CN103588223A - Method for producing high-purity ammonium chloride through multistage flash evaporation, cooling and continuous crystallization - Google Patents
Method for producing high-purity ammonium chloride through multistage flash evaporation, cooling and continuous crystallization Download PDFInfo
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Abstract
The invention discloses a method for producing high-purity ammonium chloride through multistage flash evaporation, cooling and continuous crystallization. The method comprises the following steps: 1) putting ammonium chloride with a weight content equal to or greater than 96% into a solution, heating to 100-105 DEG C to form an ammonium chloride saturated solution I, 2) allowing the ammonium chloride saturated solution I to pass through a cartridge filter for heat preservation filtration, 3) pumping an ammonium chloride saturated solution II to a single-effect flash evaporation crystallizer for flash evaporation, cooling and concentration, 4) conveying ammonium chloride slurry I to a double-effect flash evaporation crystallizer for flash evaporation, cooling and the concentration with a forced circulation pump, 5) conveying ammonium chloride slurry II to a triple-effect flash evaporation crystallizer for flash evaporation, cooling and concentration with a forced circulation pump, 6) separating ammonium chloride slurry III with a centrifuge to form an ammonium chloride wet product and an ammonium chloride mother solution I, removing the ammonium chloride mother solution I from a high-purity ammonium chloride production line at a volume ratio of 5-10%, and 7) drying the ammonium chloride wet product to form high-purity ammonium chloride.
Description
Technical field
Technology of the present invention belongs to inorganic salt evaporative crystallization field, relates to a kind of production technique of refining ammonium chloride, particularly a kind of technique of multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium.
Background technology
Ammonium chloride is colourless crystallization or white crystalline powder, odorless, and taste is salty, cool in nature, has water absorbability, easily molten in water, slightly soluble in ethanol.Mainly for the manufacture of drying battery and store battery, be also the raw material of manufacturing other ammonium salts, also as electroplate liquid additive and metal solder fusing assistant, in tanning, precision casting, candle and sizing agent preparation, all there is purposes.
The ammonium chloride solution of saturated hydrogenchloride carries out neutralization reaction with ammonia, and through crystallisation by cooling, solid-liquid separation makes ammonium chloride, also can be when soda and sociation center is produced soda ash from isolate the mother liquor of sodium bicarbonate, reclaims ammonium chloride.Hydrogenchloride and ammonia neutralization reaction generate the technique of ammonium chloride due to high cost, progressively exit suitability for industrialized production.At present main ammonium chloride source is connection alkali industry, is exactly the byproduct of method for producing potassium carbonate by ion exchange and saltpetre industry in addition.The ammonium chloride of producing due to connection alkali industry and sylvite industry contains sodium salt and sylvite, and the overwhelming majority is as chemical fertilizer.
The application of ammonium chloride aspect food more and more comes into one's own in recent years, and demand is also the trend of steady growth.Ammonium chloride generally all mixes and uses with sodium bicarbonate as dough conditioning agent, consumption is about 25% of sodium bicarbonate, add vitamins C and ammonium chloride mixt can make dough there is good elasticity, extensibility and machinability, thereby make bread there is good volume, color and luster, fragrance and elasticity.Because edible too much sodium-chlor is obviously harmful to health, series of studies shows long-term excess salt, not only cause and increase the weight of hypertension, also cause kidney disease, increase the weight of the diabetes state of an illness, can aggravate asthma, osteoporosis very easily occurs even fracture and easily cause many chronic diseases such as peptic digestion system.In west, flourishing society is progressively used the mixture replacing salt such as ammonium chloride, Repone K and partially hydrolysed protein and plant polypeptide, makes it to become a kind of trophic function type seasonings, is widely used in the middle of bread, biscuit.And a lot of countries and locally ammonium chloride and Radix Glycyrrhizae are boiled into a kind of seasonings (black crystals shape) (as are used in the chicken braised in soy sauce of Finland for varieties of food items, the solicit patrons meal of Sweden, the left special noodles of Holland, blood product delicacies of Denmark etc.), in vodka, adding ammonium chloride makes seasonings in addition.
Because agriculture ammonium chloride price is low, a lot of enterprise procurement agricultural ammonium chlorides, by the ammonium chloride of refined raw electrogenesis sub level, pharmaceutical grade, food grade and feed grade.So-called ammonium chloride is refining, by physics or chemical process, the impurity in ammonium chloride is removed exactly, and to obtain the better ammonium chloride of purity, comparatively conventional process for purification is fulling and recrystallization method at present.
In the Chinese invention patent of the applications such as the Jiang Yuanhua of Hubei Shuanghuan Science and Technology Stock Co., Ltd. (201110076713.2) " a kind of method with ammonia mother liquor washing Production of Ammonium Chloride premium grads essence ammonium ", a kind of method of producing smart ammonium is disclosed, it comprises twice washing, twice stiff, twice separation, once spray and primary drying.It is according to the unsaturated character of sodium-chlor in ammonia mother liquor, adds agriculture ammonium chloride fully to wash in ammonia mother liquor, makes the sodium salt content in agriculture ammonium chloride reduce by 60% left and right, and ammonium chloride content reaches the quality standard of smart ammonium acceptable end product; In order to improve the quality of products, carry out secondary washing, and with spray water, spray when secondary separation, further reduce the sodium salt content in smart ammonium, make the stable content of ammonium chloride 99.5%, Recycling Mother Solution after washing is used, and adds in proportion bariumchloride in two cleaning mother liquors, reduces the vitriol in ammonium chloride.This technique is because process is loaded down with trivial details, and manipulation strength is large, be unsuitable for serialization and produce, and quality product is uncontrollable.Owing to being the technique that adopts washing refining, in whole production process, ammonium chloride is all the time in solid state, even if add bariumchloride in washings, for reducing the effect of vitriol or undesirable, also easily causes barium sulfate precipitate to sneak in smart ammonium.
