CN106044798A - Ammonium sulfate preparation method - Google Patents
Ammonium sulfate preparation method Download PDFInfo
- Publication number
- CN106044798A CN106044798A CN201610716808.9A CN201610716808A CN106044798A CN 106044798 A CN106044798 A CN 106044798A CN 201610716808 A CN201610716808 A CN 201610716808A CN 106044798 A CN106044798 A CN 106044798A
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- China
- Prior art keywords
- solid
- ball milling
- ardealite
- ammonium sulfate
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crushing And Grinding (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses an ammonium sulfate preparation method. The method particularly includes: subjecting ardealite solid and ammonium carbonate solid to solid-phase reaction under a ball milling condition to obtain ammonium sulfate solid. Since the ardealite solid and the ammonium carbonate solid are subjected to solid-phase reaction under the ball milling condition, high conversion rate is realized. In addition, by adoption of the ardealite solid as a raw material, waste recycling is realized, production cost is reduced, and environment pollution caused by waste ardealite solid is avoided.
Description
Technical field
The present invention relates to the technical field of ammonium sulfate, particularly relate to a kind of method preparing ammonium sulfate.
Background technology
Ammonium sulfate industrially has purposes widely, as be 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 goods, the production of many enzyme preparations, need to there is substantial amounts of sulfur
Acid ammonium makees salting-out agents.Additionally, ammonium sulfate is also the important source material producing potassium sulfate.Along with developing rapidly of China's industrial or agricultural.Sulfur
The market demand of acid 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 prepared by ammonia neutralisation of sulphuric acid, or by oven gas
Ammonia sulfuric acid absorption that by-product separates and prepare.Due to ammonia be dissolved in the produced ammonia of water can not all ionize out ammonium from
Son, thus ammonia is difficult to all by complete for sulfuric acid reaction, causes conversion ratio limited.
Summary of the invention
In view of this, the present invention provides the synthetic method of a kind of ammonium sulfate, and this synthetic method has higher conversion ratio.
A kind of method preparing ammonium sulfate, specifically, carry out carrying out under ball milling by ardealite solid and ammonium carbonate solid
Solid state reaction, obtains ammonium sulfate solids.
The principle of above-mentioned solid phase reaction is CaSO4+(NH4)2CO3=Ca CO3+(NH4)2 SO4.The present invention with ammonium carbonate is
Reactant, compared to ammonium hydrogen carbonate, the more difficult decomposition of ammonium carbonate, thus there is preferable conversion ratio.
Ardealite is the industrial residue of discharge during Wet-process Phosphoric Acid Production, and it is mainly composed of 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
That cause and cost, can turn waste into wealth, it is to avoid the ardealite pollution to environment.
Term " solid state reaction " is the reaction between solid phase, and refer in particular to that two solid phases carry out under not solubilizer is anti-
Should, it is the concept relative with liquid phase reactor.
Term " ball milling " refers to the percussion with the abrasive body (such as steel ball, cobblestone etc.) fallen and abrasive body and ball
The abrasive action of mill inwall and by crushing material and mix.In the present invention, ball milling can use dry ball milling or wet ball grinding.This
It is preferably dry ball milling in bright, adds impact on ammonium sulfate purity with avoid solvent.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 reactant granule attenuate, contact area increases
Greatly, interior energy raises, reactivity increases, and the heat needed for also providing reaction.Under ball action, ardealite and carbonic acid
Hydrogen is sufficiently disperseed by powder and is mixed, and adds granule contact probability, thus adds the collision frequency of reactant, with
Time abrading-ball and abrading-ball, abrading-ball and grinding jar between high-speed impact and friction so that powder by impact, shear and compression etc. is made
With, energy substantially increases, and anakmetomeres sum increases, and occurs the probability of effective collision to be greatly increased, and therefore reaction generates sulphuric acid
By speed also greatly speed up.
In order to reduce the activation energy needed for solid state reaction, the mode of high-energy ball milling can be used.High-energy ball milling method is to pass through ball
The rotation of grinding machine or vibration make the method that hard sphere carries out strong shock, grinds and stir raw material.Its cardinal principle be divided into
Under several steps: (1) crystal grain refine.By mechanical milling process and impact several times with pulverize so that the starting powder put into is gradually
Diminishing until Nano grade, in powder atom, surface produces a series of bond fission subsequently, and lattice produces defect, and then defect is not
Disconnected extension, 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 spread to inside athletic meeting
Promote that the different material put into mutually invades the other side and forms new steady statue, chemical reaction occurs immediately, forms noval chemical compound.
