CN101823732A - Method for preparing ammonium chloride with seawater - Google Patents
Method for preparing ammonium chloride with seawater Download PDFInfo
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- CN101823732A CN101823732A CN200910068030A CN200910068030A CN101823732A CN 101823732 A CN101823732 A CN 101823732A CN 200910068030 A CN200910068030 A CN 200910068030A CN 200910068030 A CN200910068030 A CN 200910068030A CN 101823732 A CN101823732 A CN 101823732A
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Abstract
The invention relates to a method for preparing ammonium chloride with seawater, which comprises the following steps that: raw material seawater is absorbed by an ion exchange column filled with modified zeolite, and the seawater after absorption is discharged; ammonium chloride solution is used for eluting the adsorbate; saturated brine is fed into the ion exchange column treated through the elution procedure to be recycled, an ammonia still process is carried out to the sodium hydroxide which contains ammonium salt water which is obtained in the recycling procedure, a bi-product ammonia is obtained and the salt water is recycled; and the salt of the obtained K-rich fluid is removed through evaporation, the evaporation completion liquid is cooled, the solid and the liquid are separated, and the finished product ammonium chloride is obtained. The method for preparing ammonium chloride with seawater overcomes the problems in a traditional nitrogen and potassium compound fertilizer production process that the potassium source is restricted by importing and the cost is high, and provides a novel approach for developing rich seawater potassium resources.
Description
Technical field
The present invention relates to a kind of preparation method of ammonium chloride, particularly use the method for preparing ammonium chloride with seawater.
Technical background
Ammonium chloride is a kind of nitrogenous potash fertilizer, both can be used as nitrogen-potassium compound fertilizer and has directly used in the farmland, can be used as the raw material of making nitrogen phosphorus potassium Nitrogen, Phosphorus and Potassium again.Chinese patent CN1423624 discloses a kind of " producing the method for nitrogenous potash fertilizer ", the main points of this invention are: mixed chlorinated potassium and urea in the blending machine, select the Repone K of 1.66%-9.9% (quality) to be used for mixing, and in the form input blending machine of urea with frit, heat this mixture and granulating, at last by in prilling tower in air-flow granulation carry out granulating.The nitrogenous potash fertilizer of Sheng Chaning comprises K in this way
2O 1%-5.94% (quality) and N 41.4%-45.2% (quality).CN1122793 discloses a kind of " production method of by-product binary compound fertilizer containing nitrogen and potassium ", this invention is to be basic raw material with ammonium nitrate and Repone K, produce technical grade saltpetre and by-product binary compound fertilizer containing nitrogen and potassium by replacement(metathesis)reaction, this technical process mainly comprises gets the raw materials ready, the ammonium nitrate dissolving, heat up, add Repone K, ebuillition of heated, filter, crystallisation by cooling, filtering separation, the mixture evaporate to dryness, operations such as granulation, water in the raw material: ammonium nitrate: the consumption of Repone K is 2: 1: 1, the multiple fertile nitrogen content 19% of the binary of this method preparation, potassium content 18% is fit to the multiclass farm crop and uses.Production method that CN1294102 discloses a kind of " granular composite N-K fertilizer ", this granular composite N-K fertilizer is made by 60 one 80% carbon ammonium, the potash fertilizer of 15-35% and little fertilizer of equal amount.In sum, existing nitrogen-potassium compound fertilizer is raw material production with commodity sylvite (Repone K) with nitrogenous substances (urea, ammonium nitrate, carbon ammonium etc.) all.Because China's land potassium ore resources shortage, domestic required Repone K 70% dependence on import, cause the raw material sources of above-mentioned technology and the restriction that production cost will be subjected to import Repone K, therefore, the development natural sea-water potassium resource that utilizes total reserves the to reach 550,000,000,000,000 tons method of producing nitrogen-potassium compound fertilizer is very necessary.
