CN106745094B - 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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- CN106745094B CN106745094B CN201611251678.2A CN201611251678A CN106745094B CN 106745094 B CN106745094 B CN 106745094B CN 201611251678 A CN201611251678 A CN 201611251678A CN 106745094 B CN106745094 B CN 106745094B
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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
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- 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 the cleaning solution obtained by deionization pure water (or recycling of condensed steam water) or step 3), or in the saleratus mother liquor obtained by step 5), pass through adsorbent oil removing, refined again by bleaching agent bleaching, 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 high-purity, (sodium content is less than 500ppm, and ammonium content is less than 10ppm, and total content of organic carbon is less than 10ppm, carbon
Potassium hydrogen phthalate content >=99.5%) saleratus production method.
Background technology
Potassium carbonate and saleratus are the very clear and definite and simple compounds of structure, are both a kind of ancient and traditional chemistry
Composition, and 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
Kind new product.Saleratus is production potassium acetate, potassium fluoride, potassium arsenite and mountain as a kind of inorganic salts basic chemical industry raw material
The raw material of potassium sorbate, chemical industry, medicine, agricultural chemicals and chemical fertilizer are also commonly used for, 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 higher requirement.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 parses potassium ion using ammonium hydrogen carbonate as parsing agent under cationic ion-exchange resin,
Potassium ion combines to form saleratus with bicarbonate ion, but ammonium hydrogen carbonate excessive in exchange process is also with saleratus
Solution gets off together, subsequently through being concentrated by evaporation and drying, although can fall most ammonium bicarbonate breaks down, conventional work
Skill is difficult to accomplish requirement of the ammonium content less than 10ppm in saleratus product.Due to used in 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 require.
During electrolysis with ion-exchange film carbonizatin method production saleratus, raw material potassium chloride is dense by refinement treatment, electrolysis, evaporation
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 by refinement treatment so that ammonium thoroughly to be removed, therefore ammonium content overproof in saleratus can be caused.It was carbonated simultaneously
Carbon dioxide used, the typically carbon dioxide with the flue gas after lime stone high-temperature calcination after purified in journey, either
Synthesize ammonia and synthesize the carbon dioxide of the waste gas of urea element as gained after net, wherein sulphur is difficult thoroughly to remove, and is eaten although can use
Grade carbon dioxide or the carbon dioxide of higher level are 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), this method uses organic amine
Method produces potassium carbonate and saleratus.Having using silica as immobilized body is added into the Klorvess Liquid after refinement treatment
Machine amine solid-carried catalyst, carbon dioxide is passed through, caused hydrogen chloride absorption is removed in organic amine solid-carried catalyst, reaction solution
Then saleratus is produced by being concentrated by evaporation.This method has the advantages of technique is simple, and three wastes are few, but organic amine is poisonous
Organic chemical reagent, the saleratus produced is only used for producing regular industrial product, and the industry such as food, medicine can not answer
With, and poor product quality, impurity is more, and the potassium chloride for largely 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,
Potassium-enriched rock through broken, ore dressing, is obtained the powder using potassium feldspar as main thing phase by this method.By K-feldspar powder and sodium carbonate
After combined grinding, calcined first at 750 DEG C -850 DEG C, suitable quantity of water is added in the clinker powder then obtained to calcining and is filled
Divide and be stirred, formation contains potassium solution.By being passed through CO to containing potassium solution2Carry out acidifying neutralization reaction, make silicon therein, aluminium and
Other impurities component forms precipitation, is used to prepare a kind of novel inorganic nonmetallic materials mineral polymeric material after filtering.Filtering
Obtained clarification, through evaporating, crystallizing, separating, obtains the excellent pure sodium carbonate of byproduct containing potassium solution.Remaining a small amount of sodium carbonate is formed
Potassium sodium double salt, calcining dispensing can be used as to recycle.Remaining high concentration solution of potassium carbonate cleans, after purification through further, then
Through after-souring, crystallization, calcining, that is, election class potassium carbonate finished product is made.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, this method after water dust-removal and desulfurizing
In, (NH is made4)2CO3Solution, add 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, and solution layering, 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, filter out after deamination residual
The NiCO stayed3After be evaporated to obtain K2CO3Product；Ni(NH3)Cl2Water is dissolved in, adds lime, after heating evaporation deamination is complete, filters out Ni
(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, this method institute are public
The technique opened mainly include desorption, evaporation, absorb, carbonating, crystallization, dry etc. unit, processing step be：Ion exchange is completed