(2) localized bumps point heats up.The moment of collision can produce the biggest 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 will be far above 70 DEG C.The ultra-high temperature of indivedual points of impingement can help the defect produced to be diffused；Help heterogeneity invades
The other side；Help to reconfigure between atom；Help bond energy reorganizes.Scientist is had to find the mechanochemical process wink in effect
Between namely 10-8～10-9In the range of s, local can produce high temperature, can enough reach 1000K, and the high pressure of generation is
Height can reach 1 ~ 10 GPa.Such as planetary mills grinding ZrO2Being 24 hours, distortion of lattice reaches 6 × 10-3～10 × 10-3。
(3) lattice relaxation cracks with structure.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 inspires high-energy electron and plasma area subsequently, and original complete structure is broken
And crack.High-energy ball mill being inspired to 10 eV is feasible, but this energy is heated to 1000 at typical condition
More than Du all it is extremely difficult to, so likely carrying out, by mechanical force, the reaction that normal conditions heat chemistry can not be carried out.
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, if rotating speed is less than this scope,
Then it is unable to reach the activation energy needed for reaction；If rotating speed exceedes this scope, the raising of conversion ratio also will not be brought significantly.
In order to reach preferable conversion ratio and reduce energy consumption, with 1～5 preferably, such as ratio of grinding media to material is the ratio of grinding media to material of above-mentioned ball milling
1,1.2,1.5,2,2.5,3,4,4.5 or 5 etc..Herein, ratio of grinding media to material refers to the ratio of abrasive body and inventory.
In order to reach preferable conversion ratio and reduce 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 be 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, then it is unable to reach the activation energy needed for reaction, if temperature is too low, then causes
The decomposition of ammonium carbonate solid and reduce the conversion ratio of reaction.
In order to reach preferable conversion ratio, the thing mass ratio of ardealite solid and ammonium carbonate can be 0.9～1.1.Such as
The material amount 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, this
In the material amount of ardealite solid refer to the calcium sulphate dihydrate in ardealite solid for counting.
Above-mentioned do not address part, it is adaptable to prior art.
As used herein, above-mentioned term:
" mass parts " refers to represent the basic measurement unit of the mass ratio relation of multiple component, and 1 part can represent arbitrary unit matter
Amount, as being expressed as 1g, it is possible to represents 2.689g etc..If we say that the mass parts of component A is a part, the mass parts of B component
For b part, then it represents that the quality of component A and mass ratio a:b of B component.Or ground, represents that the quality of component A is aK, B component
Quality be bK(K be Arbitrary Digit, represent multiplying factor).Can not misread, unlike mass fraction, all components
Mass parts sum is not limited to the restriction of 100 parts.
" one ", " a kind of " and " described " are used interchangeably and refer to one or more.
"and/or" for represent the one or both of illustrated situation all it may happen that, such as, A and/or B includes (A
And B) and (A or B).
It addition, all numerical value that the scope stated by end points herein is comprised in the range of including this (such as, 1 to 10 bag
Include 1.4,1.9,2.33,5.75,9.98 etc.).
It addition, the statement of " at least one " herein include one and above all numbers (such as, 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 ardealite solid and ammonium carbonate solid carries out carrying out under ball milling admittedly
Phase reaction, thus has higher conversion ratio.It addition, with ardealite solid as raw material, can turn waste into wealth, reduce and produce into
This, it also avoid the discarded pollution to environment of ardealite solid.
Detailed description of the invention
Technical scheme is further illustrated below in conjunction with embodiment.
Embodiment 1
Proportioning raw material.I.e. weigh ardealite powder (purity is 85.67%) and (analysis of ammonium carbonate crystal that thing mass ratio is 0.9
Pure).
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).Setting the rotating speed of high energy ball mill as 500 rpm, at 40 DEG C, the time of ball milling is 20min.After question response terminates, by thing
Material air-dries, and i.e. obtains ammonium sulfate solids.
Embodiment 2
Proportioning raw material.I.e. weigh ardealite powder (purity is 85.67%) and (analysis of ammonium carbonate crystal that thing mass ratio is 1.1
Pure).
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).Setting the rotating speed of high energy ball mill as 800 rpm, at 40 DEG C, the time of ball milling is 10min.After question response terminates, by thing
Material air-dries, and i.e. obtains ammonium sulfate solids.
Embodiment 3
Proportioning raw material.I.e. weigh ardealite powder (purity is 85.67%) and ammonium carbonate crystal (analytical pure) that thing mass ratio is 1.
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).Setting the rotating speed of high energy ball mill as 500 rpm, at 10 DEG C, the time of ball milling is 20min.After question response terminates, by thing
Material air-dries, and i.e. obtains ammonium sulfate solids.