The Jiang Yuanhua of Hubei Shuanghuan Science and Technology Stock Co., Ltd. etc., in order to improve the quality of ammonium chloride, be take agricultural ammonium chloride as raw material, adopt three stage countercurrent washing methods to produce electronic-grade ammonium chloride.They have applied for Chinese invention patent (201210304113.1) " a kind of method of producing electronic-grade ammonium chloride " in 2012, concrete operation step is as follows: the first step adopts agriculture ammonium chloride and the mix and blend washing by a certain percentage of cold ammonia mother liquor I in the production of connection alkali; The second stage adopts the washing of circulating mother liquor I; The third stage adopts hot deionized water wash.Although Jiang Yuanhua etc. to ammonium chloride process for refining capable improvement, but there are many problems, process is loaded down with trivial details, labour intensity is large, being not suitable for serialization produces etc., because it still adopts traditional mode of washing, refine, because sodium-chlor and vitriol are wrapped in agriculture ammonia chloride crystal, be difficult to remove by washing.
Recrystallization method is divided into again crystallisation by cooling and evaporative crystallization, crystallisation by cooling is exactly by the molten input water of raw material ammonium chloride, by heating it is all dissolved, be mixed with saturated solution or near saturated solution, by cooling by ammonium chloride crystallize out from solution, centrifugation obtains ammonia chloride crystal and ammonium chloride mother liquor, this method has advantages of that technique is simple, constant product quality and investment low, but production efficiency is low, labour intensity is high, be unsuitable for serialization and produce, be only suitable in small-scale production; Evaporative crystallization method is along with the improvement of evaporation technology progressively develops, and due to selected evaporation equipment and the difference of technical process, quality product and energy consumption exist very large gap, and single-action, two effects and multiple-effect evaporation crystallization all adopt in ammonium chloride evaporative crystallization very much.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium, adopts method of the present invention can make purity >=99.5% of the ammonium chloride of gained.
In order to solve the problems of the technologies described above, the invention provides a kind of method of multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium, comprise the steps:
1), by weight content (purity) for >=96% ammonium chloride (byproduct that belongs to method for producing potassium carbonate by ion exchange) drops in solution and is heated to 100～105 ℃, obtain 100～105 ℃ of ammonium chloride saturated solution I at temperature; Described solution is tap water or is the ammonium chloride mother liquor I after the preheating of following step 6) gained;
Remarks explanation: when initial, use tap water, then all can use the ammonium chloride mother liquor I after the preheating of step 6) gained;
2), at 100～105 ℃ of temperature, make described ammonium chloride saturated solution I be incubated filtration through cartridge filter (thering is heat-insulating property), obtain ammonium chloride saturated solution II;
3), that ammonium chloride saturated solution II is carried out flash distillation cooling by pump delivery to I effect flash evaporation crystallizer is concentrated, processing parameter is as follows:
Temperature is controlled at 76～80 ℃, and vacuum degree control is at-0.080Mpa～-0.086Mpa, circular flow be I effect flash evaporation crystallizer material amount 0.5～1 times of volume/hour;
Until the ammonium chloride slurry I of gained contains the ammonia chloride crystal that accounts for ammonium chloride slurry I gross weight 3.5～5%;
4), ammonium chloride slurry I is transported to II effect flash evaporation crystallizer by forced circulation pump to carry out flash distillation cooling concentrated, processing parameter is as follows:
Temperature is controlled at 48～52 ℃, and vacuum degree control is at-0.094Mpa～-0.096Mpa, circular flow be II effect flash evaporation crystallizer material amount 0.5～1 times of volume/hour;
Until contain the ammonia chloride crystal that accounts for ammonium chloride slurry II gross weight 9.5～11% in the ammonium chloride slurry II of gained;
5), ammonium chloride slurry II is transported to III effect flash evaporation crystallizer by another forced circulation pump to carry out flash distillation cooling concentrated, processing parameter is as follows:
Temperature is controlled at 18～22 ℃, and vacuum degree control is at-0.098Mpa～-0.099Mpa, circular flow be III effect flash evaporation crystallizer material amount 0.5～1 times of volume/hour;
Until contain the ammonia chloride crystal that accounts for ammonium chloride slurry III gross weight 15～16.8% in the ammonium chloride slurry III of gained;
6), ammonium chloride slurry III carries out separation by whizzer (centrifugal rotational speed is 1000～1200 revs/min, and the time is 8～12 minutes), obtains ammonium chloride wet product and ammonium chloride mother liquor I;
Ammonium chloride mother liquor I is moved out of high purity chlorination ammonium production line with 5～10% volume ratio (per hour), as producing the stock liquid of agricultural with ammonium chloride; The object shifting out is to be less than 2.0% in order to ensure KCE content in ammonium chloride mother liquor I);
The secondary steam that remaining ammonium chloride mother liquor I utilizes II effect flash evaporation crystallizer and I effect flash evaporation crystallizer to produce successively carries out preheating, thereby return to step 1), as solution, uses;
Remarks explanation:
Shift out the ammonium chloride mother liquor I of system as the stock liquid of producing agriculture ammonium chloride, by producing agricultural ammonium chloride after conventional evaporative crystallization, if the ammonium chloride content of producing is greater than 96% raw material that can be used as step 1), if content lower than 96% directly as fertilizer application;
Owing to containing micro-Repone K in the ammonium chloride raw material described in step 1), by obtaining after ammonium chloride after above-mentioned evaporative crystallization, Repone K is stayed in mother liquor, and Repone K accumulation volume can be more and more higher, therefore need to mother liquor be shifted out to production system with the ratio of 5-10%, to reduce the accumulation volume of Repone K;
7), ammonium chloride wet product is by dry (drying temperature is 120～130 ℃, and dried ammonium chloride water content is less than 0.1%), obtains high purity chlorination ammonium.
Improvement as the method for multistage flash evaporation of the present invention cooling continuous crystallisation production high purity chlorination ammonium:
When the ammonium chloride mother liquor I after the preheating of step 6) gained is in shortage as the solution of step 1), with tap water, supply.
