CN106745094A - The non-caking production method without the high-purity saleratus of ammonium - Google Patents
The non-caking production method without the high-purity saleratus of ammonium Download PDFInfo
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- CN106745094A CN106745094A CN201611251678.2A CN201611251678A CN106745094A CN 106745094 A CN106745094 A CN 106745094A CN 201611251678 A CN201611251678 A CN 201611251678A CN 106745094 A CN106745094 A CN 106745094A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/10—Preparation of bicarbonates from carbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/22—Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/22—Purification
- C01D7/26—Purification by precipitation or adsorption
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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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Abstract
The invention discloses a kind of non-caking production method without the high-purity saleratus of ammonium, the leftover bits and pieces in the industrial magnesium phosphate of content >=98% or potassium carbonate production process is first dissolved in deionization pure water (or recycling of condensed steam water) or step 3) obtained by cleaning solution, or step 5) obtained by saleratus mother liquor in, by adsorbent oil removing, it is refined by bleaching agent bleaching again, solution of potassium carbonate after refined is again through carbonation reaction, potassium carbonate is converted into saleratus, saleratus crystallization is separated out and purified, obtain saleratus wet product, saleratus finished product is dried to obtain through high gas flow.
Description
Technical field
The invention belongs to chemical field, be related to the manufacturing technology of inorganic chemical saleratus, more particularly to it is a kind of not
Caking without ammonium it is high-purity (sodium content be less than 500ppm, ammonium content be less than 10ppm, total content of organic carbon be less than 10ppm, carbon
The production method of the saleratus of potassium hydrogen phthalate content >=99.5%).
Background technology
Potassium carbonate and saleratus are the very clearly simple compounds of structure, are both a kind of ancient and traditional chemistry
Composition, be also it is a kind of with enter generation science and technology progress and constantly assign the one of its New function, new feature and new application
Plant new product.Saleratus, as a kind of inorganic salts basic chemical industry raw material, is production potassium acetate, potassium fluoride, potassium arsenite and mountain
The raw material of potassium sorbate, is also commonly used for chemical industry, medicine, agricultural chemicals and chemical fertilizer, with the development of science and technology, the purposes of potassium carbonate is increasingly
Extensively, particularly higher-end businesses such as medicine, demand rapid growth in recent years, but to product quality it is also proposed that requirement higher.Its
In tightened up requirement is proposed to ammonium content, carbonic acid potassium content (pH value), clarity, potassium chloride and sulphates content.
Commercialization saleratus production technology has two methods of ion-exchange and electrolysis with ion-exchange film carbonizatin method at present.
However, ion-exchange is parsing agent with ammonium hydrogen carbonate, potassium ion is parsed under cationic ion-exchange resin,
Potassium ion combines to form the ammonium hydrogen carbonate of excess in saleratus, but exchange process also with saleratus with bicarbonate ion
Solution gets off together, subsequently through evaporation and concentration and drying, although most ammonium bicarbonate breaks down can be fallen, but conventional work
Skill is difficult to accomplish requirement of the ammonium content less than 10ppm in saleratus product.Due to used by ion-exchange production saleratus
Ammonium hydrogen carbonate in be added with anticaking agent, cause also to remain ammonium hydrogen carbonate anti-caking in produced saleratus product
Agent, therefore product clarity is extremely difficult to requirement.
During electrolysis with ion-exchange film carbonizatin method production saleratus, raw material potassium chloride by refinement treatment, be electrolysed, evaporate dense
Contracting, carbonating and drying process.Due to containing ammonium chloride and organic amine (floating suspension and anticaking agent) in raw material potassium chloride, even if
It also is difficult to thoroughly be removed with by ammonium by refinement treatment, therefore ammonium content overproof in saleratus can be caused.It was carbonated simultaneously
Carbon dioxide used in journey, the typically all carbon dioxide with the flue gas after lime stone high-temperature calcination after purified, or
The carbon dioxide that the waste gas of synthesis ammonia and synthesis urea element passes through gained after net, wherein sulphur is difficult thoroughly removing, although can use and eat
The carbon dioxide of grade carbon dioxide or higher level is used to produce saleratus, but production cost is clearly to be difficult to what is born.
It is specific as follows：
The inventions such as Wang Wei《A kind of preparation method of potassium carbonate》(CN201110095073.X), the method uses organic amine
Method produces potassium carbonate and saleratus.It is having for immobilized body to be added in Klorvess Liquid toward after through refinement treatment with silica
Machine amine solid-carried catalyst, is passed through carbon dioxide, and the hydrogen chloride absorption of generation is removed in organic amine solid-carried catalyst, reaction solution
Then saleratus is produced by being concentrated by evaporation.It is poisonous that the method has process is simple, the few advantage of three wastes, but organic amine
Organic chemical reagent, the saleratus for being produced is only used for producing regular industrial product, and the industry such as food, medicine cannot be answered
With and poor product quality, impurity is more, and the substantial amounts of potassium chloride for having neither part nor lot in reaction is contained in saleratus.
" method that election class potassium carbonate is produced using potassium-enriched rock " of the inventions such as The Chinese Geology Univ.'s horse great writing,
The method through broken, ore dressing, obtains with powder that potassium feldspar is main thing phase potassium-enriched rock.By K-feldspar powder and sodium carbonate
After combined grinding, calcined first at 750 DEG C -850 DEG C, addition suitable quantity of water and filled in the clinker powder for then obtaining to calcining
Divide stirring mixing, formed and contain potassium solution.CO is passed through by containing potassium solution2Carry out acidifying neutralization reaction, make silicon therein, aluminium and
Other impurities component forms precipitation, after filtering for preparing a kind of novel inorganic nonmetallic materials mineral polymeric material.Filtering
The clarification for obtaining, through evaporation, crystallization, separation, obtains the excellent pure sodium carbonate of byproduct containing potassium solution.Remaining a small amount of sodium carbonate is formed
Potassium sodium double salt, can recycle as calcining dispensing.Remaining high concentration solution of potassium carbonate through further removal of impurities, after purification, then
Through after-souring, crystallization, calcining, that is, election class potassium carbonate finished product is obtained.The process operating procedure is numerous and diverse, product quality
Difference, it is difficult to industrialize operation.
A kind of " preparation method of potassium carbonate " of Zhong Jingguang inventions discloses that a kind of technological equipment investment is few, energy consumption is low and nothing
Coal combustion flue gas or lime-kiln gas are passed through ammoniacal liquor by the potassium carbonate preparation method of disposal of pollutants, the method after water dust-removal and desulfurizing
In, it is made (NH4)2CO3Solution, adds Ni (OH)2And KCl, it is passed through ammonia and isolates Ni (NH3)Cl2Precipitation, K2CO3Ammonia spirit
Container is then transferred to, pressurization is passed through ammonia or liquid feeding ammonia, solution layering, and upper strata is supersaturated ammoniacal liquor, and lower floor is saturation K2CO3Contain
Ammonia solution, K is obtained with extraction2CO3Saturated solution containing ammonia；By K2CO3The heating evaporation of saturated solution containing ammonia, filters out residual after deamination
The NiCO for staying3After be evaporated to obtain K2CO3Product；Ni(NH3)Cl2Water, plus lime are dissolved in, after heating evaporation deamination is complete, Ni is filtered out
(OH)2Recycle, filtrate is concentrated to give CaCl2Product, the complex operation, it is difficult to realize industrialization.
" process of method for producing potassium carbonate by ion exchange " of the inventions such as Hebei University of Technology Liu swan goose, the method institute is public
The technique opened mainly includes desorption, evaporation, absorbs, carbonating, crystallization, the unit such as dries, and processing step is：Ion exchange is completed
Decomposed in desorber after liquid preheating, subsequently into triple effect evaporation unit, complete evaporation of liquid enters carbon dioxide absorption tower, carbonic acid
It is saleratus that potassium is all carbonated.Carbonating carbon dioxide gas used comes from desorber and drier, and desorber is decomposed
Ammonia be absorbed as ammoniacal liquor by ammonia absorber and do to be used with liquid.Saleratus crystallization is dried through centrifuge, and dry packing is finished product
Potassium carbonate.The present invention cancels existing ash furnace workshop section, reduces environmental pollution, improves heat transfer coefficient, titanium dioxide except fixed gas thoroughly
Carbon centralized collection concentration is high, reduces carbonation time, and improve production efficiency economizes in raw materials, and reduces cost significantly improves economy
Benefit and social benefit.Although what the technology solved carbon dioxide carrys out source problem, two of the generation in its drying process
Carbonoxide contains substantial amounts of water vapour and ammonia, adds in the saleratus ion exchanged soln used by it containing substantial amounts of carbonic acid
Hydrogen ammonium, therefore the high-purity saleratus without ammonium cannot be produced, add the removal of anticaking agent in its unresolved saleratus
Technology, product clarity is also difficult to reach requirement.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of non-caking production method without the high-purity saleratus of ammonium.
