purity is 90.27%) for 1:1 and the (analysis of ammonium carbonate crystal
Pure) and 0.8(counted with the gross mass of ardealite and ammonium carbonate for 1) deionized water.
Mill ball and above-mentioned raw materials are added high energy ball mill (U.S. spex sampleprep 8000m according to ball milling than 5
Type).Set the rotating speed of high energy ball mill as 500 rpm, the time of ball milling is 20min at 10 DEG C.After question response terminates, to anti-
Answer product mixture to be filtered, filtration is carried out concentrating under reduced pressure, be evaporated under reduced pressure to separate out ammonia sulfate crystal.
Embodiment 4
Proportioning raw material.Weigh amount of substance than the ardealite powder (purity is 90.27%) for 1.1:1 and the (analysis of ammonium carbonate crystal
Pure) and 0.55(counted with the gross mass of ardealite and ammonium carbonate for 1) water.
Mill ball and above-mentioned raw materials are added high energy ball mill (U.S. spex sampleprep 8000m according to ball milling than 3
Type).Set the rotating speed of high energy ball mill as 650 rpm, the time of ball milling is 15min at 25 DEG C.After question response terminates, to anti-
Answer product mixture to be filtered, filtration is carried out concentrating under reduced pressure, be evaporated under reduced pressure to separate out ammonia sulfate crystal.
Embodiment 5
Proportioning raw material.Weigh amount of substance than the ardealite powder (purity is 90.27%) for 1:1 and the (analysis of ammonium carbonate crystal
Pure) and 0.55(counted with the gross mass of ardealite and ammonium carbonate for 1) water.
Mill ball and above-mentioned raw materials are added high energy ball mill (U.S. spex sampleprep 8000m according to ball milling than 3
Type).Set the rotating speed of high energy ball mill as 800 rpm, the time of ball milling is 20min at 25 DEG C.After question response terminates, to anti-
Answer product mixture to be filtered, filtration is carried out concentrating under reduced pressure, be evaporated under reduced pressure to separate out ammonia sulfate crystal.
In accordance with the following methods the conversion ratio of the reaction through embodiment 1～5 is measured:
After reaction terminates, the calcium sulfate in ardealite is converted into sulphuric acid by, calcium sulfate indissoluble, and sulphuric acid is by easily dissolving, therefore,
The conversion ratio of reaction can be measured according to the content of solubility sulfate radical in product.Specifically, accurately weigh under room temperature air-dry
Ammonium sulfate masterbatch 2.000g, first distills water dissolution with 100ml, then with the multiple washing and filtering of 200ml distilled water, filtrate collection is in burning
In cup；Add 12ml lm hcl, cap upper surface ware to filtrate, heating is closely stroked, under slow agitation, be added dropwise over 10% bacl2
Solution;To be precipitated completely after, cap upper surface ware, be placed in heating ageing 1～2h in water-bath, and frequently stir；Solution is cooled to room temperature
Afterwards, filtered with quantitative filter paper decantation, washed with hot distilled water to be precipitated to and no (use agno till chloride ion3-hno3Solution is examined
Look into)；Precipitation and filter paper are moved into oneself in the porcelain Citrus chachiensis Hort. of 800～850 DEG C of calcinations to constant weight exhausts, dries, after ashing, then 800～
850 DEG C of calcinations are to constant weight.According to gained baso4Quality, calculate sample in sulfate radical content.Calculate according to below equation:
Percentage composition=the baso of sulfate ion4Quality × (sulfate radical molal weight/baso4Molal weight)/weigh sample
The quality (as 2g) × 100% of product.The percentage composition/completely of the conversion ratio=sulfate ion of reaction react after sulphuric acid in sample
Theoretical percentage composition × 100% of root.
The conversion ratio of the reaction of embodiment 1～5 and purity, its result is as follows:
Numerical range due to involved each technological parameter in the present invention can not possibly all embody in the above-described embodiments, but this
As long as the completely envisioned any numerical value falling in this numerical range above-mentioned of the technical staff in field all can implement the present invention,
Certainly also include the combination in any of occurrence in the range of some numerical value.Herein, for the consideration of length, eliminate be given a certain
The embodiment of occurrence in item or multinomial numerical range, this is not to be construed as the insufficient disclosure of technical scheme.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The interpolation of the equivalence replacement to each raw material of product of the present invention and auxiliary element, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (8)
1. a kind of preparation method of ammonium sulfate is it is characterised in that comprise the following steps:
Be there is solid-liquid phase reaction under ball milling in aqueous phase in ardealite and ammonium carbonate, obtain product mixture；
Ammonium carbonate is isolated from product mixture.
2. preparation method according to claim 1 is it is characterised in that the rotating speed of described ball milling is 500～800 rpm.
3. preparation method according to claim 1 is it is characterised in that the ratio of grinding media to material of described ball milling is 1～5.
4. preparation method according to claim 1 is it is characterised in that described ball milling adopts high-energy ball milling.
5. preparation method according to claim 1 is it is characterised in that the time of described ball milling is 10～20min.
6. preparation method according to claim 5 is it is characterised in that the temperature of described ball milling is 10～40 DEG C.
7. preparation method according to claim 1 is it is characterised in that the amount of substance ratio of described ardealite and ammonium carbonate is
0.9～1.1:1.
8. preparation method according to claim 1 is it is characterised in that the consumption of water in described aqueous phase is 0.3～0.8,
Counted with the gross mass of ardealite and ammonium carbonate for 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610716758.4A CN106348316A (en) | 2016-08-25 | 2016-08-25 | Preparation method of ammonium sulfate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610716758.4A CN106348316A (en) | 2016-08-25 | 2016-08-25 | Preparation method of ammonium sulfate |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005118222A2 (en) * | 2004-05-28 | 2005-12-15 | Cargill, Incorporated | Phosphogypsum treatment process |
| CN101269823A (en) * | 2008-05-07 | 2008-09-24 | 瓮福（集团）有限责任公司 | Method for producing ammonium sulphate with phosphogypsum as raw material |
| CN101481222A (en) * | 2009-02-28 | 2009-07-15 | 四川宏达股份有限公司 | Method for preparing sulphoaluminate cement by-product ammonia sulfate by partly converting phosphogypsum |
| CN101792154A (en) * | 2010-03-04 | 2010-08-04 | 华南理工大学 | Method for producing ammonium sulfur and potassium-calcium-silicon fertilizer by using phosphogypsum |
-
2016
- 2016-08-25 CN CN201610716758.4A patent/CN106348316A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005118222A2 (en) * | 2004-05-28 | 2005-12-15 | Cargill, Incorporated | Phosphogypsum treatment process |
| CN101269823A (en) * | 2008-05-07 | 2008-09-24 | 瓮福（集团）有限责任公司 | Method for producing ammonium sulphate with phosphogypsum as raw material |
| CN101481222A (en) * | 2009-02-28 | 2009-07-15 | 四川宏达股份有限公司 | Method for preparing sulphoaluminate cement by-product ammonia sulfate by partly converting phosphogypsum |
| CN101792154A (en) * | 2010-03-04 | 2010-08-04 | 华南理工大学 | Method for producing ammonium sulfur and potassium-calcium-silicon fertilizer by using phosphogypsum |
Non-Patent Citations (2)
| Title |
|---|
| 王艳梅等: "磷石膏转氨法制硫酸技术原理与过程评价", 《化工进展》 * |
| 许春凤: "磷石膏基硫氮肥的球磨制备及其控释技术研究", 《中国优秀硕士学位论文数据库 工程科技I辑》 * |
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