Embodiment 4
Proportioning raw material.I.e. weigh ardealite powder (purity is 85.67%) and (analysis of ammonium carbonate crystal that thing mass ratio is 1.1
Pure).
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).Setting the rotating speed of high energy ball mill as 650 rpm, at 25 DEG C, the time of ball milling is 15min.After question response terminates, by thing
Material air-dries, and i.e. obtains ammonium sulfate solids.
Embodiment 5
Proportioning raw material.I.e. weigh ardealite powder (purity is 85.67%) and ammonium carbonate crystal (analytical pure) that thing mass ratio is 1.
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).Setting the rotating speed of high energy ball mill as 800 rpm, at 25 DEG C, the time of ball milling is 20min.After question response terminates, by thing
Material air-dries, and i.e. obtains ammonium sulfate solids.
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 dissolves with 100mL distilled water, then with 200mL distilled water repeatedly washing and filtering, filtrate collection is in burning
In Bei；Adding 12mL lM HCl, cap upper surface ware to filtrate, heating is closely stroked, and under slowly agitation, is added dropwise over 10% BaCl2
Solution;To be precipitated completely after, cap upper surface ware, be placed in water-bath and add thermal aging 1～2h, and frequently stir；Solution is cooled to room temperature
After, filter with quantitative filter paper decantation, be precipitated to without (using AgNO till chloride ion with hot distilled water washing3-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, after drying, being ashed, then 800～
850 DEG C of calcinations are to constant weight.According to gained BaSO4Quality, calculate the content of sulfate radical in sample.Calculate according to below equation:
Percentage composition=the BaSO of sulfate ion4Quality × (sulfate radical molal weight/BaSO4Molal weight)/weigh sample
The quality (being 2g) × 100% of product.Sulphuric acid in sample after the reaction of percentage composition/completely of the conversion ratio=sulfate ion of reaction
Theoretical percentage composition × 100% of root.
The conversion ratio of the reaction of embodiment 1～5 and purity, its result such as following table:
Owing to the numerical range of each technological parameter involved in the present invention can not all embody in the above-described embodiments, but this
As long as the most envisioned any numerical value fallen in this numerical range above-mentioned of the technical staff in field all can implement the present invention,
Certainly the combination in any of occurrence in the range of some numerical value is also included.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, i.e. do not mean that the present invention have to rely on above-mentioned in detail
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 equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within the present invention's
Within the scope of protection domain and disclosure.
Claims (7)
1. the method preparing ammonium sulfate, it is characterised in that specifically, ardealite solid and ammonium carbonate solid are carried out at ball
Carry out solid state reaction under mill, obtain ammonium sulfate solids.
Method the most according to claim 1, it is characterised in that the rotating speed of described ball milling is 500～800 rpm.
Method the most according to claim 1, it is characterised in that the ratio of grinding media to material of described ball milling is 1～5.
Method the most according to claim 1, it is characterised in that described ball milling uses high-energy ball milling.
Method the most according to claim 1, it is characterised in that the time of described ball milling is 10～20min.
Method the most according to claim 5, it is characterised in that the temperature of described ball milling is 10～40 DEG C.
Method the most according to claim 1, it is characterised in that the thing mass ratio of described ardealite solid and ammonium carbonate is
0.9～1.1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610716808.9A CN106044798A (en) | 2016-08-25 | 2016-08-25 | Ammonium sulfate preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610716808.9A CN106044798A (en) | 2016-08-25 | 2016-08-25 | Ammonium sulfate preparation method |
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| CN106044798A true CN106044798A (en) | 2016-10-26 |
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| CN201610716808.9A Pending CN106044798A (en) | 2016-08-25 | 2016-08-25 | Ammonium sulfate preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467331A (en) * | 2018-12-12 | 2019-03-15 | 中国电力科学研究院有限公司 | A kind of concrete 's air-containing compensation and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585547A (en) * | 2009-06-23 | 2009-11-25 | 西南科技大学 | Method for preparing ammonium sulfate as fertilizer by phosphogypsum through ball milling |
-
2016
- 2016-08-25 CN CN201610716808.9A patent/CN106044798A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585547A (en) * | 2009-06-23 | 2009-11-25 | 西南科技大学 | Method for preparing ammonium sulfate as fertilizer by phosphogypsum through ball milling |
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全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109467331A (en) * | 2018-12-12 | 2019-03-15 | 中国电力科学研究院有限公司 | A kind of concrete 's air-containing compensation and preparation method thereof |
| CN109467331B (en) * | 2018-12-12 | 2022-08-19 | 中国电力科学研究院有限公司 | Concrete gas content compensation agent and preparation method thereof |
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Application publication date: 20161026 |