Decomposed after liquid preheating in desorber, subsequently into triple effect evaporation unit, complete evaporation of liquid enters carbon dioxide absorption tower, carbonic acid
Potassium is all carbonated as saleratus.Carbonating carbon dioxide gas used comes from desorber and drier, and desorber decomposes
Ammonia by ammonia absorber be absorbed as ammoniacal liquor do with liquid use.Saleratus crystallization dries through centrifuge, and dry packing is finished product
Potassium carbonate.The present invention cancels existing ash furnace workshop section, reduces environmental pollution, except fixed gas is thorough, improves heat transfer coefficient, titanium dioxide
Carbon centralized collection concentration is high, reduces carbonation time, improves production efficiency, saves raw material, reduces cost, significantly improve economy
Benefit and social benefit.Although what the technology solved carbon dioxide carrys out source problem, two caused by its drying process
Carbonoxide contains substantial amounts of water vapour and ammonia, plus containing substantial amounts of carbonic acid in the saleratus ion exchanged soln used in it
Hydrogen ammonium, therefore high-purity saleratus without ammonium can not be produced, the removal of anticaking agent in saleratus is not solved plus it
Technology, product clarity are 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, present invention offer one kind is non-caking is free of the high-purity saleratus (bicarbonate of ammonium
Potassium content >=99.65%) production method, comprise 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%) cleaning solution or step obtained by input dissolving tank, addition deionization pure water or recycling of condensed steam water or step 3)
5) at least one of saleratus mother liquor obtained by, heating (generally >=70 DEG C) the extremely 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 the only deionization pure water or recycling of condensed steam water of addition, 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)；
When using the saleratus mother liquor obtained by cleaning solution or the step 5) obtained by step 3) when added, carbon is controlled
Potassium carbonate and saleratus concentration sum are 550~655g/L in sour potassium solution I；
2) solution of potassium carbonate I obtained by step 1), is crossed into adsorbent post and carries out absorption oil removing, it is molten to obtain the potassium carbonate after oil removing
Liquid II；
3) (being slowly added to), under agitation, is added into the solution of potassium carbonate II after oil removing obtained by step 2) to decolourize
Agent is decolourized, and is then filtered (press filtration or suction filtration), obtains filtrate and filter residue I 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) it is used to dissolve
Potassium carbonate；
4) solution of potassium carbonate III after refined obtained by step 3), is pumped into carbonating column, under the oxygen free condition of sealing in
Carbonation reaction is carried out under 50~60 DEG C of temperature, 0.4~0.5Mpa pressure, 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 carry out centrifuge dripping, during centrifuge dripping, drenched by the use of deionization pure water or recycling of condensed steam water as washings
Wash, obtain high-purity saleratus wet product without ammonium；
Collected mixing liquid during centrifuge dripping (including liquid caused by crystallisation by cooling gains centrifuge dripping
With elution caused by leacheate) be referred to as saleratus mother liquor；
6), high-purity saleratus wet product without ammonium obtained by step 5) is done by vibrated fluidized bed pneumatic conveyer dryer
Dry (low temperature drying), packaging (can select screen sizes according to customer requirement, packed again after sieving) after natural cooling, obtaining to tie
Block is free of the high-purity saleratus of ammonium.
Remarks explanation：After drying, transfer bag is transferred to after first can suitably cooling down, then naturally cools to sieving packaging after room temperature.
Improvement as the non-caking production method without the high-purity saleratus of ammonium of the present invention：Portion obtained by step 5)
The saleratus mother liquor divided, which is back in step 1), to be used to dissolve the leftover bits and pieces 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：It is dense that Na ion concentration is less than 8g/L, chlorion
Degree is less than 1.0g/L less than 1.0g/L, sulfate concentration, ammonium ion concentration is less than 50ppm, iron concentration is less than 100ppm,
Heavy metal concentration is less than 100ppm, arsenic concentration and is limited 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).
Further improvement as the non-caking production method without the high-purity saleratus of ammonium of the present invention：
In the step 1), the saleratus obtained by cleaning solution or the step 5) obtained by step 3) has been used when added
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 are 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.
Further improvement as the non-caking production method without the high-purity saleratus of ammonium of the present invention：
The adsorbent column packing of the step 2) is 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 are the treasure for accounting for adsorbent pillar height degree 58~62% (preferably 60%)
Zhu Yan (600~800 mesh), the lower floor are the absorbent cotton for accounting for adsorbent pillar height degree 19~21% (preferably 20%).
Further improvement as the non-caking production method without the high-purity saleratus of ammonium of the present invention：
Solution of potassium carbonate II after oil removing obtained by step 2) need to meet following condition：Organic carbon content must not exceed
50ppm, it must not visually see oil trace；
When the conditions set forth above are not met, it is necessary to repeat the absorption oil removing of adsorbent post progress again.