In order to solve the above-mentioned technical problem, the present invention provides a kind of non-caking without the high-purity saleratus (bicarbonate of ammonium
The production method of potassium content >=99.65%), comprises the following steps successively：
1), by the leftover bits and pieces (mass content in the industrial magnesium phosphate of mass content >=98% or potassium carbonate production process
>=98%) put into dissolving tank, add deionization pure water or recycling of condensed steam water or step 3) obtained by cleaning solution or step
5) at least one in saleratus mother liquor obtained by, in heating up (generally >=70 DEG C) to above-mentioned industrial carbonic acid under stirring condition
Leftover bits and pieces in potassium or potassium carbonate production process is dissolved almost completely, and obtains solution of potassium carbonate I；
When only deionization pure water or the recycling of condensed steam water that add, potassium carbonate is dense in control solution of potassium carbonate I
>=550 g/l of degree；
That is, in order to improve single batch of the product yield, reduce subsequent evaporation concentration energy consumption, the concentration of the solution of potassium carbonate I should connect
Nearly saturation (that is, concentration >=550 g/l of potassium carbonate)；
Use step 3 when added) obtained by cleaning solution or step 5) obtained by saleratus mother liquor when, control carbon
Potassium carbonate and saleratus concentration sum are 550~655g/L in sour potassium solution I；
2), by step 1) obtained by solution of potassium carbonate I cross adsorbent post carry out absorption oil removing, obtain the potassium carbonate after oil removing molten
Liquid II；
3), under agitation, to step 2) gained oil removing after solution of potassium carbonate II in add (being slowly added to) decolourize
Agent is decolourized, and is then filtered (press filtration or suction filtration), and filtrate and filter residue I are obtained respectively, and the filtrate is refined rear potassium carbonate
Solution III；
Filter residue I is washed with deionization pure water (or recycling of condensed steam water), cleaning solution return to step 1) for dissolving
Potassium carbonate；
4), by step 3) obtained by refined rear solution of potassium carbonate III pump into carbonating column, sealing oxygen free condition under in
Carbonation reaction is carried out under 50~60 DEG C of temperature, the pressure of 0.4~0.5Mpa, all the time to carbonators during carbonation reaction
Carbon dioxide is inside passed through, until terminating above-mentioned carbonation reaction during the pH to 8.0~8.2 of reaction gained feed liquid；
Reaction gained feed liquid is material after carbonization；
5) material is transferred to cooler crystallizer by infusion pump after, being carbonized, and is cooled to 25~35 DEG C (preferably 28~32 DEG C),
Then centrifuge dripping is carried out, during centrifuge dripping, is drenched as washings with deionization pure water or recycling of condensed steam water
Wash, obtain the high-purity saleratus wet product without ammonium；
Collected mixing liquid during centrifuge dripping (including the liquid produced during crystallisation by cooling gains centrifuge dripping
The leacheate produced during with drip washing) it is referred to as saleratus mother liquor；
6), step 5) obtained by the high-purity saleratus wet product without ammonium done by vibrated fluidized bed pneumatic conveyer dryer
Dry (low temperature drying), packaging (screen sizes can be selected according to customer requirement, packed again after sieving) after natural cooling, obtaining to tie
Block without the high-purity saleratus of ammonium.
Remarks explanation：After drying, transfer bag is transferred to after first can suitably cooling down, then naturally cool to sieving packaging after room temperature.
As the improvement of the non-caking production method without the high-purity saleratus of ammonium of the invention：Step 5) obtained by portion
Point saleratus mother liquor be back to step 1) in for the leftover bits and pieces that dissolves in industrial magnesium phosphate or potassium carbonate production process,
Its back amount is with rate-determining steps 1) obtained by solution of potassium carbonate I meet following index：Na ion concentration is dense less than 8g/L, chlorion
Degree less than 1.0g/L, sulfate concentration less than 1.0g/L, ammonium ion concentration less than 50ppm, iron concentration less than 100ppm,
Heavy metal concentration is limited less than 100ppm, arsenic concentration less than 100ppm, when in solution of potassium carbonate I any one index exceed it is above-mentioned
During limit value, then stop the return of saleratus mother liquor；
Remaining saleratus mother liquor is used to produce technical grade saleratus or potassium carbonate (that is, is transferred to technical grade carbonic acid
Hydrogen potassium or potassium carbonate production line).
As the further improvement of the non-caking production method without the high-purity saleratus of ammonium of the invention：
The step 1) in, step 3 has been used when added) obtained by cleaning solution or step 5) obtained by saleratus
During mother liquor, it is 550~655g/L that potassium carbonate and saleratus concentration sum are controlled in solution of potassium carbonate I, and Na ion concentration is less than
10.5g/L (preferably 8g/L), chlorine ion concentration be less than 1.1g/L (preferable 1.0g/L), sulfate concentration less than 1.1g/L (compared with
Good 1.0g/L), ammonium ion concentration is less than 50ppm, and iron concentration is less than 114ppm (preferably 100ppm), heavy metal concentration
Less than 100ppm, arsenic concentration is less than 100ppm, and temperature is not less than 70 DEG C.
As the further improvement of the non-caking production method without the high-purity saleratus of ammonium of the invention：
The step 2) adsorbent column packing combined by perlite (600-800 mesh) and absorbent cotton；
Described adsorbent column packing is made up of upper strata, intermediate layer and lower floor；The upper strata is to account for adsorbent pillar height degree 19
The absorbent cotton of~21% (preferably 20%), the intermediate layer is the treasure for accounting for adsorbent pillar height degree 58~62% (preferably 60%)
Zhu Yan (600~800 mesh), the lower floor is the absorbent cotton for accounting for adsorbent pillar height degree 19~21% (preferably 20%).
As the further improvement of the non-caking production method without the high-purity saleratus of ammonium of the invention：
Step 2) obtained by oil removing after solution of potassium carbonate II need to meet following condition：Organic carbon content must not exceed
50ppm, must not visually be shown in oil trace；
When the conditions set forth above are not met, it is necessary to repeat the absorption oil removing that adsorbent post carries out again.
As the further improvement of the non-caking production method without the high-purity saleratus of ammonium of the invention：
The step 3) in decolorising agent be the activated carbon of powdered sieve of 300 mesh (can cross), often the potassium carbonate of 100ml is molten
The activated carbon of II adapted of liquid >=0.05g；
Solution of potassium carbonate III after gained is refined otherwise needs weight it is ensured that light transmittance is more than 99.9% (i.e. without activated carbon)
Step 3 is carried out again) (that is, it needs to needing to re-start decolorization operations).
As the further improvement of the non-caking production method without the high-purity saleratus of ammonium of the invention：
The step 3) in, the carbonic acid potassium content of the filter residue I after washing should be less than 0.5% (in terms of butt), after washing
Filter residue I is mixed into coal and is burnt.
As the further improvement of the non-caking production method without the high-purity saleratus of ammonium of the invention：
The step 5) drip washing：The drip washing time is 5~30 seconds, and (saleratus is solid for the crystallisation by cooling gains per 100g
The scale of construction) 5~20ml of adapted washings (that is, wash water for saleratus amount 5-20%, the % envelope-bulk to weight ratios).
Remarks explanation：Drip washing is carried out in the manner described above, and high-purity saleratus of the gained without ammonium is wet after controlling washing
Product can meet following condition substantially：Sodium content is less than 500ppm, and ammonium content is less than 5ppm, and chloride ion content is less than 20ppm, sulfuric acid
Radical ion content is less than 20ppm, and iron ion content is less than 5ppm, and content of beary metal is less than 5ppm, and arsenic content is less than 1ppm, organic
Carbon content is less than 5ppm, and clarity reaches pure No. 1 standard of analysis.
As the further improvement of the non-caking production method without the high-purity saleratus of ammonium of the invention：
The step 6) in, using vibrated fluidized bed pneumatic conveying drying, 140~150 DEG C of EAT, bed temperature 105~
120 DEG C, 80~90 DEG C of air outlet temperature, the dry materials time is no more than 5 minutes.
Remarks explanation：Dried moisture content can ensure that less than 0.2% using above-mentioned drying mode, carbonic acid potassium content is no more than
0.5%, pH value is less than 8.3.