Further improvements in methods as multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium of the present invention:
Cartridge filter has heat-insulating property, and material is titanium material, and aperture is 5 microns.
That is, described cartridge filter can be held back the particle of particle diameter >=5 micron.
Further improvements in methods as multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium of the present invention:
The III effect flash evaporation crystallizer using in the II effect flash evaporation crystallizer using in the I effect flash evaporation crystallizer using in described step 3), step 4), step 5) is DTB type crystallizer.
Remarks explanation:
Steam is exactly the raw steam that boiler is come first, and secondary steam just refers in evaporative process, and material passes through raw steam heating, the steam producing after material boiling;
The Btu utilization mode of I effect flash evaporation crystallizer, II effect flash evaporation crystallizer is as described below: the secondary steam of generation is taken out solidifying by steam-jet compression pump, what be used for step 6) carries out preheating to described remaining ammonium chloride mother liquor I, heat is after being used, tail gas is taken away through vertical pipe type condenser water circulation vacuum pump, and the steam condensate of formation can be used as pure water and returns to boiler or production process recycling; Steam-jet compression pump adopts the raw steam that comes from boiler to extract secondary steam as power.
The secondary steam that III effect flash evaporation crystallizer produces is taken out solidifying by steam-jet compression pump, tail gas is taken away by water cycle vacuum pump after vertical pipe type condenser is cooling; The steam condensate forming can be used as pure water and returns to boiler or production process recycling; Steam-jet compression pump adopts the raw steam that comes from boiler to extract secondary steam as power; Because the flash vaporization point of III effect flash evaporation crystallizer is too low, therefore cannot be reused.
Further improvements in methods as multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium of the present invention:
On the vapour liquid separator top duct of described I effect flash evaporation crystallizer, II effect flash evaporation crystallizer and III effect flash evaporation crystallizer, install ammonium chloride evaporation gas washing apparatus (patent No. CN200620101864.3) additional, guarantee not contain in secondary steam ammonium chloride.The steam condensate producing returns to boiler, has solved the problem of boiler feed water.
Further improvements in methods as multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium of the present invention: vapor pressure 0.9～1.1Mpa(that the steam-jet compression pump of the III effect flash evaporation crystallizer using in the II effect flash evaporation crystallizer using in the I effect flash evaporation crystallizer using in described step 3), step 4), step 5) is selected is for example 1.0Mpa).
Further improvements in methods as multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium of the present invention: being dried described in step 7), adopts vibrated fluidized bed to carry out.
Further improvements in methods as multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium of the present invention:
In described step 6):
The secondary steam that remaining ammonium chloride mother liquor I utilizes II effect flash evaporation crystallizer and I effect flash evaporation crystallizer to produce successively carries out preheating, temperature by 20 ℃ rise to >=50 ℃.
In the present invention, by regulating step 3), step 4) and step 5) crystallizer in temperature, vacuum tightness and the solid circulating rate of material, realized ammonium chloride crystals particle diameter and quality controlled.
The present invention compares with common process, adopt three grades of flash distillation continuous cooling crystallization production high purity chlorination ammoniums to have that energy consumption is low (to be compared with existing production technique, can steam saving more than 20%), controlled (ammonium chloride granularity can be controlled in 0.7-1.0mm to constant product quality, uniform particles, smooth surface) and the advantage such as totally-enclosed serialization production.The secondary steam that extracts I effect flash evaporation crystallizer and the generation of II effect flash evaporation crystallizer by steam-jet compression pump is as ammonium chloride mother liquor preheating, can save a large amount of steam, adopt steam-jet compression pump Refrigeration Technique, make III effect flash crystallization actuator temperature be reduced to 18～22 ℃, greatly improve ammonium chloride crystals performance, avoid the interpolation of caking and the chemical anti-hard caking agent of ammonium chloride product.Selecting pressure is that 0.9～1.1Mpa(is for example for 1.0Mpa) steam by steam-jet compression pump, extract the secondary steam that III effect flash evaporation crystallizer produces, can save 20% above steam.By regulating step 3), step 4) and step 5) temperature, vacuum tightness and the solid circulating rate of material in crystallizer, realized ammonium chloride crystals particle diameter and quality controlled.The method of multistage flash evaporation cooling continuous crystallisation production food grade ammonium chloride of the present invention is a kind of green production technique, has both reduced energy consumption, improves again quality product, reduces environmental pollution simultaneously, is worth large-scale promotion application.
In sum, the present invention be take agricultural ammonium chloride as raw material, adopts triple effect to add the method for vapo(u)r blasting flash distillation cooling continuous crystallisation explained hereafter food grade ammonium chloride, significantly reduces steam mono-consumption, produce ton ammonium chloride steam mono-consumption and be reduced to 1.5 tons by original 2.0 tons, saving ratio reaches more than 25%; Ammonium chloride product steady quality, disposable production qualification rate reaches more than 98%, and median size is at 0.7-1.0mm; Realize totally-enclosed serialization and produce, the corresponding raising of production capacity approximately 60%; Owing to adopting evaporative crystallization process for refining, the water-insoluble in ammonium chloride product and other impurity index are far superior to fulling quality product.
Embodiment
In following examples, all on the vapour liquid separator top duct of described I effect flash evaporation crystallizer, II effect flash evaporation crystallizer and III effect flash evaporation crystallizer, install ammonium chloride evaporation gas washing apparatus (patent No. CN200620101864.3) additional, guarantee not contain in secondary steam ammonium chloride.The steam condensate producing returns to boiler, thereby has solved the problem of boiler feed water.