Further improvement as the non-caking production method without the high-purity saleratus of ammonium of the present invention：
Decolorising agent in the step 3) is the activated carbon of powdered (sieve that can cross 300 mesh), and the potassium carbonate per 100ml is molten
II adapted of liquid >=0.05g activated carbon；
Otherwise solution of potassium carbonate III after gained is refined is needed again it is ensured that light transmittance is more than 99.9% (i.e. without activated carbon)
Step 3) (that is, it needs to needing to re-start decolorization operations) is carried out again.
Further improvement as the non-caking production method without the high-purity saleratus of ammonium of the present invention：
In the step 3), 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 burnt.
Further improvement as the non-caking production method without the high-purity saleratus of ammonium of the present invention：
The elution of the step 5)：It is 5~30 seconds to elute the time, 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 be saleratus amount 5-20%, the % envelope-bulk to weight ratios).
Remarks explanation：Eluted in the manner described above, 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.
Further improvement as the non-caking production method without the high-purity saleratus of ammonium of the present invention：
In the step 6), 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：It can ensure that dried moisture content is 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.
Further improvement as the non-caking production method without the high-purity saleratus of ammonium of the present invention：
In the step 6), dried saleratus, which is cooled to after 50~60 DEG C, is first transferred to transfer bag, enters in warehouse certainly
So (sieving packaging) is packed in cooling for 0~30 day again after (preferably 15 days), so that it is guaranteed that saleratus product is not added with anticaking agent
It can not lump.
Further improvement as the non-caking production method without the high-purity saleratus of ammonium of the present invention：
In the step 4), carbon dioxide used in carbonation, it is derived from industrial magnesium phosphate calcination process
Caused by-product carbon dioxide or food-grade carbon-dioxide；When caused by-product dioxy in use industrial magnesium phosphate calcination process
Change carbon, due to containing substantial amounts of ammonia and water vapour in caused by-product carbon dioxide in industrial magnesium phosphate calcination process, therefore
Need to carry out removing ammonia and water removal；It is removed in ammonia and removal process, is first condensed out substantial amounts of water vapour so as to shape with condenser
Into recycling of condensed steam water, then ammonia is removed with sulfuric acid (mass concentration >=30%) for adsorbent again；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, the by-product carbon dioxide after above-mentioned processing meets following condition：Pressure is more than 0.8MPa, and ammonia density is less than
10ppm, moisture content are less than 30%, and oil content is less than 10ppm.
The non-caking of the present invention is free of the high-purity saleratus production method of ammonium, 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
In the saleratus mother liquor obtained by cleaning solution or step 5) obtained, adsorbent oil removing is first passed through, then passes through bleaching agent bleaching essence
Potassium carbonate is converted into saleratus, saleratus crystallization separates out simultaneously by system, the solution of potassium carbonate after refining again through carbonation reaction
Purified, obtain saleratus wet product, saleratus finished product is dried to obtain through high gas flow.
The present invention it is a kind of it is non-caking be free of the high-purity saleratus production method of ammonium, with production cost it is low, be 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 high (sodium content is less than 500ppm, and ammonium content is less than 10ppm, and total content of organic carbon is less than 10ppm), and with work
The advantages that by-product carbon dioxide and industrial magnesium phosphate or its leftover bits and pieces in industry potassium carbonate calcination process are raw material, meet circulation warp
The production requirement of Ji and green chemical industry.
Brief description of the drawings
The embodiment of the present 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 present invention.
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, it is a kind of it is non-caking be free of the high-purity saleratus production method of ammonium, follow the steps below successively：
1), by 100 kilograms of mass contents be 98% industrial magnesium phosphate (all other indexs meet GB/T1587-
2000 certified products quality standards) input dissolving tank, (147 liters) deionization pure water is added, is warming up under 75 DEG C of stirrings and is 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 are 75 DEG C.
2) solution of potassium carbonate I obtained by step 1), is crossed into adsorbent post and carries out absorption oil removing, obtains the solution of potassium carbonate after oil removing
Ⅱ；
Described adsorbent post, absorption column packing are perlite (600-800 mesh) and absorbent cotton combination, and upper strata is absorbent cotton
Layer height 20cm, intermediate layer are 600-800 mesh perlite layer height 60cm, and lower floor's degreasing cotton layer is highly 20cm, and column diameter is
5cm, pillar material are 304 stainless steels.
Flow velocity during the mistake adsorbent post of solution of potassium carbonate I is about 10 times of column volume/hours (19.6 ls/h).
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 13ppm, visually has no oil trace.