As the further improvement of the non-caking production method without the high-purity saleratus of ammonium of the invention：
The step 6) in, dried saleratus is first transferred to transfer bag after being cooled to 50~60 DEG C, enter in warehouse from
(sieving packaging) is packed in so cooling for 0~30 day again after (preferably 15 days), so that it is guaranteed that saleratus product is not added with anticaking agent
Can not lump.
As the further improvement of the non-caking production method without the high-purity saleratus of ammonium of the invention：
The step 4) in, carbon dioxide used in carbonation, it is derived from industrial magnesium phosphate calcination process
The by-product carbon dioxide or food-grade carbon-dioxide of generation；The by-product dioxy produced in using industrial magnesium phosphate calcination process
Change carbon, due to containing substantial amounts of ammonia and water vapour in the by-product carbon dioxide of generation in industrial magnesium phosphate calcination process, therefore
Needs are carried out except ammonia and water removal；It is removed in ammonia and removal process, is first condensed out so as to shape substantial amounts of water vapour with condenser
Into recycling of condensed steam water, then again with sulfuric acid (mass concentration >=30%) for adsorbent removes ammonia；Control removes ammonia and water removal
Ammonia concentration is no more than 10ppm in carbon dioxide afterwards, and steam partial pressure (that is, moisture accounts for the ratio of carbon dioxide) is no more than
30%.
That is, following condition is met by the by-product carbon dioxide after above-mentioned treatment：Pressure is more than 0.8MPa, and ammonia density is less than
10ppm, moisture content is less than 30%, and oil content is less than 10ppm.
It is of the invention non-caking without the high-purity saleratus production method of ammonium, it is exactly first by the industrial carbon of content >=98%
Leftover bits and pieces in sour potassium or potassium carbonate production process is dissolved in deionization pure water (or recycling of condensed steam water) or step 3) institute
Cleaning solution or step 5) obtained by saleratus mother liquor in, first pass through adsorbent oil removing, then by bleaching agent bleaching essence
Potassium carbonate is converted into saleratus by system, the solution of potassium carbonate after refining again through carbonation reaction, and saleratus crystallization is separated out simultaneously
Purified, obtained saleratus wet product, saleratus finished product is dried to obtain through high gas flow.
One kind of the invention is non-caking without the high-purity saleratus production method of ammonium, with low production cost, is not required to spy
Different equipment, does not increase the three wastes newly, and saleratus good product quality (will not cause new impurity to bring carbonic acid into because of addition treatment agent
Hydrogen potassium), purity it is (sodium content is less than 500ppm, and ammonium content is less than 10ppm, and total content of organic carbon is less than 10ppm) high, and with work
The advantages of by-product carbon dioxide and industrial magnesium phosphate or its leftover bits and pieces in industry potassium carbonate calcination process are raw material, meets circulation warp
The production requirement of Ji and green chemical industry.
Brief description of the drawings
Specific embodiment of the invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the non-caking process chart without the high-purity saleratus production method of ammonium of the invention.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This.
Embodiment 1, one kind are non-caking without the high-purity saleratus production method of ammonium, follow the steps below successively：
1), by industrial magnesium phosphate that 100 kilograms of mass contents are 98%, (all other indexs meet GB/T1587-
2000 certified products quality standards) input dissolving tank, add (147 liters) deionization pure water, be warming up to 75 DEG C stirring under dissolved,
Obtain 181 liters of solution of potassium carbonate I；
The solution of potassium carbonate I, concentration of potassium carbonate in 550g/L, Na ion concentration 4.8g/L, chlorine ion concentration 0.5g/L,
Sulfate ion concentration 0.5g/L, ammonium ion concentration 6ppm, iron concentration 50ppm, heavy metal concentration 10ppm, arsenic concentration
5ppm, temperature is 75 DEG C.
2), by step 1) gained solution of potassium carbonate I cross adsorbent post carry out absorption oil removing, obtain the solution of potassium carbonate after oil removing
Ⅱ；
Described adsorbent post, absorption column packing is perlite (600-800 mesh) and absorbent cotton combination, and upper strata is absorbent cotton
Layer height 20cm, intermediate layer is 600-800 mesh perlite layer height 60cm, and lower floor's degreasing cotton layer is highly 20cm, and column diameter is
5cm, pillar material is 304 stainless steels.
Flow velocity during the mistake adsorbent post of solution of potassium carbonate I is for about 10 times of column volume/hours (19.6 ls/h).
Through the solution of potassium carbonate II after oil removing, total organic carbon is carried out using high-frequency heating Far-infrared Absorption (TOC detectors)
Content analysis, total content of organic carbon is 13ppm, visually has no oil trace.
3), to step 2) gained oil removing after solution of potassium carbonate II, under agitation, be slowly added to 90.5 grams of Powdered Activated Carbons
(can cross the sieve of 300 mesh) is decolourized, and carries out press filtration or suction filtration again after being incubated 30min at 75 DEG C, solution of potassium carbonate after must refining
III and filter residue I；
Solution of potassium carbonate III after gained is refined has no activated carbon by detection, and light transmittance is 99.94%, total organic carbon
Content is 9ppm, and concentration of potassium carbonate is in 550g/L, and Na ion concentration 4.8g/L, chlorine ion concentration 0.5g/L, sulfate ion is dense
Degree 0.5g/L, ammonium ion concentration 6ppm, iron concentration 42ppm, heavy metal concentration 10ppm, arsenic concentration 5ppm, temperature is 72
℃。
Filter residue I (activated carbon) carries out washing suction filtration with 1 liter of deionization pure water points for 3 times, and the filter residue after must wash is (active
Charcoal) 130 grams, it is 0.12% containing potassium carbonate.1 liter of cleaning solution is obtained, step 1 is can return to) for dissolving potassium carbonate.
4), step 3) solution of potassium carbonate III (about 181 liters) pumps into carbonating column after gained is refined, in the oxygen free condition of sealing
Under carry out carbonation reaction in 50~60 DEG C of temperature, the pressure of 0.4~0.5Mpa, all the time to carbonization during carbonation reaction
Carbon dioxide is passed through in tower, until terminating above-mentioned carbonation reaction during the pH to 8.0~8.2 of reaction gained feed liquid；Reaction gained
Feed liquid is material after carbonization.
Carbon dioxide used in described carbonation, it derives from the pair produced in industrial magnesium phosphate calcination process
Produce carbon dioxide.The by-product carbon dioxide that will be produced in industrial magnesium phosphate calcination process, first with condenser by substantial amounts of water vapour
Condense out, then adsorbed by sulfuric acid (mass concentration >=30%) again and remove ammonia, except in the carbon dioxide after ammonia and water removal
Ammonia concentration is no more than 10ppm, and steam partial pressure is no more than 30%.Then be pressure is increased to by oilless (oil free) compressor again
0.8Mpa, by pipeline by the carbon dioxide input filter and oil removing dehydrater after compression, to remove oil droplet and water droplet.
That is, following condition is met by the by-product carbon dioxide after above-mentioned treatment：Pressure is more than 0.8MPa, and ammonia density is less than 10ppm, water
Part is less than 30%, and oil content is less than 10ppm.
5) material is transferred to cooler crystallizer by infusion pump after, being carbonized carries out crystallisation by cooling, is cooled to 28~32 DEG C, crystallization
Gained saleratus (that is, crystallizing gains) concentration is 550 g/l.With scraper self-tipping type centrifuge (band programming automatic control function,
It is capable of achieving automatic cleaning) it is centrifuged.
During centrifuge dripping, first crystallization gained saleratus in mother liquor be centrifuged off, then with deionization pure water (or
Recycling of condensed steam water) drip washing is carried out, the drip washing time is about 5 seconds, and washing water is the 5% of crystallization gained saleratus amount
(the % envelope-bulk to weight ratios, i.e. the washings of the crystallization gained saleratus adapted 5ml per 100g), obtains the high-purity carbon without ammonium
Potassium hydrogen phthalate wet product (102 kilograms).
Collected mixing liquid during centrifuge dripping (including the liquid produced during crystallisation by cooling gains centrifuge dripping
The leacheate produced during with drip washing) it is saleratus mother liquor；150 liters altogether.
High-purity saleratus wet product of the above-mentioned gained without ammonium, sodium content 342ppm, ammonium content 0.6ppm, chloride ion content
6ppm, sulfate ion content 8ppm, iron ion content 0.6ppm, content of beary metal 0.21ppm, arsenic content 0.013ppm, have
Machine carbon content 3.84ppm, clarity reaches GB/T1397-1995 and analyzes pure No. 1 standard of potassium carbonate.