Aspect potassium from sea water, scientist successively proposes to comprise the kinds of processes method of four kinds of technological lines such as chemical precipitation method, solvent extration, membrane separation process and ion exchange method both at home and abroad.In the Extracting Potash from Seawater by Ion Exchange Method technology that with the natural zeolite is ion-exchanger, ZL 200510133689.6 has proposed a kind of " extracting the method for vitriolate of tartar with seawater ", this method is to be raw material with seawater and ammonium sulfate, at first adopt ammoniumsulphate soln that the wash-out operation that the adsorptive in the ion exchange column of filling sodium type clinoptilolite carries out wash-out is prepared rich potassium liquid, adopt then in rich potassium liquid, to feed ammonia and analyse operation with the ammonia of separating out vitriolate of tartar and produce vitriolate of tartar.
CN101323457A discloses a kind of " producing the method for Repone K with seawater ", and this method is to use the potassium in the natural zeolite adsorbing seawater; With the magnesium chloride solution that contains ammonium chloride is eluent, and the normal temperature wash-out is inhaled saspachite, makes the rich potassium mother liquor that contains potassium, magnesium, ammonium, chlorion; Rich potassium mother liquid evaporation concentrates, and complete evaporation of liquid cooling, centrifugation get carnallitite and magnesium chloride solution; Carnallitite adds water decomposition and gets Repone K.Because this method K in the rich potassium mother liquor that rich potassium operation makes
+Content the 19.45-21.45 grams per liter is only arranged, cause the higher energy consumption of evaporation concentration separation circuit needs of back, add that follow-up carnallitite decomposes and operations such as thick potassium washing need be added more water, make the overall energy consumption height of this method.
Summary of the invention
The object of the invention is to provide a kind of method with preparing ammonium chloride with seawater.This method has overcome that potassium usually is subjected to import restriction and the high problem of cost in the source in the existing nitrogen-potassium compound fertilizer production technique on the one hand; On the other hand, by a large amount of process optimization experiments, prepare K
+Content at the rich potassium liquid of 28-45 grams per liter, and behind evaporative removal sodium-chlor, utilize make the ammonium chloride product direct one step of process for cooling, thereby reduced the energy consumption of technological process significantly, provide a new approach for developing abundant seawater potassium resource.
A kind of method with preparing ammonium chloride with seawater provided by the invention is through following step:
1) it is complete at room temperature raw material seawater to be fed the sodium ion generation permutoid reaction that is adsorbed on potassium ion and the clinoptilolite in the ion exchange column of filling sodium type clinoptilolite;
2) wash seawater in the deionization exchange column with water after, feed 25～95 ℃ ammonium chloride solution again, the potassium ion in the ion exchange column is carried out wash-out, elution flow rate is 4～10 meters/hour, obtains rich potassium liquid;
3) rich potassium liquid evaporation concentration to 115 ℃～122 ℃, then 101 ℃～110 ℃ insulation sedimentations down, supernatant liquid is 20～50 ℃ of cooling, crystallizations down.
The step that comprises with the method for preparing ammonium chloride with seawater provided by the invention:
1) under 0～35 ℃, carry out absorption reaction in the ion exchange column with raw material seawater feeding filling sodium type clinoptilolite, potassium ion in the seawater and the sodium ion on the clinoptilolite exchange, the mass ratio of raw material seawater and sodium type clinoptilolite is 6～150: 1, and the absorption flow velocity of raw material seawater (void tower flow velocity) is 5～45 meters/hour; The density range of raw material seawater is 2 ° of Be '～25 ° Be ' (degree Beaume).
2) water cleans the seawater in the deionizing exchange column, is that 15%～30% ammonium chloride solution carries out wash-out as eluent to the potassium ion in the ion exchange column with weight percent concentration under 25 ℃～95 ℃ temperature, obtains rich potassium liquid;
The mass ratio of eluent and sodium type clinoptilolite is 0.39～0.70: 1.The elution flow rate of eluent (void tower flow velocity) is controlled at 4～10 meters/hour.
3) under the normal pressure rich potassium liquid is carried out evaporation concentration, control evaporation final temperature is at 115 ℃～122 ℃, be incubated sedimentation 20-60 minute down in 101 ℃～110 ℃ then, isolate solid, supernatant liquid is cooled to 20 ℃～50 ℃, crystallization, centrifugation solid, be the ammonium chloride finished product, mother liquor returns evaporative crystallization desalination operation and continues to concentrate desalination.Lower floor is the salt slurry, and the salt slurry washs with the rich potassium liquid of 1: 1 weight, and centrifugation gets sodium-chlor, is used to prepare saturated brine.