3), to the solution of potassium carbonate II after oil removing obtained by step 2), under agitation, 90.5 grams of Powdered Activated Carbons are slowly added to
(sieve that can cross 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, light transmittance 99.94%, total organic carbon by detection
Content is 9ppm, and concentration of potassium carbonate is dense in 550g/L, Na ion concentration 4.8g/L, chlorine ion concentration 0.5g/L, sulfate ion
Spend 0.5g/L, ammonium ion concentration 6ppm, iron concentration 42ppm, heavy metal concentration 10ppm, arsenic concentration 5ppm, temperature 72
℃。
1 liter of deionization pure water of filter residue I (activated carbon), divides 3 times and carries out washing suction filtration, the filter residue (activity after must washing
Charcoal) 130 grams, it is 0.12% containing potassium carbonate.1 liter of cleaning solution is obtained, step 1) is can return to and is used to dissolve potassium carbonate.
4), refined rear solution of potassium carbonate III (about 181 liters) is pumped into carbonating column obtained by step 3), in the oxygen free condition of sealing
Under in 50~60 DEG C temperature, 0.4~0.5Mpa pressure carry out carbonation reaction, 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 caused pair in industrial magnesium phosphate calcination process
Produce carbon dioxide.By caused by-product carbon dioxide in industrial magnesium phosphate calcination process, first with condenser by substantial amounts of water vapour
Condense out, then adsorbed again by sulfuric acid (mass concentration >=30%) 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 pressure is increased to again by oilless (oil free) compressor
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, the by-product carbon dioxide after above-mentioned processing meets following condition：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 and carries out crystallisation by cooling after, being carbonized, and 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,
Automatic cleaning can be achieved) 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) eluted, the elution time is about 5 seconds, and washing water is the 5% of crystallization gained saleratus amount
(the % envelope-bulk to weight ratios, i.e. saleratus adapted 5ml washings obtained by the crystallization per 100g), obtains the high-purity carbon without ammonium
Potassium hydrogen phthalate wet product (102 kilograms).
Collected mixing liquid during centrifuge dripping (including liquid caused by crystallisation by cooling gains centrifuge dripping
With elution caused by leacheate) be saleratus mother liquor；150 liters altogether.
Above-mentioned gained is free of high-purity saleratus wet product of 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 reach GB/T1397-1995 and analyze 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) and be used to dissolve potassium carbonate or for producing industrial magnesium phosphate, carbonic acid
Hydrogen potassium.
6), 102 kilograms of high-purity saleratus wet products for being free of ammonium obtained by step 5), pass through 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, thing
Expect that drying time is no more than 5 minutes.
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 be free of the high-purity saleratus of ammonium.
This 100 kilograms will not lump be free of the high-purity saleratus of ammonium, quality index such as table 1 below：
What table 1, the gained of embodiment 1 will not lump is free of 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, it is a kind of it is non-caking be free of the high-purity saleratus production method of ammonium, follow the steps below successively：
1), by 100 kilograms of contents be 98% industrial magnesium phosphate (all other indexs meet GB/T1587-2000 close
Lattice quality standard) input dissolving tank, add 150 liters of saleratus mother liquor obtained by step 5), 15 liters of deionizations in embodiment 1
Pure water, it is warming up under 75 DEG C of stirrings and is 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), cross adsorbent post toward solution of potassium carbonate I obtained by step 1) and carry out absorption oil removing, obtain the solution of potassium carbonate after oil removing
Ⅱ；
Described adsorbent post, absorption column packing are perlite (600-800 mesh) and absorbent cotton combination, and upper strata is absorbent cotton
Layer height 20cm, intermediate layer are 600-800 mesh perlite layer height 60cm, and lower floor's degreasing cotton layer is highly 20cm, and column diameter is
5cm, pillar material are 304 stainless steels.
Flow velocity during the mistake adsorbent post of solution of potassium carbonate I is about 10 times of column volume/hours (19.6 ls/h).
The described solution of potassium carbonate II after oil removing, carried out using high-frequency heating Far-infrared Absorption (TOC detectors) total
Organic carbon content is analyzed, and total content of organic carbon 11ppm, visually has no oil trace.
3), to the solution of potassium carbonate II after oil removing obtained by step 2), under agitation, 109 grams of Powdered Activated Carbons are slowly added to
(sieve that can cross 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, light transmittance 99.96%, total organic carbon by detection
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
8ppm is spent, temperature is 73 DEG C.
1 liter of deionization pure water of filter residue I (activated carbon), divides 3 times and carries out washing suction filtration, the filter residue (activity after must washing
Charcoal) 140 grams, it is 0.11% containing potassium carbonate.Obtain 1 liter of cleaning solution, return to step 1) it is used to dissolve potassium carbonate.
4), refined rear solution of potassium carbonate III (about 218 liters) is pumped into carbonators obtained by step 3), under the oxygen free condition of sealing
Carbonation reaction is carried out under 50~60 DEG C of temperature, 0.4~0.5Mpa pressure, 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 is expected
Liquid is material after carbonization.