Above-mentioned gained saleratus mother liquor, saleratus concentration is in 300g/L, Na ion concentration 5.8g/L, chlorine ion concentration
0.6g/L, sulfate ion concentration 0.6g/L, ammonium ion concentration 8ppm, iron concentration 60ppm, heavy metal concentration 12ppm,
Arsenic concentration 6ppm.Saleratus mother liquor can return to step 1) for dissolving potassium carbonate or for producing industrial magnesium phosphate, carbonic acid
Hydrogen potassium.
6), step 5) 102 kilograms of high-purity saleratus wet products without ammonium of gained, by vibrated fluidized bed pneumatic conveyer dryer
Low temperature drying is carried out, 140~150 DEG C of EAT, 105~120 DEG C of bed temperature, 80~90 DEG C of air outlet temperature, thing is controlled
Material drying time is no more than 5 minutes.
Through the saleratus after pneumatic conveying drying, transfer bag, natural cooling 15 days, then re-sieving are transferred to after being cooled to 50 DEG C
Packaging, obtain 100 kilograms will not lump without the high-purity saleratus of ammonium.
This 100 kilograms will not lump without the high-purity saleratus of ammonium, quality index such as table 1 below：
Table 1, the gained of embodiment 1 will not lump without the high-purity saleratus testing result of ammonium
| Project | Quality index required value | Actual measured value |
| Saleratus (KHCO3)/%, w/w >= | 99.5 | 99.71 |
| Potassium carbonate (K2CO3)/%, w/w≤ | 0.5 | 0.28 |
| Sodium content (Na)/ppm≤ | 500 | 342 |
| Chloride (CL)/ppm≤ | 20 | 6 |
| Sulphur compound is (with SO4Meter)/ppm≤ | 20 | 8 |
| Iron (in terms of Fe)/ppm≤ | 5 | 0.6 |
| Ammonium is (with NH4Meter)/ppm≤ | 5 | 0.6 |
| Heavy metal (in terms of Pb)/ppm≤ | 5 | 0.21 |
| Arsenic (in terms of As)/ppm≤ | 1 | 0.013 |
| Total organic carbon (in terms of C)/ppm≤ | 5 | 3.84 |
| PH value (20g/L, 25 DEG C)≤ | 8.3 | 8.2 |
| Moisture content/%, w/w≤ | 0.2 | 0.11 |
| Clarity≤ | 1# | Meet |
Note：These parameters, especially, remaining is in terms of butt for water removal.
Embodiment 2, one kind are non-caking without the high-purity saleratus production method of ammonium, follow the steps below successively：
1), by industrial magnesium phosphate that 100 kilograms of contents are 98%, (all other indexs meet GB/T1587-2000 and close
Lattice quality standard) input dissolving tank, add embodiment 1 in step 5) obtained by 150 liters of saleratus mother liquor, 15 liters of deionizations
Pure water, be warming up to 75 DEG C stirring under dissolved, obtain 218 liters of solution of potassium carbonate I；
The solution of potassium carbonate I, concentration of potassium carbonate in 450g/L, saleratus 200g/L, Na ion concentration 7.9g/L, chlorine from
Sub- concentration 0.8g/L, sulfate ion concentration 0.8g/L, ammonium ion concentration 7ppm, iron concentration 83ppm, heavy metal concentration
16ppm, arsenic concentration 8ppm, temperature are 75 DEG C.
2), toward step 1) gained solution of potassium carbonate I crosses adsorbent post carries out absorption oil removing, obtains the solution of potassium carbonate after oil removing
Ⅱ；
Described adsorbent post, absorption column packing is perlite (600-800 mesh) and absorbent cotton combination, and upper strata is absorbent cotton
Layer height 20cm, intermediate layer is 600-800 mesh perlite layer height 60cm, and lower floor's degreasing cotton layer is highly 20cm, and column diameter is
5cm, pillar material is 304 stainless steels.
Flow velocity during the mistake adsorbent post of solution of potassium carbonate I is for about 10 times of column volume/hours (19.6 ls/h).
It is described through the solution of potassium carbonate II after oil removing, carried out always using high-frequency heating Far-infrared Absorption (TOC detectors)
Organic carbon content is analyzed, and total content of organic carbon is 11ppm, visually has no oil trace.
3), to step 2) gained oil removing after solution of potassium carbonate II, under agitation, be slowly added to 109 grams of Powdered Activated Carbons
(can cross the sieve of 300 mesh) is decolourized, and carries out press filtration or suction filtration again after being incubated 30min at 75 DEG C, solution of potassium carbonate after must refining
III and filter residue I；
Solution of potassium carbonate III after gained is refined has no activated carbon by detection, and light transmittance is 99.96%, total organic carbon
Content is 8ppm, and concentration of potassium carbonate is in 450g/L, saleratus 200g/L, Na ion concentration 7.9g/L, chlorine ion concentration 0.8g/
L, sulfate ion concentration 0.8g/L, ammonium ion concentration 7ppm, iron concentration 81ppm, heavy metal concentration 16ppm, arsenic are dense
Degree 8ppm, temperature is 73 DEG C.
Filter residue I (activated carbon) carries out washing suction filtration with 1 liter of deionization pure water points for 3 times, and the filter residue after must wash is (active
Charcoal) 140 grams, it is 0.11% containing potassium carbonate.Obtain 1 liter of cleaning solution, return to step 1) for dissolving potassium carbonate.
4), step 3) solution of potassium carbonate III (about 218 liters) pumps into carbonators after gained is refined, under the oxygen free condition of sealing
In carbonation reaction is carried out under 50~60 DEG C of temperature, the pressure of 0.4~0.5Mpa, all the time to carbonators during carbonation reaction
Carbon dioxide is inside passed through, until terminating above-mentioned carbonation reaction during the pH to 8.0~8.2 of reaction gained feed liquid；Reaction gained material
Liquid is material after carbonization.
Carbon dioxide used in described carbonation, it derives from the pair produced in industrial magnesium phosphate calcination process
Produce carbon dioxide.The by-product carbon dioxide that will be produced in industrial magnesium phosphate calcination process, first with condenser by substantial amounts of water vapour
Condense out, then adsorbed by sulfuric acid (mass concentration >=30%) again and remove ammonia, except in the carbon dioxide after ammonia and water removal
Ammonia concentration is no more than 10ppm, and steam partial pressure is no more than 30%.Then be pressure is increased to by oilless (oil free) compressor again
0.8MPa, by pipeline by the carbon dioxide input filter and oil removing dehydrater after compression, to remove oil droplet and water droplet.
That is, following condition is met by the by-product carbon dioxide after above-mentioned treatment：Pressure is more than 0.8MPa, and ammonia density is less than 10ppm, water
Part is less than 30%, and oil content is less than 10ppm.
5) material is transferred to cooler crystallizer by infusion pump after, being carbonized carries out crystallisation by cooling, is cooled to 28~32 DEG C, crystallization
The solids content of gained saleratus (that is, crystallizing gains) is 580 g/l.With (the band programming automatic control of scraper self-tipping type centrifuge
Function, is capable of achieving automatic cleaning) it is centrifuged.
During centrifuge dripping, first crystallization gained saleratus in mother liquor be centrifuged off, then with deionization pure water (or
Recycling of condensed steam water) drip washing is carried out, the drip washing time is about 30 seconds, and washing water is the 20% of crystallization gained saleratus amount
(the % envelope-bulk to weight ratios, i.e. the washings of the crystallization gained saleratus adapted 20ml per 100g), obtains the high-purity carbon without ammonium
Potassium hydrogen phthalate wet product (132 kilograms).
Collected liquid during centrifuge dripping (including the liquid that is produced during crystallisation by cooling gains centrifuge dripping and pouring
The leacheate produced when washing) it is saleratus mother liquor；180 liters altogether；
High-purity saleratus wet product of the above-mentioned gained without ammonium, sodium content 483ppm, ammonium content 1.6ppm, chloride ion content
18ppm, sulfate ion content 16ppm, iron ion content 1.8ppm, content of beary metal 0.49ppm, arsenic content 0.063ppm,
Organic carbon content 3.92ppm, clarity reaches GB/T1397-1995 and analyzes pure No. 1 standard of potassium carbonate.
Above-mentioned gained saleratus mother liquor, saleratus concentration is in 306g/L, Na ion concentration 9.6g/L, chlorine ion concentration
1.0g/L, sulfate ion concentration 1.0g/L, ammonium ion concentration 12ppm, iron concentration 100ppm, heavy metal concentration
20ppm, arsenic concentration 10ppm.Saleratus mother liquor return to step 1) for dissolve potassium carbonate or for produce industrial magnesium phosphate,
Saleratus.