It is to be under 30～101 ℃ in temperature that the na-pretreated zeolite of ion exchange column carries out step that renovation process comprises, feed the ion exchange column that contains sodium type clinoptilolite with saturated brine, flow velocity (void tower flow velocity) is 4～10 meters/hour, and the mass ratio of saturated brine and zeolite is 1.8～4.5: 1.The ammonium salt-containing water that obtains in the step for regeneration adds sodium hydroxide and carries out ammonia still process processing recovery ammonia, the adding metering of sodium hydroxide is for containing the mole number that waits of ammonia total amount in the salt solution, the ammonia still process temperature is controlled at 100～112 ℃, the ammonia that steams gets byproduct ammoniacal liquor after water absorbs, the gained ammonia concn is controlled at 15～20%, and salt solution after the ammonia still process (recovered brine) is also for recycling.
The substantive distinguishing features that the present invention gives prominence to marked improvement is: the inventive method is compared with the various preparation ammonium chloride methods that with Repone K are raw material, having raw material is easy to get, the advantage that cost is low, and, thereby can not be subjected to the restriction of Repone K raw material sources with the output that the inventive method is produced ammonium chloride because the potassium reserves of seawater are inexhaustible.
The inventive method " is extracted the method for vitriolate of tartar " with CN 200510133689.6 and is compared with seawater, because the eluent raw material is changed into ammonium chloride solution, significant change takes place thereby cause rich potassium liquid to be formed, the contriver is through a large amount of experimental studies, develop and comprise earlier by sodium-chlor in the rich potassium liquid of evaporative removal and will remove the high temperature clear liquid that obtains behind the sodium-chlor and make the brand-new separating technology of product ammonium chloride through direct one step of crystallisation by cooling again, also avoided the ammonia of " extracting the method for vitriolate of tartar with seawater " employing to analyse in the potassium sulfate process and may produce the ammonia pollution problems simultaneously operating environment; " produce the method for Repone K with seawater " with CN101323457A and compare, the present invention is by adopting the elution processes such as concentration eluent of high temperature and high ammonium ion, K in the rich potassium liquid that zeolite wash-out operation is prepared
+Content doubles, and direct one step of crystallisation by cooling technology of the high temperature clear liquid utilization that obtains after should richness potassium liquid evaporative removal sodium-chlor make the ammonium chloride product, having avoided carnallitite in " producing the method for Repone K with seawater " to add water decomposition and thick potassium adds operation such as water washing and increases to the water yield that system brings, thereby reduced the energy consumption of technological process significantly, and simplified technical process.
The product ammonium chloride total nutrient (K that the inventive method makes
2O+N) reach more than 40% K
2O:24.38%-25.24%, N:15.68%-14.93%, its quality reaches the index of composite fertilizer (compound manure) standard GB 15063-2001 middle and high concentration composite fertilizer.In addition, the technological process of the inventive method is simple, does not have discharging of waste liquid in the technological process, zeolite, ammoniacal liquor, salt solution are all taked to reclaim, and it is recycled, and have further reduced cost, improved economic benefit, opened up new approach for realizing the agricultural potash fertilizer self-sufficiency of China.
Description of drawings
Fig. 1 is the process flow diagram of the inventive method.
Embodiment
The present invention is described further in conjunction with the accompanying drawings, but they can not impose any restrictions the present invention.