Carbon dioxide used in described carbonation, it derives from caused pair in industrial magnesium phosphate calcination process
Produce carbon dioxide.By caused by-product carbon dioxide in industrial magnesium phosphate calcination process, first with condenser by substantial amounts of water vapour
Condense out, then adsorbed again by sulfuric acid (mass concentration >=30%) 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 pressure is increased to again by oilless (oil free) compressor
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, the by-product carbon dioxide after above-mentioned processing meets following condition：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 and carries out crystallisation by cooling after, being carbonized, and 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, automatic cleaning can be achieved) 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) eluted, the elution time is about 30 seconds, and washing water is the 20% of crystallization gained saleratus amount
(the % envelope-bulk to weight ratios, i.e. saleratus adapted 20ml washings obtained by the crystallization per 100g), obtains the high-purity carbon without ammonium
Potassium hydrogen phthalate wet product (132 kilograms).
Collected liquid during centrifuge dripping (including liquid and leaching caused by crystallisation by cooling gains centrifuge dripping
Wash caused leacheate) it is saleratus mother liquor；180 liters altogether；
Above-mentioned gained is free of high-purity saleratus wet product of 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 reach GB/T1397-1995 and analyze 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) be used for dissolve potassium carbonate or for produce industrial magnesium phosphate,
Saleratus.
6), 133 kilograms of high-purity saleratus wet products for being free of ammonium obtained by step 5), pass through 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, thing
Expect that drying time is no more than 5 minutes.Saleratus after pneumatic conveying drying, transfer bag, natural cooling are transferred to after being cooled to 50 DEG C
15 days, then re-sieving pack, obtain 130 kilograms will not lump be free of the high-purity saleratus of ammonium.
This 130 kilograms will not lump be free of the high-purity saleratus of ammonium, quality index such as table 2 below：
What table 2, the gained of embodiment 2 will not lump is free of the high-purity saleratus testing result of ammonium
Note：These parameters, especially, remaining is in terms of butt for water removal.
Embodiment 3, it is a kind of it is non-caking be free of the high-purity saleratus production method of ammonium, comprise the following steps successively：
1), by 100 kilograms of mass contents be 98% industrial magnesium phosphate (all other indexs meet GB/T1587-
2000 certified products quality standards) input dissolving tank, add 150 liters, 15 liters of saleratus mother liquor obtained by step 5) in embodiment 2
Deionization pure water, it is warming up under 75 DEG C of stirrings and is 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
Belong to concentration 22ppm, arsenic concentration 11ppm, temperature is 75 DEG C.
2) solution of potassium carbonate I obtained by step 1), is crossed into adsorbent post and carries out absorption oil removing, obtains the solution of potassium carbonate after oil removing
Ⅱ；Described adsorbent post, absorption column packing are perlite (600-800 mesh) and absorbent cotton combination, and upper strata is absorbent cotton floor height
20cm is spent, intermediate layer is 600-800 mesh perlite layer height 60cm, and lower floor's degreasing cotton layer is highly 20cm, column diameter 5cm,
Pillar material is 304 stainless steels.
Flow velocity during the mistake adsorbent post of solution of potassium carbonate I is about 10 times of column volume/hours (19.6 ls/h).
The described solution of potassium carbonate II after oil removing, carried out using high-frequency heating Far-infrared Absorption (TOC detectors) total
Organic carbon content is analyzed, and total content of organic carbon 12ppm, visually has no oil trace.
3), to the solution of potassium carbonate II after oil removing obtained by step 2), under agitation, 109 grams of Powdered Activated Carbons are slowly added to
(sieve that can cross 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, light transmittance 99.95%, total organic carbon by detection
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.
1 liter of deionization pure water of filter residue I (activated carbon), divides 3 times and carries out washing suction filtration, the filter residue (activity after must washing
Charcoal) 140 grams, it is 0.10% containing potassium carbonate.Obtain 1 liter of cleaning solution, return to step 1) it is used to dissolve potassium carbonate.
4), 216 liters of refined rear solution of potassium carbonate III are pumped into carbonators obtained by step 3), in 50 under the oxygen free condition of sealing
Carbonation reaction is carried out under~60 DEG C of temperature, 0.4~0.5Mpa pressure, during carbonation reaction all the time into carbonators
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
For material after carbonization.