The method of embodiment 1-1, a kind of multistage (three grades) flash distillation cooling continuous crystallisation production high purity chlorination ammonium, carry out successively following steps:
1), by 7500 kilogram weights of content (purity), be that 96.5% ammonium chloride (byproduct that belongs to method for producing potassium carbonate by ion exchange) drops in 9000L tap water and is heated to 100～105 ℃, obtain 100～105 ℃ of ammonium chloride saturated solution I at temperature;
2), at 100～105 ℃ of temperature, the cartridge filter with heat-insulating property that is 5 microns by aperture by whole ammonium chloride solution I (about 15000L) of step 1 gained filters (object is in order to remove insoluble substance), obtain ammonium chloride solution II (after testing, suspended substance is less than 0.5mg/l, ammonium chloride concentration is about 43.2%, potassium chloride concentration is 1.36%, Ca
2+: 0.0012%, Mg
2+: 0.0011%, Fe≤0.0005%, heavy metal≤0.0005%).
The above-mentioned % of remarks is % by weight.
3), by temperature, be the ammonium chloride solution II of 100～105 ℃ by take away pump with 15m per hour
3the flow I effect flash evaporation crystallizer that is delivered to DTB type to carry out flash distillation cooling concentrated.I effect flash evaporation crystallizer is selected DTB type crystallizer, in I effect flash evaporation crystallizer, the temperature of material is controlled at 76～80 ℃, vacuum degree control is at-0.080Mpa～-0.086Mpa, circular flow be ammonium chloride slurry in crystallizer (being I effect flash evaporation crystallizer material amount) 1 times of volume/hour; Until contain the ammonia chloride crystal that accounts for ammonium chloride slurry I gross weight 4.5% in the ammonium chloride slurry I of gained;
Remarks explanation:
Steam is exactly the raw steam that boiler is come first, and secondary steam just refers in evaporative process, and material passes through raw steam heating, the steam producing after material boiling;
The secondary steam that above-mentioned I effect flash evaporation crystallizer produces is taken out solidifying by steam-jet compression pump, what be used for following step 6) carries out preheating to described remaining Repone K mother liquor I, heat is after being used, tail gas is taken away through vertical pipe type condenser water circulation vacuum pump, and the steam condensate of formation can be used as pure water and returns to boiler or production process recycling; Steam-jet compression pump adopts the raw steam that comes from boiler to extract secondary steam as power; The vapor pressure that steam-jet compression pump adopts is 1.0Mpa.
4), ammonium chloride slurry I is transported to II effect flash evaporation crystallizer by slurries formula forced circulation pump and carries out flash concentration cooling; This II effect flash evaporation crystallizer is selected DTB type crystallizer; In II effect flash evaporation crystallizer, temperature of charge is controlled at 48～52 ℃, and vacuum degree control is at-0.094Mpa～-0.096Mpa; Circular flow be ammonium chloride slurry in crystallizer (II effect flash evaporation crystallizer material amount) 1 times of volume/hour; Until contain the ammonia chloride crystal that accounts for ammonium chloride slurry II gross weight 10.6% in the ammonium chloride slurry II of gained;
Remarks explanation:
The secondary steam that above-mentioned II effect flash evaporation crystallizer produces is taken out solidifying by steam-jet compression pump, what be used for following step 6) carries out preheating to described remaining Repone K mother liquor I, heat is after being used, tail gas is taken away through vertical pipe type condenser water circulation vacuum pump, and the steam condensate of formation can be used as pure water and returns to boiler or production process recycling; Steam-jet compression pump adopts the raw steam that comes from boiler to extract secondary steam as power; The vapor pressure that steam-jet compression pump adopts is 1.0Mpa.
5), ammonium chloride slurry II is transported in III effect flash evaporation crystallizer and carried out flash distillation decrease temperature crystalline by slurries formula forced circulation pump, this III effect flash evaporation crystallizer is selected DTB type crystallizer; In III effect flash evaporation crystallizer, temperature of charge is controlled at 18～22 ℃, and vacuum degree control is at-0.098Mpa～-0.099Mpa, circular flow be ammonium chloride slurry in crystallizer (III effect flash evaporation crystallizer material amount) 1 times of volume/hour; Until contain the ammonia chloride crystal that accounts for ammonium chloride slurry III gross weight 16.8% in the ammonium chloride slurry III of gained;
Remarks explanation:
The secondary steam that III effect flash evaporation crystallizer produces is taken out solidifying by steam-jet compression pump, tail gas is taken away by water cycle vacuum pump after vertical pipe type condenser is cooling; The steam condensate forming can be used as pure water and returns to boiler or production process recycling; Steam-jet compression pump adopts the raw steam that comes from boiler to extract secondary steam as power;
Because the flash vaporization point of III effect flash evaporation crystallizer is too low, therefore no longer utilize.
6), ammonium chloride slurry III is by centrifugation (centrifugal rotational speed is about 1200 revs/min, and the time is about 10 minutes), obtains the ammonium chloride wet product that 4140 kilograms of water content are 2.8%, temperature is the ammonium chloride mother liquor I 11m altogether of 20 ℃
3.
10%(11m wherein
3* 10%=1.1m
3) ammonium chloride mother liquor I is moved out of high purity chlorination ammonium production line, as producing the stock liquid (thereby guarantee in ammonium chloride mother liquor I KCE content be less than 2.0%) of agricultural with ammonium chloride.
Remarks explanation: shift out the ammonium chloride mother liquor I of system as the stock liquid of producing agriculture ammonium chloride, by producing agricultural ammonium chloride after conventional evaporative crystallization, if the ammonium chloride content of producing is greater than 96.5% raw material that can be used as step 1), if content lower than 96.5% directly as fertilizer application;
Remaining 90%(11m
3* 90%=9.9m
3) the ammonium chloride mother liquor I secondary steam that utilizes successively II effect flash evaporation crystallizer and I effect flash evaporation crystallizer to produce carry out preheating, temperature rises to 50-52 ℃ of left and right by 20 ℃, returns in step 1) as solution for dissolving raw material ammonium chloride.
7) the ammonium chloride wet product that is, 2.8% by 4140 kilograms of water content of centrifugal gained is by vibra fluidized bed drying (temperature during vibra fluidized bed drying is 125 ℃), after crossing 40 mesh sieves, obtain 4015 kilograms of high purity chlorination ammonium products, in this finished product, ammonium chloride content is 99.8%, sodium chloride content is 0.08%, sulfate radical content is less than 0.003%, and calcium magnesium is all less than 0.0001%, and heavy metal and arsenic are all less than 1ppm, water content is 0.12%, and median size is 0.9mm.