The present invention is the ion exchange column absorption of raw material seawater with the filling modified zeolite, and seawater after absorption is discharged.With containing ammonium chloride solution adsorptive is carried out wash-out.Finish and feed saturated brine in the ion exchange column of wash-out operation and regenerated.The ammonium salt-containing water hydro-oxidation sodium that obtains in the step for regeneration carries out ammonia still process to be handled, and gets byproduct ammoniacal liquor, and recovered brine; The rich potassium liquid that obtains is through evaporative removal salinity wherein, and the gained complete evaporation of liquid is after cooling, and the solid-liquid separation of carrying out obtains the finished product ammonium chloride again, and specific embodiment is as follows:
Embodiment 1
The first step, the preparation of rich potassium liquid
At first 6000 gram sodium type using natural clinoptilolites are loaded among the ion exchange column of φ 30 * 12000mm strap clamp cover, constituted ion exchange unit.To ion exchange column 900 liters of (914 kilograms) 2 ° of Be ' raw material seawater of flow velocity (void tower flow velocity) feeding with 45 meters/hour, adsorb then, adsorption temp is 0 ℃.Containing potassium concn in the raw material seawater is 0.32 grams per liter, and containing potassium concn in the seawater that discharge the absorption back is 0.19 grams per liter, and the potassium ion in the seawater is switched in the zeolite.With fresh water the seawater in the zeolite column is all washed out.Press the data in the table 1, feeding temperature to above-mentioned ion exchange column with 10 meters/hour flow velocity (void tower flow velocity) is that 95 ℃ eluent 3790ml (4200 gram) carries out wash-out, stops wash-out when obtaining rich potassium liquid 3500ml (4070 gram).This richness potassium liquid composition is as shown in table 1, contains K
+: 30.23 grams per liters.Be that 30 ℃ saturated brine 22500ml (27000 gram) feeds in the ion exchange column of modified zeolite with 10 meters/hour flow velocity (void tower flow velocity) with temperature then, this moment, zeolite regeneration transferred the sodium type again to, can recycle repeatedly, meanwhile obtain ammonium salt-containing water 22500ml, it contains NH
4 +Be 4.32 grams per liters.Ammonium salt-containing water adds sodium hydroxide 216 grams, 100 ℃ of ammonia still processs, gets 20% ammoniacal liquor 466 grams, gets recovered brine 22300ml after the ammonia still process and recycles.Material composition in the potassium enrichment process sees Table 1.
Second step, the producing of finished product ammonium chloride
The rich potassium liquid 3500ml (4070g) that the first step is made carries out evaporation concentration, when reaching 115 ℃, the evaporation feed temperature stops evaporation, put into baking oven and keep 101 ℃ of sedimentations of temperature 20 minutes, after finishing, sedimentation pours out supernatant liquid 2231 gram residual salts slurries 205 grams, carry out centrifugation after clear liquid is cooled to 20 ℃ and obtain ammonium chloride solid 336 grams, mother liquor 1895 grams; Took by weighing rich potassium liquid 205 gram washing salt slurries 15 minutes, through obtaining separated salt 101 grams after the centrifugation, desalinization of soil by flooding or leaching mother liquor 309 grams.Desalinization of soil by flooding or leaching mother liquor later continues evaporation.Material component in the ammonium chloride sepn process sees Table 2.
Table 1 potassium enrichment process material component table
Table 2 ammonium chloride sepn process material component table
Embodiment 2
The first step, the preparation of rich potassium liquid
At first 6000 gram sodium type using natural clinoptilolites are loaded among the ion exchange column of φ 30 * 12000mm strap clamp cover, constituted ion exchange unit.To ion exchange column 500 liters of (525 kilograms) 7 ° of Be ' raw material seawater of flow velocity (void tower flow velocity) feeding with 35 meters/hour, adsorb then, adsorption temp is 10 ℃.Containing potassium concn in the raw material seawater is 0.71 grams per liter, and containing potassium concn in the seawater that discharge the absorption back is 0.47 grams per liter, and the potassium ion in the seawater is switched in the zeolite.With fresh water the seawater in the zeolite column is all washed out.Press the data in the table 3, feeding temperature to above-mentioned ion exchange column with 5 meters/hour flow velocity (void tower flow velocity) is that 50 ℃ eluent 2600ml (2900 gram) carries out wash-out, stops wash-out when obtaining rich potassium liquid 2500ml.This richness potassium liquid composition is as shown in table 3, contains K
+: 28.69 grams per liters.Be that 50 ℃ saturated brine 18000ml (21600 gram) feeds in the ion exchange column of modified zeolite with 5 meters/hour flow velocity (void tower flow velocity) with temperature then, this moment, zeolite regeneration transferred the sodium type again to, can recycle repeatedly, meanwhile obtain ammonium salt-containing water 18000ml, it contains NH
+ 4Be 3.68 grams per liters.Ammonium salt-containing water adds sodium hydroxide 147.2 grams, 110 ℃ of ammonia still processs, gets 18% ammoniacal liquor 368 grams, gets recovered brine 17900ml after the ammonia still process and recycles.Material composition in the potassium enrichment process sees Table 3.