Carbon dioxide used in described carbonation, it derives from caused pair in industrial magnesium phosphate calcination process
Produce carbon dioxide.By caused by-product carbon dioxide in industrial magnesium phosphate calcination process, first with condenser by substantial amounts of water vapour
Condense out, then adsorbed again by sulfuric acid (mass concentration >=30%) 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 pressure is increased to again by oilless (oil free) compressor
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, the by-product carbon dioxide after above-mentioned processing meets following condition：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 and carries out crystallisation by cooling after, being carbonized, and 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, automatic cleaning can be achieved) 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) eluted, the elution time is about 30 seconds, and washing water is the 20% of crystallization gained saleratus amount
(the % envelope-bulk to weight ratios, i.e. saleratus adapted 20ml washings obtained by the crystallization per 100g), obtains the high-purity carbon without ammonium
Potassium hydrogen phthalate wet product (134 kilograms).
Collected liquid during centrifuge dripping (including liquid and leaching caused by crystallisation by cooling gains centrifuge dripping
Wash caused leacheate) it is saleratus mother liquor；181 liters altogether.
Above-mentioned gained is free of high-purity saleratus wet product of 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 reach GB/T1397-1995 and analyze pure No. 1 standard of potassium carbonate.
Above-mentioned gained saleratus mother liquor, saleratus concentration are dense in 298g/L, Na ion concentration 11.8g/L, chlorion
Spend 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) be used for dissolve potassium carbonate or for produce industrial magnesium phosphate,
Saleratus.
6), 134 kilograms of high-purity saleratus wet products for being free of ammonium obtained by step 5), pass through 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, thing
Expect that drying time is no more than 5 minutes.Saleratus after pneumatic conveying drying, transfer bag, natural cooling are transferred to after being cooled to 50 DEG C
15 days, then re-sieving pack, obtain 132 kilograms will not lump be free of the high-purity saleratus of ammonium.
This 132 kilograms will not lump be free of the high-purity saleratus of ammonium, quality index such as table 3 below：
What table 3, the gained of embodiment 3 will not lump is free of 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, it is a kind of it is non-caking be free of the high-purity saleratus production method of ammonium, comprise the following steps successively：
1), by 100 kilograms of mass contents be 98% industrial magnesium phosphate (all other indexs meet GB/T1587-
2000 certified products quality standards) input dissolving tank, add 50 liters, 125 liters of saleratus mother liquor obtained by step 5) in embodiment 3
Deionization pure water, it is warming up under 75 DEG C of stirrings and is 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) solution of potassium carbonate I obtained by step 1), is crossed into adsorbent post and carries out absorption oil removing, obtains the solution of potassium carbonate after oil removing
Ⅱ；Described adsorbent post, absorption column packing are perlite (600-800 mesh) and absorbent cotton combination, and upper strata is absorbent cotton floor height
20cm is spent, intermediate layer is 600-800 mesh perlite layer height 60cm, and lower floor's degreasing cotton layer is highly 20cm, column diameter 5cm,
Pillar material is 304 stainless steels.
Flow velocity during the mistake adsorbent post of solution of potassium carbonate I is about 10 times of column volume/hours (19.6 ls/h).
The described solution of potassium carbonate II after oil removing, carried out using high-frequency heating Far-infrared Absorption (TOC detectors) total
Organic carbon content is analyzed, and total content of organic carbon 11ppm, visually has no oil trace.
3), to the solution of potassium carbonate II after oil removing obtained by step 2), under agitation, 100 grams of Powdered Activated Carbons are slowly added to
(sieve that can cross 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, light transmittance 99.98%, total organic carbon by detection
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
8ppm is spent, temperature is 72 DEG C.
1 liter of deionization pure water of filter residue I (activated carbon), divides 3 times and carries out washing suction filtration, the filter residue (activity after must washing
Charcoal) 140 grams, it is 0.13% containing potassium carbonate.Obtain 1 liter of cleaning solution, return to step 1) it is used to dissolve potassium carbonate.
4), 198 liters of refined rear solution of potassium carbonate III are pumped into carbonators obtained by step 3), in 50 under the oxygen free condition of sealing
~60 DEG C of temperature, 0.4~0.5Mpa pressure carry out carbonation reaction, lead to all the time into carbonators 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 caused pair in industrial magnesium phosphate calcination process
Produce carbon dioxide.By caused by-product carbon dioxide in industrial magnesium phosphate calcination process, first with condenser by substantial amounts of water vapour
Condense out, then adsorbed again by sulfuric acid (mass concentration >=30%) 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 pressure is increased to again by oilless (oil free) compressor
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, the by-product carbon dioxide after above-mentioned processing meets following condition：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 and carries out crystallisation by cooling after, being carbonized, and 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, automatic cleaning can be achieved) 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) eluted, the elution time is about 25 seconds, and washing water is the 20% of crystallization gained saleratus amount
(the % envelope-bulk to weight ratios, i.e. saleratus adapted 20ml washings obtained by the crystallization per 100g), obtains the high-purity carbon without ammonium
Potassium hydrogen phthalate wet product (104 kilograms).