In the present embodiment, dissolution process consumes 1680 kilograms of steam altogether, 920 kilograms of flash cooling crystallisation process consumption steam, and 1280 kilograms of drying process consumption steam, folding steam mono-consumption is 966 kgs/tonne of ammonium chlorides.
Embodiment 1-2: the method for a kind of multistage (three grades) flash distillation cooling continuous crystallisation production high purity chlorination ammonium, carry out successively following steps:
1) by 5400 kilograms of content, be, the byproduct that 96.5%(belongs to method for producing potassium carbonate by ion exchange) ammonium chloride drop into the 10m that the secondary steam producing through II effect flash evaporation crystallizer and I effect flash evaporation crystallizer successively described in the step 6) of embodiment 1-1 carries out (temperature is 50-52 ℃) after preheating
3ammonium chloride mother liquor I and 1.5m
3in water, be mixed with ammonium chloride supersaturated solution, utilize recycle pump that material is sent into well heater, by heating material to 100 ℃, after ammonia chloride crystal dissolves, obtain ammonium chloride solution I;
2), at 100～105 ℃ of temperature, the cartridge filter with heat-insulating property that is 5 microns by aperture by whole ammonium chloride solution I (about 15900L) of step 1) gained filters (object is in order to remove insoluble substance), obtain ammonium chloride solution II (after testing, suspended substance is less than 0.5mg/l, ammonium chloride concentration is about 43.6%, potassium chloride concentration is 1.58%, Ca
2+: 0.0012%, Mg
2+: 0.0011%, Fe≤0.0005%, heavy metal≤0.0005%).
The above-mentioned % of remarks is % by weight.
3), by temperature, be the ammonium chloride solution II of 100～105 ℃ by take away pump with 15m per hour
3the flow I effect flash evaporation crystallizer that is delivered to DTB type to carry out flash distillation cooling concentrated.I effect flash evaporation crystallizer is selected DTB type crystallizer, and in I effect flash evaporation crystallizer, the temperature of material is controlled at 76-80 ℃, and vacuum degree control is at-0.080Mpa～-0.086Mpa, circular flow be ammonium chloride slurry in crystallizer 1 times of volume/hour; Until contain the ammonia chloride crystal that accounts for ammonium chloride slurry I gross weight 4.5% in the ammonium chloride slurry I of gained;
Remarks explanation:
Steam is exactly the raw steam that boiler is come first, and secondary steam just refers in evaporative process, and material passes through raw steam heating, the steam producing after material boiling;
The secondary steam that above-mentioned I effect flash evaporation crystallizer produces is taken out solidifying by steam-jet compression pump, what be used for following step 6) carries out preheating to described remaining Repone K mother liquor I, heat is after being used, tail gas is taken away through vertical pipe type condenser water circulation vacuum pump, and the steam condensate of formation can be used as pure water and returns to boiler or production process recycling; Steam-jet compression pump adopts the raw steam that comes from boiler to extract secondary steam as power; The vapor pressure that steam-jet compression pump adopts is 1.0Mpa.
4), ammonium chloride slurry I is transported to II effect flash evaporation crystallizer by slurries formula forced circulation pump and carries out flash concentration cooling; This II effect flash evaporation crystallizer is selected DTB type crystallizer; In II effect flash evaporation crystallizer, temperature of charge is controlled at 48～52 ℃, and vacuum degree control is at-0.094Mpa～-0.096Mpa; Circular flow be ammonium chloride slurry in crystallizer 1 times of volume/hour; Until contain the ammonia chloride crystal that accounts for ammonium chloride slurry II gross weight 10.6% in the ammonium chloride slurry II of gained;
Remarks explanation:
The secondary steam that above-mentioned II effect flash evaporation crystallizer produces is taken out solidifying by steam-jet compression pump, what be used for following step 6) carries out preheating to described remaining Repone K mother liquor I, heat is after being used, tail gas is taken away through vertical pipe type condenser water circulation vacuum pump, and the steam condensate of formation can be used as pure water and returns to boiler or production process recycling; Steam-jet compression pump adopts the raw steam that comes from boiler to extract secondary steam as power; The vapor pressure that steam-jet compression pump adopts is 1.0Mpa.
5), ammonium chloride slurry II is transported in III effect flash evaporation crystallizer and carried out flash distillation decrease temperature crystalline by slurries formula forced circulation pump, this III effect flash evaporation crystallizer is selected DTB type crystallizer; In III effect flash evaporation crystallizer, temperature of charge is controlled at 18～22 ℃, and vacuum degree control is at-0.098Mpa～-0.099Mpa, circular flow be ammonium chloride slurry in crystallizer 1 times of volume/hour; Until contain the ammonia chloride crystal that accounts for ammonium chloride slurry III gross weight 16.8% in the ammonium chloride slurry III of gained;
Remarks explanation:
The secondary steam that III effect flash evaporation crystallizer produces is taken out solidifying by steam-jet compression pump, tail gas is taken away by water cycle vacuum pump after vertical pipe type condenser is cooling; The steam condensate forming can be used as pure water and returns to boiler or production process recycling; Steam-jet compression pump adopts the raw steam that comes from boiler to extract secondary steam as power;
Because the flash vaporization point of III effect flash evaporation crystallizer is too low, therefore no longer utilize.
6), ammonium chloride slurry III is by centrifugation (centrifugal rotational speed is about 1200 revs/min, and the time is about 10 minutes), obtains the ammonium chloride wet product that 4220 kilograms of water content are 2.8%, temperature is the about 11m of ammonium chloride mother liquor I of 20 ℃
3.
10%(11m wherein
3* 10%=1.1m
3) ammonium chloride mother liquor I is moved out of high purity chlorination ammonium production line, as producing the stock liquid (thereby guarantee in ammonium chloride mother liquor I KCE content be less than 2.0%) of agricultural with ammonium chloride.