Second step, the producing of finished product ammonium chloride
The rich potassium liquid 2500ml (2900 gram) that the first step is made carries out evaporation concentration, when reaching 116 ℃, the evaporation feed temperature stops evaporation, put into baking oven and keep 110 ℃ of sedimentations of temperature 30 minutes, after finishing, sedimentation pours out supernatant liquid 1663 gram residual salts slurries 222 grams, carry out centrifugation after clear liquid is cooled to 30 ℃ and obtain ammonium chloride solid 189 grams, mother liquor 1474 grams; Took by weighing rich potassium liquid 222 gram washing salt slurries 15 minutes, through obtaining separated salt 105 grams after the centrifugation, desalinization of soil by flooding or leaching mother liquor 339 grams.Desalinization of soil by flooding or leaching mother liquor later continues evaporation.Material component in the ammonium chloride sepn process sees Table 4.
Table 3 potassium enrichment process material component table
Table 4 ammonium chloride sepn process material component table
Embodiment 3
The first step, the preparation of rich potassium liquid
At first 6000 gram sodium type using natural clinoptilolites are loaded among the ion exchange column of φ 30 * 12000mm strap clamp cover, constituted ion exchange unit.To ion exchange column 150 liters of (164 kilograms) 12 ° of Be ' raw materials concentrated seawaters of flow velocity (void tower flow velocity) feeding with 15 meters/hour, adsorb then, adsorption temp is 0 ℃.Containing potassium concn in the raw material seawater is 1.52 grams per liters, and containing potassium concn in the seawater that discharge the absorption back is 0.70 grams per liter.Potassium ion in the seawater is switched in the zeolite.With fresh water the seawater in the zeolite column is all washed out.Press table 5 ' in data, feeding temperature to above-mentioned ion exchange column with 8 meters/hour flow velocity (void tower flow velocity) is that 90 ℃ eluent 2100ml (2344 gram) carries out wash-out, stops wash-out when obtaining rich potassium liquid 2000ml.This richness potassium liquid composition is as shown in table 1, contains K
+: 45.03 grams per liters.Be that 101 ℃ saturated brine 9000ml (10800 gram) feeds in the ion exchange column of modified zeolite with 4 meters/hour flow velocity (void tower flow velocity) with temperature then, this moment, zeolite regeneration transferred the sodium type again to, can recycle repeatedly, meanwhile obtain ammonium salt-containing water 9000ml, it contains NH
+ 4Be 9.24 grams per liters.Ammonium salt-containing water adds sodium hydroxide 184.8 grams, 112 ℃ of ammonia still processs, gets 15% ammoniacal liquor 520 grams, gets recovered brine 14900ml after the ammonia still process and recycles.Material composition in the potassium enrichment process sees Table 5.
Second step, the producing of finished product ammonium chloride
The rich potassium liquid 2000ml (2360g) that the first step is made carries out evaporation concentration, when reaching 117 ℃, the evaporation feed temperature stops evaporation, put into baking oven and keep 101 ℃ of sedimentations of temperature 40 minutes, after finishing, sedimentation pours out supernatant liquid 992 gram residual salts slurries 235 grams, carry out centrifugation after clear liquid is cooled to 30 ℃ and obtain ammonium chloride solid 356 grams, mother liquor 636 grams; Took by weighing rich potassium liquid 235 gram washing salt slurries 15 minutes, through obtaining separated salt 118 grams after the centrifugation, desalinization of soil by flooding or leaching mother liquor 352 grams.Desalinization of soil by flooding or leaching mother liquor later continues evaporation.Material component in the ammonium chloride sepn process sees Table 6.