Collected liquid during centrifuge dripping (including liquid and leaching caused by crystallisation by cooling gains centrifuge dripping
Wash caused leacheate) it is saleratus mother liquor；160 liters altogether.
Above-mentioned gained is free of high-purity saleratus wet product of 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 reach GB/T1397-1995 and analyze 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) be used for dissolve potassium carbonate or for produce industrial magnesium phosphate,
Saleratus.
6), 104 kilograms of high-purity saleratus wet products for being free of ammonium obtained by step 5), pass through 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 is done
The dry time is no more than 5 minutes.Saleratus after pneumatic conveying drying, is transferred to transfer bag after being cooled to 50 DEG C, natural cooling 15 days,
Then re-sieving pack, obtain 102 kilograms will not lump be free of the high-purity saleratus of ammonium.
This 102 kilograms will not lump be free of the high-purity saleratus of ammonium, quality index such as table 4 below：
What table 4, the gained of embodiment 4 will not lump is free of 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), so that " solution of potassium carbonate I " is substituted " after oil removing obtained by step 2) obtained by step 1)
Solution of potassium carbonate II "；Remaining is equal to embodiment 1.
Solution of potassium carbonate III after gained is refined is by detection, though having no activated carbon, light transmittance is only 98.26%, always
Organic carbon content reaches 198ppm, considerably beyond technological requirement index.
The final dried saleratus of gained, quality index are as follows：
What table 5, the gained of comparative example 1 will not lump is free of 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.
It can be seen that from above-mentioned analysis result and carry out absorption oil removing without step 2) adsorbent post, gained saleratus
Total organic carbon and clarity are all difficult to reach requirement.
Comparative example 2, for embodiment 2, simply step 5) wash time (washing water consumption) is adjusted pair
Than remaining operation is the same as embodiment 2.
The test result such as table 6 below contrasted with different wash times (washing water consumption).
What table 6, the gained of comparative example 2 will not lump is free of 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) washing water consumption (wash time length) is can be seen that to product quality from the comparing result of above-mentioned table 6
Influence is very big, because the impurity content in the saleratus mother liquor after carbonating is very high, and during centrifuge dripping, also has
A small amount of residue of mother is in saleratus crystal, the mother liquor that will can be remained in by pure water on saleratus plane of crystal
Washing displaces, to improve product quality.
Washing water consumption (wash time length) directly affects clean result, and washing water consumption very few (time is too short) then produces
Quality is unqualified, and washs water consumption excessive (overlong time) although product quality can improve, 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's saleratus wet product；And wash water and be
When 33%, gained saleratus wet product is only 119 kilograms, and yield substantially reduces, so as to also increase the evaporation energy consumption of subsequent mother liquor.
And it 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 washing simply puts the mother liquor washing that saleratus plane of crystal is remained
Change, the impurity for crystallizing the inside can not be removed, therefore control washing water can within the specific limits.
Comparative example 3, for embodiment 1, simply to step 6) the dried saleratus natural cooling time grow
Short that product caking situation is contrasted, remaining operation is the same as embodiment 1.
Saleratus after pneumatic conveying drying, is transferred to transfer bag, natural cooling after being cooled to 50 DEG C, cool time contrast is set
It is set to 0,1,5,10,15,20 and 30 day, 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) packs, and is placed on planar deck, presses 9 layers 25 kilograms again above
The saleratus product of packaging, storage are removed after 30 days and see whether to lump, and assess degree of agglomeration.
Table 7, the comparative example 3 different natural cooling times contrast to the influence 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 can not flow |
| 1 day | 32 | Caking is serious, and hand pressure is not broken | Caking can not flow |
| 5 days | 28 | Part is lumpd, and hand pressure can disperse substantially | Caking can not flow |
| 10 days | 25 | A small amount of false caking, light pressure are scattered | 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 the funnel required time that nozzle diameter is 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, packed by re-sieving after the natural coolings of 15 days, product does not lump substantially.
Comparative example 4, for embodiment 1, it is only pre- to carbon dioxide used in step 4) carbonation
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 the same as 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
Caused by-product carbon dioxide 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 the same as embodiment 1.
Gained saleratus product quality analysis result such as table 8 below：
What table 8, the gained of comparative example 4 will not lump is free of 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.