6), step 5) 133 kilograms of high-purity saleratus wet products without ammonium of gained, by vibrated fluidized bed pneumatic conveyer dryer
Low temperature drying is carried out, 140~150 DEG C of EAT, 105~120 DEG C of bed temperature, 80~90 DEG C of air outlet temperature, thing is controlled
Material drying time is no more than 5 minutes.Through the saleratus after pneumatic conveying drying, transfer bag, natural cooling are transferred to after being cooled to 50 DEG C
15 days, then re-sieving packaging, obtain 130 kilograms will not lump without the high-purity saleratus of ammonium.
This 130 kilograms will not lump without the high-purity saleratus of ammonium, quality index such as table 2 below：
Table 2, the gained of embodiment 2 will not lump without the high-purity saleratus testing result of ammonium
Note：These parameters, especially, remaining is in terms of butt for water removal.
Embodiment 3, one kind are non-caking without the high-purity saleratus production method of ammonium, comprise the following steps successively：
1), by industrial magnesium phosphate that 100 kilograms of mass contents are 98%, (all other indexs meet GB/T1587-
2000 certified products quality standards) input dissolving tank, add embodiment 2 in step 5) obtained by 150 liters, 15 liters of saleratus mother liquor
Deionization pure water, be warming up to 75 DEG C stirring under dissolved, obtain 218 liters of solution of potassium carbonate I；
The solution of potassium carbonate I, concentration of potassium carbonate in 452g/L, saleratus 203g/L, Na ion concentration 10.5g/L,
Chlorine ion concentration 1.1g/L, sulfate ion concentration 1.1g/L, ammonium ion concentration 10ppm, iron concentration 114ppm, a huge sum of money
Category concentration 22ppm, arsenic concentration 11ppm, temperature is 75 DEG C.
2), by step 1) gained solution of potassium carbonate I cross adsorbent post carry out absorption oil removing, obtain the solution of potassium carbonate after oil removing
Ⅱ；Described adsorbent post, absorption column packing is perlite (600-800 mesh) and absorbent cotton combination, and upper strata is absorbent cotton floor height
Degree 20cm, intermediate layer is 600-800 mesh perlite layer height 60cm, and lower floor's degreasing cotton layer is highly 20cm, and column diameter is 5cm,
Pillar material is 304 stainless steels.
Flow velocity during the mistake adsorbent post of solution of potassium carbonate I is for about 10 times of column volume/hours (19.6 ls/h).
It is described through the solution of potassium carbonate II after oil removing, carried out always using high-frequency heating Far-infrared Absorption (TOC detectors)
Organic carbon content is analyzed, and total content of organic carbon is 12ppm, visually has no oil trace.
3), to step 2) gained oil removing after solution of potassium carbonate II, under agitation, be slowly added to 109 grams of Powdered Activated Carbons
(can cross the sieve of 300 mesh) is decolourized, and carries out press filtration or suction filtration again after being incubated 30min at 75 DEG C, solution of potassium carbonate after must refining
III and filter residue I；
Solution of potassium carbonate III after gained is refined has no activated carbon by detection, and light transmittance is 99.95%, total organic carbon
Content is 9ppm, and concentration of potassium carbonate is in 452g/L, saleratus 203g/L, Na ion concentration 10.5g/L, chlorine ion concentration
1.1g/L, sulfate ion concentration 1.1g/L, ammonium ion concentration 10ppm, iron concentration 110ppm, heavy metal concentration
22ppm, arsenic concentration 11ppm, temperature are 73 DEG C.
Filter residue I (activated carbon) carries out washing suction filtration with 1 liter of deionization pure water points for 3 times, and the filter residue after must wash is (active
Charcoal) 140 grams, it is 0.10% containing potassium carbonate.Obtain 1 liter of cleaning solution, return to step 1) for dissolving potassium carbonate.
4), step 3) solution of potassium carbonate III pump into carbonators after 216 liters of gained is refined, in 50 under the oxygen free condition of sealing
Carbonation reaction is carried out under~60 DEG C of temperature, the pressure of 0.4~0.5Mpa, all the time in carbonators during carbonation reaction
Carbon dioxide is passed through, until terminating above-mentioned carbonation reaction during the pH to 8.0~8.2 of reaction gained feed liquid；Reaction gained feed liquid
It is material after carbonization.
Carbon dioxide used in described carbonation, it derives from the pair produced in industrial magnesium phosphate calcination process
Produce carbon dioxide.The by-product carbon dioxide that will be produced in industrial magnesium phosphate calcination process, first with condenser by substantial amounts of water vapour
Condense out, then adsorbed by sulfuric acid (mass concentration >=30%) again and remove ammonia, except in the carbon dioxide after ammonia and water removal
Ammonia concentration is no more than 10ppm, and steam partial pressure is no more than 30%.Then be pressure is increased to by oilless (oil free) compressor again
0.8MPa, by pipeline by the carbon dioxide input filter and oil removing dehydrater after compression, to remove oil droplet and water droplet.
That is, following condition is met by the by-product carbon dioxide after above-mentioned treatment：Pressure is more than 0.8MPa, and ammonia density is less than 10ppm, water
Part is less than 30%, and oil content is less than 10ppm.
5) material is transferred to cooler crystallizer by infusion pump after, being carbonized carries out crystallisation by cooling, is cooled to 28~32 DEG C, crystallization
The solids content of gained saleratus (that is, crystallizing gains) is 590 g/l.With (the band programming automatic control of scraper self-tipping type centrifuge
Function, is capable of achieving automatic cleaning) it is centrifuged.
During centrifuge dripping, first crystallization gained saleratus in mother liquor be centrifuged off, then with deionization pure water (or
Recycling of condensed steam water) drip washing is carried out, the drip washing time is about 30 seconds, and washing water is the 20% of crystallization gained saleratus amount
(the % envelope-bulk to weight ratios, i.e. the washings of the crystallization gained saleratus adapted 20ml per 100g), obtains the high-purity carbon without ammonium
Potassium hydrogen phthalate wet product (134 kilograms).
Collected liquid during centrifuge dripping (including the liquid that is produced during crystallisation by cooling gains centrifuge dripping and pouring
The leacheate produced when washing) it is saleratus mother liquor；181 liters altogether.
High-purity saleratus wet product of the above-mentioned gained without ammonium, sodium content 500ppm, ammonium content 2.7ppm, chloride ion content
20ppm, sulfate ion content 20ppm, iron ion content 3.4ppm, content of beary metal 0.69ppm, arsenic content 0.13ppm, have
Machine carbon content 3.79ppm, clarity reaches GB/T1397-1995 and analyzes pure No. 1 standard of potassium carbonate.
Above-mentioned gained saleratus mother liquor, saleratus concentration is in 298g/L, and Na ion concentration 11.8g/L, chlorion is dense
Degree 1.21g/L, sulfate ion concentration 1.20g/L, ammonium ion concentration 14ppm, iron concentration 132ppm, heavy metal concentration
27ppm, arsenic concentration 14ppm.Saleratus mother liquor return to step 1) for dissolve potassium carbonate or for produce industrial magnesium phosphate,
Saleratus.
6), step 5) 134 kilograms of high-purity saleratus wet products without ammonium of gained, by vibrated fluidized bed pneumatic conveyer dryer
Low temperature drying is carried out, 140~150 DEG C of EAT, 105~120 DEG C of bed temperature, 80~90 DEG C of air outlet temperature, thing is controlled
Material drying time is no more than 5 minutes.Through the saleratus after pneumatic conveying drying, transfer bag, natural cooling are transferred to after being cooled to 50 DEG C
15 days, then re-sieving packaging, obtain 132 kilograms will not lump without the high-purity saleratus of ammonium.
This 132 kilograms will not lump without the high-purity saleratus of ammonium, quality index such as table 3 below：
Table 3, the gained of embodiment 3 will not lump without the high-purity saleratus testing result of ammonium
| Project | Quality index required value | Actual measured value |
| Saleratus (KHCO3)/%, w/w >= | 99.5 | 99.65 |
| Potassium carbonate (K2CO3)/%, w/w≤ | 0.5 | 0.32 |
| Sodium content (Na)/ppm≤ | 500 | 500 |
| Chloride (CL)/ppm≤ | 20 | 20 |
| Sulphur compound is (with SO4Meter)/ppm≤ | 20 | 20 |
| Iron (in terms of Fe)/ppm≤ | 5 | 3.4 |
| Ammonium is (with NH4Meter)/ppm≤ | 5 | 2.7 |
| Heavy metal (in terms of Pb)/ppm≤ | 5 | 0.69 |
| Arsenic (in terms of As)/ppm≤ | 1 | 0.13 |
| Total organic carbon (in terms of C)/ppm≤ | 5 | 3.79 |
| PH value (20g/L, 25 DEG C)≤ | 8.3 | 8.2 |
| Moisture content/%, w/w≤ | 0.2 | 0.11 |
| Clarity≤ | 1# | Meet |
Note：These parameters, especially, remaining is in terms of butt for water removal.