Table 5 potassium enrichment process material component table
Table 6 ammonium chloride sepn process material component table
Embodiment 4
The first step, the preparation of rich potassium liquid
At first 6000 gram sodium type using natural clinoptilolites are loaded among the ion exchange column of φ 30 * 12000mm strap clamp cover, constituted ion exchange unit.To ion exchange column 90 liters of (102 kilograms) 17 ° of Be ' raw materials concentrated seawaters of flow velocity (void tower flow velocity) feeding with 25 meters/hour, adsorb then, adsorption temp is 20 ℃.Containing potassium concn in the raw material seawater is 2.72 grams per liters, and containing potassium concn in the seawater that discharge the absorption back is 1.41 grams per liters.Potassium ion in the seawater is switched in the zeolite.With fresh water the seawater in the zeolite column is all washed out.Press the data in the table 7, feeding temperature to above-mentioned ion exchange column with 4 meters/hour flow velocity (void tower flow velocity) is that 65 ℃ eluent 3000ml (3338 gram) carries out wash-out, stops wash-out when obtaining rich potassium liquid 2800ml.This richness potassium liquid composition is as shown in table 1, contains K
+: 36.41 grams per liters.Be that 70 ℃ saturated brine 12000ml (14400 gram) feeds in the ion exchange column of modified zeolite with 5 meters/hour flow velocity (void tower flow velocity) with temperature then, this moment, zeolite regeneration transferred the sodium type again to, can recycle repeatedly, meanwhile obtain ammonium salt-containing water 12000ml, it contains NH
+ 4Be 7.82 grams per liters.Ammonium salt-containing water adds sodium hydroxide 208.6 grams, 110 ℃ of ammonia still processs, gets 20% ammoniacal liquor 462 grams, gets recovered brine 11900ml after the ammonia still process and recycles.Material composition in the potassium enrichment process sees Table 7.
Second step, the producing of finished product ammonium chloride
The rich potassium liquid 2800ml (3293g) that the first step is made carries out evaporation concentration, when reaching 120 ℃, the evaporation feed temperature stops evaporation, put into baking oven and keep 110 ℃ of sedimentations of temperature 50 minutes, after finishing, sedimentation pours out supernatant liquid 1379 gram residual salts slurries 268 grams, carry out centrifugation after clear liquid is cooled to 40 ℃ and obtain ammonium chloride solid 236 grams, mother liquor 1143 grams; Took by weighing rich potassium liquid 268 gram washing salt slurries 15 minutes, through obtaining separated salt 122 grams after the centrifugation, desalinization of soil by flooding or leaching mother liquor 414 grams.Desalinization of soil by flooding or leaching mother liquor later continues evaporation.Material component in the ammonium chloride sepn process sees Table 8.
Table 7 potassium enrichment process material component table
Table 8 ammonium chloride sepn process material component table
Embodiment 5
The first step, the preparation of rich potassium liquid
At first the 6000g modified zeolite is loaded among the ion exchange column of φ 30 * 12000mm strap clamp cover, constituted ion exchange unit.To ion exchange column 30 liters of (36249g) 25 ° of Be ' raw material concentrated seawaters of flow velocity (void tower flow velocity) feeding with 5 meters/hour, adsorb then, adsorption temp is 35 ℃.Containing potassium concn in the raw material concentrated seawater is 4.30 grams per liters, and containing potassium concn in the seawater that discharge the absorption back is 1.15 grams per liters.Potassium ion in the seawater is switched in the zeolite.With fresh water the seawater in the zeolite column is all washed out.Press the data in the table 9, feeding temperature to above-mentioned ion exchange column with 4 meters/hour flow velocity (void tower flow velocity) is that 25 ℃ eluent 3200ml (3600 gram) carries out wash-out, stops wash-out when obtaining rich potassium liquid 3100ml.This richness potassium liquid composition is as shown in table 1, contains K
+: 29.02 grams per liters.Be that 95 ℃ saturated brine 9000ml (10796 gram) feeds in the ion exchange column of modified zeolite with 4 meters/hour flow velocity with temperature then, this moment, zeolite regeneration transferred the sodium type again to, can recycle repeatedly, meanwhile obtained ammonium salt-containing water 9000ml, and it contains NH
+ 4Be 9.20 grams per liters.Ammonium salt-containing water adds sodium hydroxide 184 grams, 100 ℃ of ammonia still processs, gets 18% ammoniacal liquor 460 grams, gets recovered brine 8900ml after the ammonia still process and recycles.Material composition in the potassium enrichment process sees Table 9.