Remarks explanation: shift out the ammonium chloride mother liquor I of system as the stock liquid of producing agriculture ammonium chloride, by producing agricultural ammonium chloride after conventional evaporative crystallization, if the ammonium chloride content of producing is greater than 96.5% raw material that can be used as step 1), if content lower than 96.5% directly as fertilizer application;
Remaining 90%(11m
3* 90%=9.9m
3) the ammonium chloride mother liquor I secondary steam that utilizes successively II effect flash evaporation crystallizer and I effect flash evaporation crystallizer to produce carry out preheating, temperature rises to 50-52 ℃ of left and right by 20 ℃, returns in step 1) as solution for dissolving raw material ammonium chloride.
7) the ammonium chloride wet product that is, 2.8% by 4220 kilograms of water content of centrifugal gained is by vibra fluidized bed drying (temperature during vibra fluidized bed drying is 125 ℃), after crossing 40 mesh sieves, obtain 4090 kilograms of high purity chlorination ammonium products, in this finished product, ammonium chloride content is 99.7%, sodium chloride content is 0.08%, sulfate radical content is less than 0.003%, and calcium magnesium is all less than 0.0001%, and heavy metal and arsenic are all less than 1ppm, water content is 0.12%, and median size is 0.9mm.
In the present embodiment, dissolution process consumes 1480 kilograms of steam altogether, 950 kilograms of flash cooling crystallisation process consumption steam, and 1290 kilograms of drying process consumption steam, folding steam mono-consumption is 882 kgs/tonne of ammonium chlorides.
The method of embodiment 2, a kind of multistage (three grades) flash distillation cooling continuous crystallisation production high purity chlorination ammonium, carry out successively following steps:
1) by 5200 kilograms of content, be, the byproduct that 96.5%(belongs to method for producing potassium carbonate by ion exchange) ammonium chloride drop into the 10.5m that the secondary steam producing through II effect flash evaporation crystallizer and I effect flash evaporation crystallizer successively described in the step 6) of above-described embodiment 1-1 carries out (temperature is 50-52 ℃) after preheating
3ammonium chloride mother liquor I and 1m
3in water, be mixed with ammonium chloride supersaturated solution, utilize recycle pump that material is sent into well heater, by heating material to 100 ℃, after ammonia chloride crystal dissolves, obtain ammonium chloride solution I;
2), at 100～105 ℃ of temperature, the cartridge filter with heat-insulating property that is 5 microns by aperture by whole ammonium chloride solution I (about 15800L) of step 1) gained filters (object is in order to remove insoluble substance), obtain ammonium chloride solution II (after testing, suspended substance is less than 0.5mg/l, ammonium chloride concentration is about 43.3%, potassium chloride concentration is 1.72%, Ca
2+: 0.0013%, Mg
2+: 0.0011%, Fe≤0.0005%, heavy metal≤0.0005%).
The above-mentioned % of remarks is % by weight.
Step 3)～step 5) is equal to embodiment 1-2;
6), by step 5) gained ammonium chloride slurry III by centrifugation (centrifugal rotational speed is about 1200 revs/min, and the time is about 10 minutes), obtain the ammonium chloride wet product that 4180 kilograms of water content are 3%, temperature is the about 11m of ammonium chloride mother liquor I of 20 ℃
3.
5%(11m wherein
3* 5%=0.55m
3) ammonium chloride mother liquor I is moved out of high purity chlorination ammonium production line, as producing the stock liquid (thereby guarantee in ammonium chloride mother liquor I KCE content be less than 2.0%) of agricultural with ammonium chloride.
Remarks explanation: shift out the ammonium chloride mother liquor I of system as the stock liquid of producing agriculture ammonium chloride, by producing agricultural ammonium chloride after conventional evaporative crystallization, if the ammonium chloride content of producing is greater than 96.5% raw material that can be used as step 1), if content lower than 96.5% directly as fertilizer application;
Remaining 95%(11m
3* 95%=10.45m
3) the ammonium chloride mother liquor I secondary steam that utilizes successively II effect flash evaporation crystallizer and I effect flash evaporation crystallizer to produce carry out preheating, temperature rises to 50-52 ℃ of left and right by 20 ℃, returns in step 1) as solution for dissolving raw material ammonium chloride.
Step 7) is equal to embodiment 1-2.
Final 4050 kilograms of ammonium chloride finished products, wherein ammonium chloride content is 99.6%, and sodium chloride content is 0.12%, and sulfate radical content is less than 0.004%, and calcium magnesium is all less than 0.0001%, and heavy metal and arsenic are all less than 1ppm, and water content is 0.12%, and median size is 0.7mm.
In the present embodiment, dissolution process consumes 1420 kilograms of steam altogether, 920 kilograms of flash cooling crystallisation process consumption steam, and 1260 kilograms of drying process consumption steam, folding steam mono-consumption is 889 kgs/tonne of ammonium chlorides.
The method of embodiment 3, a kind of multistage (three grades) flash distillation cooling continuous crystallisation production high purity chlorination ammonium, carry out successively following steps:
With respect to embodiment 1-2, do following change:
1) by 3600 kilograms of content, be, the byproduct that 96.5%(belongs to method for producing potassium carbonate by ion exchange) ammonium chloride drop into the 13m that the secondary steam producing through II effect flash evaporation crystallizer and I effect flash evaporation crystallizer successively described in step 6) carries out (temperature is 50-52 ℃) after preheating
3in ammonium chloride mother liquor I, be mixed with ammonium chloride supersaturated solution, utilize recycle pump that material is sent into well heater, by heating material to 100 ℃, after ammonia chloride crystal dissolves, obtain ammonium chloride solution I;
2), at 100～105 ℃ of temperature, the cartridge filter with heat-insulating property that is 5 microns by aperture by the ammonium chloride solution I of above-mentioned whole 15000L filters (object is in order to remove insoluble substance), obtain ammonium chloride solution II (after testing, suspended substance is less than 0.5mg/l, ammonium chloride concentration is about 43.5%, potassium chloride concentration is 1.82%, Ca
2+: 0.0011%, Mg
2+: 0.0010%, Fe≤0.0005%, heavy metal≤0.0005%).