Embodiment 4, one kind are non-caking without the high-purity saleratus production method of ammonium, comprise the following steps successively：
1), by industrial magnesium phosphate that 100 kilograms of mass contents are 98%, (all other indexs meet GB/T1587-
2000 certified products quality standards) input dissolving tank, add embodiment 3 in step 5) obtained by 50 liters, 125 liters of saleratus mother liquor
Deionization pure water, be warming up to 75 DEG C stirring under dissolved, obtain 198 liters of solution of potassium carbonate I；
The solution of potassium carbonate I, concentration of potassium carbonate is in 495g/L, saleratus 76g/L, Na ion concentration 7.3g/L, chlorine
Ion concentration 0.76g/L, sulfate ion concentration 0.76g/L, ammonium ion concentration 9ppm, iron concentration 79ppm, heavy metal
Concentration 16ppm, arsenic concentration 8ppm, temperature are 75 DEG C.
2), by step 1) gained solution of potassium carbonate I cross adsorbent post carry out absorption oil removing, obtain the solution of potassium carbonate after oil removing
Ⅱ；Described adsorbent post, absorption column packing is perlite (600-800 mesh) and absorbent cotton combination, and upper strata is absorbent cotton floor height
Degree 20cm, intermediate layer is 600-800 mesh perlite layer height 60cm, and lower floor's degreasing cotton layer is highly 20cm, and column diameter is 5cm,
Pillar material is 304 stainless steels.
Flow velocity during the mistake adsorbent post of solution of potassium carbonate I is for about 10 times of column volume/hours (19.6 ls/h).
It is described through the solution of potassium carbonate II after oil removing, carried out always using high-frequency heating Far-infrared Absorption (TOC detectors)
Organic carbon content is analyzed, and total content of organic carbon is 11ppm, visually has no oil trace.
3), to step 2) gained oil removing after solution of potassium carbonate II, under agitation, be slowly added to 100 grams of Powdered Activated Carbons
(can cross the sieve of 300 mesh) is decolourized, and carries out press filtration or suction filtration again after being incubated 30min at 75 DEG C, solution of potassium carbonate after must refining
III and filter residue I；
Solution of potassium carbonate III after gained is refined has no activated carbon by detection, and light transmittance is 99.98%, total organic carbon
Content is 8ppm, and concentration of potassium carbonate is in 495g/L, saleratus 76g/L, Na ion concentration 7.3g/L, chlorine ion concentration 0.76g/
L, sulfate ion concentration 0.76g/L, ammonium ion concentration 9ppm, iron concentration 74ppm, heavy metal concentration 16ppm, arsenic are dense
Degree 8ppm, temperature is 72 DEG C.
Filter residue I (activated carbon) carries out washing suction filtration with 1 liter of deionization pure water points for 3 times, and the filter residue after must wash is (active
Charcoal) 140 grams, it is 0.13% containing potassium carbonate.Obtain 1 liter of cleaning solution, return to step 1) for dissolving potassium carbonate.
4), step 3) solution of potassium carbonate III pump into carbonators after 198 liters of gained is refined, in 50 under the oxygen free condition of sealing
~60 DEG C of temperature, the pressure of 0.4~0.5Mpa carry out carbonation reaction, lead to in carbonators all the time during carbonation reaction
Enter carbon dioxide, until terminating above-mentioned carbonation reaction during the pH to 8.0~8.2 of reaction gained feed liquid；Reacting gained feed liquid is
Material after carbonization.
Carbon dioxide used in described carbonation, it derives from the pair produced in industrial magnesium phosphate calcination process
Produce carbon dioxide.The by-product carbon dioxide that will be produced in industrial magnesium phosphate calcination process, first with condenser by substantial amounts of water vapour
Condense out, then adsorbed by sulfuric acid (mass concentration >=30%) again and remove ammonia, except in the carbon dioxide after ammonia and water removal
Ammonia concentration is no more than 10ppm, and steam partial pressure is no more than 30%.Then be pressure is increased to by oilless (oil free) compressor again
0.8MPa, by pipeline by the carbon dioxide input filter and oil removing dehydrater after compression, to remove oil droplet and water droplet.
That is, following condition is met by the by-product carbon dioxide after above-mentioned treatment：Pressure is more than 0.8MPa, and ammonia density is less than 10ppm, water
Part is less than 30%, and oil content is less than 10ppm.
5) material is transferred to cooler crystallizer by infusion pump after, being carbonized carries out crystallisation by cooling, is cooled to 28~32 DEG C, crystallization
Gained saleratus (that is, crystallizing gains) solids content is 556 g/l.With scraper self-tipping type centrifuge (band programming automatic control work(
Can, it is capable of achieving automatic cleaning) it is centrifuged.
During centrifuge dripping, first crystallization gained saleratus in mother liquor be centrifuged off, then with deionization pure water (or
Recycling of condensed steam water) drip washing is carried out, the drip washing time is about 25 seconds, and washing water is the 20% of crystallization gained saleratus amount
(the % envelope-bulk to weight ratios, i.e. the washings of the crystallization gained saleratus adapted 20ml per 100g), obtains the high-purity carbon without ammonium
Potassium hydrogen phthalate wet product (104 kilograms).
Collected liquid during centrifuge dripping (including the liquid that is produced during crystallisation by cooling gains centrifuge dripping and pouring
The leacheate produced when washing) it is saleratus mother liquor；160 liters altogether.
High-purity saleratus wet product of the above-mentioned gained without ammonium, sodium content 396ppm, ammonium content 2.3ppm, chloride ion content
11ppm, sulfate ion content 10ppm, iron ion content 1.9ppm, content of beary metal 0.31ppm, arsenic content 0.046ppm,
Organic carbon content 3.73ppm, clarity reaches GB/T1397-1995 and analyzes pure No. 1 standard of potassium carbonate.
Above-mentioned gained saleratus mother liquor, saleratus concentration is in 303g/L, Na ion concentration 8.9g/L, chlorine ion concentration
0.89g/L, sulfate ion concentration 0.88g/L, ammonium ion concentration 13ppm, iron concentration 92ppm, heavy metal concentration
27ppm, arsenic concentration 19ppm.Saleratus mother liquor return to step 1) for dissolve potassium carbonate or for produce industrial magnesium phosphate,
Saleratus.
6), step 5) 104 kilograms of high-purity saleratus wet products without ammonium of gained, by vibrated fluidized bed pneumatic conveyer dryer
Low temperature drying is carried out, controls 140-150 DEG C of EAT, 105-120 DEG C of bed temperature, 80-90 DEG C of air outlet temperature, material to do
The dry time is no more than 5 minutes.Through the saleratus after pneumatic conveying drying, be transferred to after being cooled to 50 DEG C transfer bag, natural cooling 15 days,
Then re-sieving packaging, obtain 102 kilograms will not lump without the high-purity saleratus of ammonium.
This 102 kilograms will not lump without the high-purity saleratus of ammonium, quality index such as table 4 below：
Table 4, the gained of embodiment 4 will not lump without the high-purity saleratus testing result of ammonium
| Project | Quality index required value | Actual measured value |
| Saleratus (KHCO3)/%, w/w >= | 99.5 | 99.71 |
| Potassium carbonate (K2CO3)/%, w/w≤ | 0.5 | 0.27 |
| Sodium content (Na)/ppm≤ | 500 | 396 |
| Chloride (CL)/ppm≤ | 20 | 11 |
| Sulphur compound is (with SO4Meter)/ppm≤ | 20 | 10 |
| Iron (in terms of Fe)/ppm≤ | 5 | 1.9 |
| Ammonium is (with NH4Meter)/ppm≤ | 5 | 2.3 |
| Heavy metal (in terms of Pb)/ppm≤ | 5 | 0.31 |
| Arsenic (in terms of As)/ppm≤ | 1 | 0.046 |
| Total organic carbon (in terms of C)/ppm≤ | 5 | 3.73 |
| PH value (20g/L, 25 DEG C)≤ | 8.3 | 8.2 |
| Moisture content/%, w/w≤ | 0.2 | 0.10 |
| Clarity≤ | 1# | Meet |
Note：These parameters, especially, remaining is in terms of butt for water removal.