1 is tested, 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, and 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, 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
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (9)
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, added
Enter deionization pure water or recycling of condensed steam water or the cleaning solution obtained by step 3) or the saleratus mother liquor obtained by step 5)
At least one of, the leftover bits and pieces being warming up under stirring condition in above-mentioned industrial magnesium phosphate or potassium carbonate production process is complete
Portion dissolves, and obtains solution of potassium carbonate I；
What it is when addition is only deionization pure water or during recycling of condensed steam water, control the concentration of potassium carbonate in solution of potassium carbonate I >=
550 g/l；
When using the saleratus mother liquor obtained by cleaning solution or the step 5) obtained by step 3) when added, potassium carbonate is controlled
Potassium carbonate and saleratus concentration sum are 550~655g/L in solution I；
2) solution of potassium carbonate I obtained by step 1), is crossed into adsorbent post and carries out absorption oil removing, obtains the solution of potassium carbonate after oil removing
Ⅱ；
The adsorbent column packing is 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 are 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；
3) decolorising agent, under agitation, is added into the solution of potassium carbonate II after oil removing obtained by step 2) to be decolourized, then
Filtered, obtain filtrate and filter residue I 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) it is used to dissolve potassium carbonate；
4) solution of potassium carbonate III after refined obtained by step 3), is pumped into carbonating column, under the oxygen free condition of sealing in 50~
Carbonation reaction is carried out under 60 DEG C of temperature, 0.4~0.5MPa pressure, during carbonation reaction all the time into carbonators
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 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 dries, eluted by the use of deionization pure water or recycling of condensed steam water as washings, 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), high-purity saleratus wet product without ammonium obtained by step 5) is dried by vibrated fluidized bed pneumatic conveyer dryer；
Dried saleratus, which is cooled to after 50~60 DEG C, is first transferred to transfer bag, enters in warehouse natural cooling after 10-30 days again
Packaging, can not also be lumpd so that it is guaranteed that saleratus product is not added with anticaking agent, obtain will not lump be free of the high-purity bicarbonate of ammonium
Potassium.
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, which is back in step 1), to be used to dissolve in industrial magnesium phosphate or potassium carbonate production process
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 is less than 1.0g/L, sulfate concentration is less than 1.0g/L, ammonium ion concentration is less than 50ppm, iron concentration
Less than 100ppm, heavy metal concentration is less than 100ppm, arsenic concentration is limited less than 100ppm, 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：
In the step 1), the saleratus mother liquor obtained by cleaning solution or the step 5) obtained by step 3) has been used when added
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 are less than 1.1g/L, and sulfate concentration is less than 1.1g/L, and ammonium ion concentration is 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：
Solution of potassium carbonate II after oil removing obtained by step 2) 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 of adsorbent post progress again.
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：
Decolorising agent in the step 3) is powdered activated carbon, the work of II adapted of solution of potassium carbonate >=0.05g per 100ml
Property charcoal；
Solution of potassium carbonate III after gained is refined is it is ensured that otherwise light transmittance needs to repeat step 3) more than 99.9%.
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：
In the step 3), 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.
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 elution of the step 5)：It is 5~30 seconds to elute the time, and crystallisation by cooling 5~20ml's of gains adapted per 100g washes
Wash water.
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：
In the step 6), 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.
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：
In the step 4), carbon dioxide used in carbonation, it is derived from produces in industrial magnesium phosphate calcination process
By-product carbon dioxide or food-grade carbon-dioxide；When caused by-product titanium dioxide in use industrial magnesium phosphate calcination process
Carbon, due to containing substantial amounts of ammonia and water vapour in caused by-product carbon dioxide in industrial magnesium phosphate calcination process, therefore need
Carry out removing ammonia and water removal；It is removed in ammonia and removal process, is first condensed out substantial amounts of water vapour so as to be formed 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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| CN113998710B (en) * | 2020-07-28 | 2023-04-18 | 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 |
| CN115108568B (en) * | 2022-04-01 | 2023-09-01 | 浙江大洋生物科技集团股份有限公司 | Method for preparing potassium carbonate from byproduct potassium chloride of fly ash washing |
| 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 |
| CN115924938B (en) * | 2022-12-30 | 2024-07-05 | 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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| CN101538056A (en) * | 2009-04-30 | 2009-09-23 | 河北工业大学 | Technical method for producing potassium carbonate by ion exchange method |
| CN102515210A (en) * | 2011-10-27 | 2012-06-27 | 浙江大洋化工股份有限公司 | Method for producing potassium bicarbonate through self-carbonization multiple-effect cross flow continues evaporation crystallization |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101538056A (en) * | 2009-04-30 | 2009-09-23 | 河北工业大学 | Technical method for producing potassium carbonate by ion exchange method |
| CN102515210A (en) * | 2011-10-27 | 2012-06-27 | 浙江大洋化工股份有限公司 | Method for producing potassium bicarbonate through self-carbonization multiple-effect cross flow continues evaporation crystallization |
| 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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