The above-mentioned % of remarks is % by weight.
6), by step 5) gained ammonium chloride slurry III by centrifugation (centrifugal rotational speed is about 1200 revs/min, and the time is about 10 minutes), obtain the ammonium chloride wet product that 4120 kilograms of water content are 3%, temperature is the about 11m of ammonium chloride mother liquor I of 20 ℃
3.
The secondary steam that all ammonium chloride mother liquor I utilize II effect flash evaporation crystallizer and I effect flash evaporation crystallizer to produce successively carries out preheating, and temperature rises to 50-52 ℃ of left and right by 20 ℃, returns in step 1) as solution for dissolving raw material ammonium chloride.
All the other contents are equal to embodiment 1-2.
Final 3994 kilograms of ammonium chloride finished products, wherein ammonium chloride content is 99.5%, sodium chloride content is 0.38%, sulfate radical content is less than 0.005%, calcium magnesium is all less than 0.0001%, and heavy metal and arsenic are all less than 1ppm, and water content is 0.12%, ammonium chloride product particle diameter inhomogeneous (particle diameter is in 0.4mm), and surface irregularity.
In the present embodiment, dissolution process consumes 1280 kilograms of steam altogether, 880 kilograms of flash cooling crystallisation process consumption steam, and 1200 kilograms of drying process consumption steam, folding steam mono-consumption is 840 kgs/tonne of ammonium chlorides.
In invention process of the present invention, contriver also carried out following contrast experiment:
Comparative example 1,
Flash distillation cooling continuous crystallisation technique in step 3) in embodiment 1-2, step 4) and step 5) is changed into the technique of direct cooling down crystallization.The ammonium chloride saturated solution II that is 105 ℃ by temperature is cooled to room temperature naturally, by centrifugation, obtains the ammonium chloride wet product that 3420 kilograms of water content are 3.5%.The ammonium chloride wet product that is 3.5% by 3420 kilograms of water content of centrifugal gained is by vibra fluidized bed drying (temperature during vibra fluidized bed drying is 125 ℃), obtain 2140 kilograms of ammonium chloride finished products, ammonium chloride content is 99.4%, sodium chloride content is 0.48%, and sulfate radical content is less than 0.010%, and calcium magnesium is all less than 0.0009%, heavy metal and arsenic are all less than 5ppm, water content is 0.12%, ammonium chloride product particle diameter inhomogeneous (particle diameter is in 0.4mm), and surface irregularity.In this comparative example 1, dissolution process consumes 1480 kilograms of steam altogether, 1090 kilograms of drying process consumption steam, and folding steam mono-consumption is 1201 kgs/tonne of ammonium chlorides, steam mono-consumption is than high 36% left and right of embodiment of the present invention 1-2.
Comparative example 2:
With respect to embodiment 1-2, do following change:
By the circular flow in step 3) make into 0.4 times of volume into I effect flash evaporation crystallizer material amount/hour;
By the circular flow in step 4) make into 0.4 times of volume into II effect flash evaporation crystallizer material amount/hour;
By the circular flow in step 5) make into 0.4 times of volume into III effect flash evaporation crystallizer material amount/hour;
All the other are equal to embodiment 1-2.
The conclusion of final gained is: after crossing 40 mesh sieves, obtain 4020 kilograms of high purity chlorination ammonium products, in this finished product, ammonium chloride content is 99.6%, sodium chloride content is 0.12%, sulfate radical content is less than 0.003%, calcium magnesium is all less than 0.0001%, heavy metal and arsenic are all less than 1ppm, and water content is 0.12%, and median size is 0.5mm.
In this comparative example, folding steam mono-consumption is 928 kgs/tonne of ammonium chlorides.
And in this comparative example, quality product is all poor than embodiment 1-2 with steam mono-consumption.
Comparative example 3:
With respect to embodiment 1-2, do following change:
By the circular flow in step 3) make into 1.2 times of volumes into I effect flash evaporation crystallizer material amount/hour;
By the circular flow in step 4) make into 1.2 times of volumes into II effect flash evaporation crystallizer material amount/hour;
By the circular flow in step 5) make into 1.2 times of volumes into III effect flash evaporation crystallizer material amount/hour;
All the other are equal to embodiment 1-2.
The conclusion of final gained is: after crossing 40 mesh sieves, obtain 4070 kilograms of high purity chlorination ammonium products, in this finished product, ammonium chloride content is 99.6%, sodium chloride content is 0.14%, sulfate radical content is less than 0.004%, calcium magnesium is all less than 0.0001%, heavy metal and arsenic are all less than 1ppm, and water content is 0.12%, and median size is 0.6mm.
In this comparative example, folding steam mono-consumption is 9,12 kgs/tonne of ammonium chlorides.
In this comparative example, quality product is all poor than embodiment 1-2 with steam mono-consumption.
Comparative example 4,
The described method of patent of invention (201210304113.1) " a kind of method of producing electronic-grade ammonium chloride " with reference to the Jiang Yuanhua of Hubei Shuanghuan Science and Technology Stock Co., Ltd. etc., the cold ammonia mother liquor I of the agricultural level ammonium chloride that is 96.5% by 2500 kilograms of content and connection alkali production system is carried out abundant agitator treating, solid-liquid volume ratio is 20%, after washing, by whizzer, carry out solid-liquid separation, gained ammonium chloride content is 97.8%, chloride solid after once washing and circulating mother liquor I are carried out abundant agitator treating, and solid-liquid volume ratio is 20%, after washing, by whizzer, carry out solid-liquid separation, and gained ammonium chloride content is 98.4%, chloride solid after secondary washing and hot deionized water carry out agitator treating, solid-liquid volume ratio is 20%, in washing process, feed temperature is controlled at 50 ℃, after washing, by whizzer, carry out solid-liquid separation, gained ammonium chloride content is 99.3%, by centrifugal gained ammonium chloride wet product by vibra fluidized bed drying (temperature during vibra fluidized bed drying is 125 ℃), obtain 1650 kilograms of ammonium chloride finished products, ammonium chloride content is 99.3%, sodium chloride content is 0.52%, sulfate radical content 0.016%, water-insoluble is 0.048%, calcium magnesium is all less than 0.001%, heavy metal and arsenic are all less than 1ppm, water content is 0.12%.