Comparative example 1, for embodiment 1, make following change：
Cancellation step 2)；In step 3) in, with " step 1) gained solution of potassium carbonate I " replacements " step 2) obtained by after oil removing
Solution of potassium carbonate II "；Remaining is equal to embodiment 1.
By detection, though having no activated carbon, light transmittance is only 98.26% to solution of potassium carbonate III after gained is refined, always
Organic carbon content reaches 198ppm, considerably beyond technological requirement index.
The final dried saleratus of gained, quality index is as follows：
Table 5, the gained of comparative example 1 will not lump without the high-purity saleratus testing result of ammonium
| Project | Quality index required value | Actual measured value |
| Saleratus (KHCO3)/%, w/w >= | 99.5 | 99.72 |
| Potassium carbonate (K2CO3)/%, w/w≤ | 0.5 | 0.27 |
| Sodium content (Na)/ppm≤ | 500 | 349 |
| Chloride (CL)/ppm≤ | 20 | 9 |
| Sulphur compound (in terms of SO4)/ppm≤ | 20 | 9 |
| Iron (in terms of Fe)/ppm≤ | 5 | 0.8 |
| Ammonium (in terms of NH4)/ppm≤ | 5 | 0.9 |
| Heavy metal (in terms of Pb)/ppm≤ | 5 | 0.23 |
| Arsenic (in terms of As)/ppm≤ | 1 | 0.016 |
| Total organic carbon (in terms of C)/ppm≤ | 5 | 63.27 |
| PH value (20g/L, 25 DEG C)≤ | 8.3 | 8.2 |
| Moisture content/%, w/w≤ | 0.2 | 0.10 |
| Clarity≤ | 1# | It is unqualified |
Note：These parameters, especially, remaining is in terms of butt for water removal.
Being can be seen that without step 2 from above-mentioned analysis result) adsorbent post carries out absorption oil removing, gained saleratus
Total organic carbon and clarity are all difficult to reach requirement.
Comparative example 2, for embodiment 2, simply to step 5) wash time (washing water consumption) be adjusted it is right
Than remaining operation is with embodiment 2.
The test result such as table 6 below contrasted with different wash times (washing water consumption).
Table 6, the gained of comparative example 2 will not lump without the high-purity saleratus testing result of ammonium (different wash time contrasts)
Note：These parameters, especially, remaining is in terms of butt for water removal.
Step 5 is can be seen that from the comparing result of above-mentioned table 6) water consumption (wash time length) is washed to product quality
Influence is very big, because the impurity content in the saleratus mother liquor after carbonating is very high, and during centrifuge dripping, also
A small amount of residue of mother can will remain in the mother liquor on saleratus plane of crystal by pure water in saleratus crystal
Washing is displaced, with improve product quality.
Washing water consumption (wash time length) directly affects clean result, and washing water consumption very few (time is too short) is then produced
Quality is unqualified, and washs water consumption excessive (overlong time) although product quality can be improved, and product yield is too low, shadow
Ring production efficiency and production cost.
Remarks explanation：When washing water is 20% (embodiment 2), 132 kilograms of institute saleratus wet product；And wash water and be
When 33%, gained saleratus wet product is only 119 kilograms, and yield is substantially reduced, so as to also increase the evaporation energy consumption of subsequent mother liquor.
And can also be seen that washing water consumption excessively not only influences product yield and production from above-mentioned comparative test result
Cost, and quality is not significantly increased, illustrates that the mother liquor washing that washing is simply remained saleratus plane of crystal is put
Change, the impurity inside crystallization can not be removed, therefore control washing water within the specific limits just can be with.
Comparative example 3, for embodiment 1, simply to step 6) the dried saleratus natural cooling time is long
Short that product caking situation is contrasted, remaining operation is with embodiment 1.
Through the saleratus after pneumatic conveying drying, transfer bag is transferred to after being cooled to 50 DEG C, natural cooling, cool time contrast sets
It is set to 0,1,5,10,15,20 and 30 days, then sieving is packed respectively again, is obtained without the high-purity saleratus of ammonium, with 25 kilograms of bag
Pack (double-deck PE inner bags, one layer of outside Polywoven Bag) is packed, and is placed on planar deck, presses 9 layers 25 kilograms again above
The saleratus product of packaging, storage is removed after 30 days and sees whether caking, and assessment degree of agglomeration.
Table 7, the comparative example 3 different natural cooling times are to the influence contrast without the high-purity saleratus caking capacity energy of ammonium
| Project | Package temperature (DEG C) | Whether lump | Mobility |
| 0 day | 49 | Caking is serious, and hand pressure is not broken | Caking cannot flow |
| 1 day | 32 | Caking is serious, and hand pressure is not broken | Caking cannot flow |
| 5 days | 28 | Part is lumpd, and hand pressure can disperse substantially | Caking cannot flow |
| 10 days | 25 | A small amount of false caking, light pressure dispersion | 99 seconds |
| 15 days (embodiment 1) | 25 | Substantially without caking | 92 seconds |
| 20 days | 25 | Substantially without caking | 93 seconds |
| 30 days | 25 | Substantially without caking | 92 seconds |
Note：100 grams of test samples evaluate mobility full by nozzle diameter for the funnel required time of 12mm, and the time gets over
It is poorer that length represents mobility.
The dried saleratus natural cooling time is can be seen that from the contrast test result of above-mentioned table 7 to directly affect
The caking performance of product, is packed by re-sieving after the natural cooling of 15 days, and product does not lump substantially.
Comparative example 4, for embodiment 1, only to step 4) carbon dioxide used in carbonation is pre-
Processing method is adjusted；It is specific as follows：
Scheme 1 is to replace by-product carbon dioxide with food-grade carbon-dioxide；
The carbon dioxide preprocess method of scheme 2 is with embodiment 1；
In the carbon dioxide preprocessing process of scheme 3, unused concentrated sulfuric acid absorption removes ammonia, and concrete operations are as follows：By industrial carbon
The by-product carbon dioxide produced in sour potassium calcination process, is first condensed out substantial amounts of water vapour with condenser, controls titanium dioxide
Steam partial pressure is no more than 30% in carbon, then pressure is increased to 0.8MPa by oilless (oil free) compressor again, will be pressed by pipeline
Carbon dioxide input filter and oil removing dehydrater after contracting, to remove oil droplet and water droplet.
Remaining operation is with embodiment 1.
Gained saleratus product quality analysis result such as table 8 below：
Table 8, the gained of comparative example 4 will not lump without the high-purity saleratus testing result of ammonium (different carbon dioxide contrasts)
Note：These parameters, remove water especially, remaining in terms of butt
Food-grade carbon-dioxide and pretreated carbon dioxide of the present invention are can be seen that from the comparing result of table 8
It is not different.But in preprocessing process, if not removing ammonia, producing saleratus amount containing ammonium can be considerably beyond quality standard.
Experiment 1, according to the caking assessment mode informed in comparative example 3, to 1~embodiment of embodiment 4, comparative example 1, contrast
Example 2, the products therefrom of comparative example 4 are detected that acquired results are satisfied by following condition：Cooling (package temperature is within the 15th day
25 DEG C) detected, substantially without caking, mobility is each about 92 seconds.
Finally, in addition it is also necessary to it is noted that listed above is only several specific embodiments of the invention.Obviously, this hair
It is bright to be not limited to above example, there can also be many deformations.One of ordinary skill in the art can be from present disclosure
The all deformations directly derived or associate, are considered as protection scope of the present invention.