Second step, the producing of finished product ammonium chloride
The rich potassium liquid 3100ml (3613g) that the first step is made carries out evaporation concentration, when reaching 122 ℃, the evaporation feed temperature stops evaporation, put into baking oven and keep 101 ℃ of sedimentations of temperature 60 minutes, after finishing, sedimentation pours out supernatant liquid 1348 gram residual salts slurries 278 grams, carry out centrifugation after clear liquid is cooled to 50 ℃ and obtain ammonium chloride solid 217 grams, mother liquor 1131 grams; Took by weighing rich potassium liquid 278 gram washing salt slurries 15 minutes, through obtaining separated salt 140 grams after the centrifugation, desalinization of soil by flooding or leaching mother liquor 416 grams.Desalinization of soil by flooding or leaching mother liquor later continues evaporation.Material component in the ammonium chloride sepn process sees Table 10.
Table 9 potassium enrichment process material component table
Table 10 ammonium chloride sepn process material component table
Claims (5)
1. method with preparing ammonium chloride with seawater is characterized in that the step of its process:
1) it is complete at room temperature raw material seawater to be fed the sodium ion generation permutoid reaction that is adsorbed on potassium ion and the clinoptilolite in the ion exchange column of filling sodium type clinoptilolite;
2) wash seawater in the deionization exchange column with water after, feed 25～95 ℃ ammonium chloride solution again, the potassium ion in the ion exchange column is carried out wash-out, elution flow rate is 4～10 meters/hour, obtains rich potassium liquid;
3) rich potassium liquid evaporation concentration to 115 ℃～122 ℃, then 101 ℃～110 ℃ insulation sedimentations down, supernatant liquid is 20～50 ℃ of cooling, crystallizations down.
2. method with preparing ammonium chloride with seawater is characterized in that the step that it comprises:
1) under 0～35 ℃, carry out absorption reaction in the ion exchange column with raw material seawater feeding filling sodium type clinoptilolite, potassium ion in the seawater and the sodium ion on the clinoptilolite exchange, the mass ratio of raw material seawater and sodium type clinoptilolite is 6～150: 1, and the absorption flow velocity of raw material seawater is 5～45 meters/hour;
2) water cleans the seawater in the deionization exchange column, is that 15%～30% ammonium chloride solution carries out wash-out as eluent to the potassium ion in the ion exchange column with weight percent concentration under 25 ℃～95 ℃ temperature, obtains rich potassium liquid; Wherein, the mass ratio of eluent and sodium type clinoptilolite is 0.39～0.70: 1;
3) under the normal pressure rich potassium liquid is carried out evaporation concentration, the control final temperature stops evaporation when reaching 115 ℃～122 ℃, be incubated sedimentation 20-60 minute down in 101 ℃～110 ℃ then, isolate solid, supernatant liquid is cooled to 20 ℃～50 ℃, crystallization, the centrifugation solid is the ammonium chloride finished product.
3. method according to claim 2, the density range that it is characterized in that the described raw material seawater of step 1) is 2～25 degree Beaume.
4. method according to claim 2 is characterized in that step 2) elution flow rate of described eluent is 4～10 meters/hour.
5. method according to claim 2, the na-pretreated zeolite that it is characterized in that the described ion exchange column of step 1) carries out the regenerated method and is: under 30～101 ℃ of temperature, feed the ion exchange column that contains sodium type clinoptilolite with saturated brine, flow velocity is 4～10 meters/hour, and the mass ratio of saturated brine and zeolite is 1.8～4.5: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102976797A (en) * | 2012-12-14 | 2013-03-20 | 国家海洋局天津海水淡化与综合利用研究所 | Method for extracting potassium co-production liquid salt from concentrated seawater |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102976797A (en) * | 2012-12-14 | 2013-03-20 | 国家海洋局天津海水淡化与综合利用研究所 | Method for extracting potassium co-production liquid salt from concentrated seawater |
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