Finally, it is also to be noted that, what more than enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (8)
1. the method for multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium, is characterized in that comprising the steps:
1), by weight content for >=96% ammonium chloride drops in solution and is heated to 100～105 ℃, obtain 100～105 ℃ of ammonium chloride saturated solution I at temperature; Described solution is tap water or is the ammonium chloride mother liquor I after the preheating of following step 6) gained;
2), at 100～105 ℃ of temperature, make described ammonium chloride saturated solution I be incubated filtration through cartridge filter, obtain ammonium chloride saturated solution II;
3), that ammonium chloride saturated solution II is carried out flash distillation cooling by pump delivery to I effect flash evaporation crystallizer is concentrated, processing parameter is as follows:
Temperature is controlled at 76～80 ℃, and vacuum degree control is at-0.080Mpa～-0.086Mpa, circular flow be I effect flash evaporation crystallizer material amount 0.5～1 times of volume/hour;
Until the ammonium chloride slurry I of gained contains the ammonia chloride crystal that accounts for ammonium chloride slurry I gross weight 3.5～5%;
4), ammonium chloride slurry I is transported to II effect flash evaporation crystallizer by forced circulation pump to carry out flash distillation cooling concentrated, processing parameter is as follows:
Temperature is controlled at 48～52 ℃, and vacuum degree control is at-0.094Mpa～-0.096Mpa, circular flow be II effect flash evaporation crystallizer material amount 0.5～1 times of volume/hour;
Until contain the ammonia chloride crystal that accounts for ammonium chloride slurry II gross weight 9.5～11% in the ammonium chloride slurry II of gained;
5), ammonium chloride slurry II is transported to III effect flash evaporation crystallizer by another forced circulation pump to carry out flash distillation cooling concentrated, processing parameter is as follows:
Temperature is controlled at 18～22 ℃, and vacuum degree control is at-0.098Mpa～-0.099Mpa, circular flow be III effect flash evaporation crystallizer material amount 0.5～1 times of volume/hour;
Until contain the ammonia chloride crystal that accounts for ammonium chloride slurry III gross weight 15～16.8% in the ammonium chloride slurry III of gained;
6), ammonium chloride slurry III carries out separation by whizzer, obtains ammonium chloride wet product and ammonium chloride mother liquor I;
Ammonium chloride mother liquor I is moved out of high purity chlorination ammonium production line with 5～10% volume ratio;
The secondary steam that remaining ammonium chloride mother liquor I utilizes II effect flash evaporation crystallizer and I effect flash evaporation crystallizer to produce successively carries out preheating, thereby return to step 1), as solution, uses;
7), ammonium chloride wet product is by dry, obtains high purity chlorination ammonium.
2. the method for multistage flash evaporation according to claim 1 cooling continuous crystallisation production high purity chlorination ammonium, is characterized in that:
When the ammonium chloride mother liquor I after the preheating of step 6) gained is in shortage as the solution of step 1), with tap water, supply.
3. the method for described multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium according to claim 2, is characterized in that: described cartridge filter has heat-insulating property, and material is titanium material, and aperture is 5 microns.
4. the method for described multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium according to claim 3, is characterized in that:
The III effect flash evaporation crystallizer using in the II effect flash evaporation crystallizer using in the I effect flash evaporation crystallizer using in described step 3), step 4), step 5) is DTB type crystallizer.
5. the method for described multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium according to claim 4, is characterized in that:
On the vapour liquid separator top duct of described I effect flash evaporation crystallizer, II effect flash evaporation crystallizer and III effect flash evaporation crystallizer, install ammonium chloride evaporation gas washing apparatus additional, guarantee not contain in secondary steam ammonium chloride.
6. the method for described multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium according to claim 5, is characterized in that:
Vapor pressure 0.9～1.1Mpa that the steam-jet compression pump of the III effect flash evaporation crystallizer using in the II effect flash evaporation crystallizer using in the I effect flash evaporation crystallizer using in described step 3), step 4), step 5) is selected.
7. the method for described multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium according to claim 6, is characterized in that:
Being dried described in step 7), adopts vibrated fluidized bed to carry out.
8. the method for described multistage flash evaporation cooling continuous crystallisation production high purity chlorination ammonium according to claim 7, is characterized in that:
In described step 6):
The secondary steam that remaining ammonium chloride mother liquor I utilizes II effect flash evaporation crystallizer and I effect flash evaporation crystallizer to produce successively carries out preheating, temperature by 20 ℃ rise to >=50 ℃.
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| CN104386729A (en) * | 2014-11-18 | 2015-03-04 | 辽宁石化职业技术学院 | Method for quickly preparing superfine calcium carbonate with co-product of ammonium chloride |
| CN104843924A (en) * | 2015-05-13 | 2015-08-19 | 浙江大洋生物科技集团股份有限公司 | Treatment method for saliferous high-concentration organic process waste water during fosfomycin calcium production |
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| CN114590820A (en) * | 2022-03-10 | 2022-06-07 | 四川西陇科学有限公司 | Purification method of potassium-containing ammonium chloride |
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| CN102992353A (en) * | 2012-12-27 | 2013-03-27 | 衡阳市海联盐卤化工有限公司 | Technology for producing industrial-grade ammonium chloride by quadruple-effect evaporation heat method |
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| CN104386729A (en) * | 2014-11-18 | 2015-03-04 | 辽宁石化职业技术学院 | Method for quickly preparing superfine calcium carbonate with co-product of ammonium chloride |
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