Claims (11)
1. the non-caking production method without the high-purity saleratus of ammonium, it is characterized in that comprising the following steps successively：
1) leftover bits and pieces in the industrial magnesium phosphate of mass content >=98% or potassium carbonate production process, is put into dissolving tank, plus
Enter deionization pure water or recycling of condensed steam water or step 3) obtained by cleaning solution or step 5) obtained by saleratus mother liquor
In at least one, the leftover bits and pieces in above-mentioned industrial magnesium phosphate or potassium carbonate production process are warming up under stirring condition is complete
Portion dissolves, and obtains solution of potassium carbonate I；
When add be only deionization pure water or recycling of condensed steam water when, control solution of potassium carbonate I in potassium carbonate concentration >=
550 g/l；
Use step 3 when added) obtained by cleaning solution or step 5) obtained by saleratus mother liquor when, control potassium carbonate
Potassium carbonate and saleratus concentration sum are 550~655g/L in solution I；
2), by step 1) obtained by solution of potassium carbonate I cross adsorbent post carry out absorption oil removing, obtain the solution of potassium carbonate after oil removing
Ⅱ；
3), under agitation, to step 2) gained oil removing after solution of potassium carbonate II in add decolorising agent decolourized, then
Filtered, filtrate and filter residue I are obtained respectively, the filtrate is refined rear solution of potassium carbonate III；
Filter residue I is washed with deionization pure water, cleaning solution return to step 1) for dissolving potassium carbonate；
4), by step 3) obtained by refined rear solution of potassium carbonate III pump into carbonating column, under the oxygen free condition of sealing in 50~
Carbonation reaction is carried out under 60 DEG C of temperature, the pressure of 0.4~0.5Mpa, is led to in carbonators all the time during carbonation reaction
Enter carbon dioxide, until terminating above-mentioned carbonation reaction during the pH to 8.0~8.2 of reaction gained feed liquid；
Reaction gained feed liquid is material after carbonization；
5) material is transferred to cooler crystallizer by infusion pump after, being carbonized, and is cooled to 25~35 DEG C, then carries out centrifuge dripping, from
During the heart is dried, drip washing is carried out as washings with deionization pure water or recycling of condensed steam water, obtain the high-purity carbon without ammonium
Potassium hydrogen phthalate wet product；
Collected mixing liquid is referred to as saleratus mother liquor during centrifuge dripping；
6), step 5) obtained by the high-purity saleratus wet product without ammonium be dried by vibrated fluidized bed pneumatic conveyer dryer,
After natural cooling pack, obtain will not lump without the high-purity saleratus of ammonium.
2. the non-caking production method without the high-purity saleratus of ammonium according to claim 1, it is characterized in that：Step 5)
The saleratus mother liquor of the part of gained is back to step 1) in for dissolving industrial magnesium phosphate or potassium carbonate production process in
Leftover bits and pieces, its back amount is with rate-determining steps 1) obtained by solution of potassium carbonate I meet following index：Na ion concentration is less than 8g/
L, chlorine ion concentration are less than 50ppm, iron concentration less than 1.0g/L, sulfate concentration less than 1.0g/L, ammonium ion concentration
It is limited less than 100ppm less than 100ppm, arsenic concentration less than 100ppm, heavy metal concentration, when any one in solution of potassium carbonate I
When index exceedes above-mentioned limit value, then stop the return of saleratus mother liquor；
Remaining saleratus mother liquor is used to produce technical grade saleratus or potassium carbonate.
3. the non-caking production method without the high-purity saleratus of ammonium according to claim 2, it is characterized in that：
The step 1) in, step 3 has been used when added) obtained by cleaning solution or step 5) obtained by saleratus mother liquor
When, it is 550~655g/L that potassium carbonate and saleratus concentration sum are controlled in solution of potassium carbonate I, and Na ion concentration is less than
10.5g/L, chlorine ion concentration be less than 1.1g/L, sulfate concentration be less than 1.1g/L, ammonium ion concentration be less than 50ppm, iron from
Sub- concentration is less than 114ppm, and heavy metal concentration is less than 100ppm, and arsenic concentration is less than 100ppm, and temperature is not less than 70 DEG C.
4. according to any described non-caking production method without the high-purity saleratus of ammonium of claims 1 to 3, its feature
It is：
The step 2) adsorbent column packing combined by perlite and absorbent cotton；
Described adsorbent column packing is made up of upper strata, intermediate layer and lower floor；The upper strata for account for adsorbent pillar height degree 19~
21% absorbent cotton, the intermediate layer is the perlite for accounting for adsorbent pillar height degree 58~62%, and the lower floor is to account for adsorbent post
Highly 19~21% absorbent cotton.
5. according to any described non-caking production method without the high-purity saleratus of ammonium of claims 1 to 3, its feature
It is：
Step 2) obtained by oil removing after solution of potassium carbonate II need to meet following condition：Organic carbon content must not exceed 50ppm, mesh
Depending on oil trace must not be seen；
When the conditions set forth above are not met, it is necessary to repeat the absorption oil removing that adsorbent post carries out again.
6. according to any described non-caking production method without the high-purity saleratus of ammonium of claims 1 to 3, its feature
It is：
The step 3) in decolorising agent be powdered activated carbon, per 100ml II adapted of solution of potassium carbonate >=0.05g work
Property charcoal；
Solution of potassium carbonate III after gained is refined is it is ensured that light transmittance otherwise needs to repeat step 3 more than 99.9%).
7. according to any described non-caking production method without the high-purity saleratus of ammonium of claims 1 to 3, its feature
It is：
The step 3) in, the carbonic acid potassium content of the filter residue I after washing should be less than 0.5%, and the filter residue I after washing can be mixed into coal
Burnt.
8. according to any described non-caking production method without the high-purity saleratus of ammonium of claims 1 to 3, its feature
It is：
The step 5) drip washing：The drip washing time is 5~30 seconds, and the crystallisation by cooling 5~20ml's of gains adapted per 100g washes
Wash water.
9. according to any described non-caking production method without the high-purity saleratus of ammonium of claims 1 to 3, its feature
It is：
The step 6) in, using vibrated fluidized bed pneumatic conveying drying, 140~150 DEG C of EAT, bed temperature 105~120
DEG C, 80~90 DEG C of air outlet temperature, the dry materials time is no more than 5 minutes.
10. according to any described non-caking production method without the high-purity saleratus of ammonium of claims 1 to 3, its feature
It is：
The step 6) in, dried saleratus is first transferred to transfer bag after being cooled to 50~60 DEG C, enter naturally cold in warehouse
But packed again after 0-30 days, so that it is guaranteed that saleratus product is not added with anticaking agent can not also lump.
11. according to any described non-caking production method without the high-purity saleratus of ammonium of claims 1 to 3, its feature
It is：
The step 4) in, carbon dioxide used in carbonation, it is produced in deriving from industrial magnesium phosphate calcination process
By-product carbon dioxide or food-grade carbon-dioxide；The by-product titanium dioxide produced in using industrial magnesium phosphate calcination process
Carbon, due to containing substantial amounts of ammonia and water vapour in the by-product carbon dioxide of generation in industrial magnesium phosphate calcination process, therefore needs
Carry out except ammonia and water removal；It is removed in ammonia and removal process, is first condensed out so as to be formed substantial amounts of water vapour with condenser
Recycling of condensed steam water, then again with sulfuric acid be adsorbent remove ammonia；Control is except ammonia in the carbon dioxide after ammonia and water removal
Concentration is no more than 10ppm, and steam partial pressure is no more than 30%.
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| CN109174468A (en) * | 2018-08-30 | 2019-01-11 | 贺州市骏鑫矿产品有限责任公司 | One kind is for the complicated difficult efficient ore dressing impurity-removing method of potash feldspar ore |
| CN113998710A (en) * | 2020-07-28 | 2022-02-01 | 自然资源部天津海水淡化与综合利用研究所 | Method for separating potassium fluoride, potassium bromide, potassium carbonate and potassium bicarbonate mixed salt |
| CN115108568A (en) * | 2022-04-01 | 2022-09-27 | 浙江大洋生物科技集团股份有限公司 | Method for preparing potassium carbonate from fly ash washing byproduct potassium chloride |
| CN115448332A (en) * | 2022-11-11 | 2022-12-09 | 山东海化集团有限公司 | Method for preparing potassium carbonate by continuous ion exchange of fixed bed |
| CN115924938A (en) * | 2022-12-30 | 2023-04-07 | 华融化学股份有限公司 | Production process of food-grade potassium carbonate and food-grade potassium bicarbonate |
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| CN105253902A (en) * | 2015-11-12 | 2016-01-20 | 浙江大洋生物科技集团股份有限公司 | Refining purifying and recycling method for scrap potassium carbonate containing conduction oil |
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| CN109174468A (en) * | 2018-08-30 | 2019-01-11 | 贺州市骏鑫矿产品有限责任公司 | One kind is for the complicated difficult efficient ore dressing impurity-removing method of potash feldspar ore |
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| CN115108568A (en) * | 2022-04-01 | 2022-09-27 | 浙江大洋生物科技集团股份有限公司 | Method for preparing potassium carbonate from fly ash washing byproduct potassium chloride |
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| CN115448332B (en) * | 2022-11-11 | 2023-03-21 | 山东海化集团有限公司 | Method for preparing potassium carbonate by continuous ion exchange of fixed bed |
| CN115924938A (en) * | 2022-12-30 | 2023-04-07 | 华融化学股份有限公司 | Production process of food-grade potassium carbonate and food-grade potassium bicarbonate |
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