CN103449478A - Comprehensive utilization and production method of underground potassium chloride-rich brine - Google Patents
Comprehensive utilization and production method of underground potassium chloride-rich brine Download PDFInfo
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- CN103449478A CN103449478A CN2013103760261A CN201310376026A CN103449478A CN 103449478 A CN103449478 A CN 103449478A CN 2013103760261 A CN2013103760261 A CN 2013103760261A CN 201310376026 A CN201310376026 A CN 201310376026A CN 103449478 A CN103449478 A CN 103449478A
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Abstract
The invention relates to a comprehensive utilization and production method of underground potassium chloride-rich brine. The method comprises the steps: purifying the underground brine, enabling the purified underground brine to firstly enter a sodium chloride extraction device and extracting sodium chloride; after the sodium chloride is extracted, enabling mother liquor to enter a potassium chloride device, and continuously carrying out evaporation and concentration to obtain sylvine; decomposing and washing the sylvine to obtain a potassium chloride product; enabling an evaporated and concentrated solution in the potassium chloride device to enter a storage tank to be taken as an iodine blowing raw material; carrying out acidizing, oxidizing by chlorine, blowing out by air, absorption and enrichment by sulfur dioxide on the raw material, carrying out iodine dissociation procedure and refining iodine to prepare elemental iodine; enabling waste liquid obtained by iodine preparation to enter a bromine preparation device; oxidizing bromide ions in the raw material in the bromine preparation device by chlorine to enable the bromide ions to become elemental bromide, carrying out distilling by water vapor, condensation and separation, and rectification working procedure on the elemental bromide to obtain a bromine product finally; enabling mother liquor coming from the distilled bromide to enter a calcium chloride device finally, and carrying out evaporation and concentration and tabletting in the calcium chloride device to obtain a calcium chloride dihydrate product finally. The whole production process is free from waste liquid emission, so that the zero emission of the underground potassium-rich brine can be realized.
Description
Technical field
The present invention relates to underground potassium-rich brine comprehensive utilization technique field, specially refer to the underground comprehensive utilization production method that is rich in Repone K bittern.
Background technology
Current underground potassium-rich brine fully utilizes at home and abroad research and comparison early, but the industrialization of subsurface brine comprehensive utilization also seldom there is no the suitability for industrialized production of descend on a large scale potassium-rich brine to fully utilize truly at present in other words.The present invention is raw material with underground potassium-rich brine, is applicable to the minable many component bittern of underground all places containing potassium.Provided the industrialized producing technology of underground potassium-rich brine comprehensive utilization based on this.
Summary of the invention
Vacancy based on underground potassium-rich brine industrialized producing technology is necessary to propose the processing method that underground potassium-rich brine fully utilizes very much, realizes the comprehensive utilization of underground potassium-rich brine, is applicable to the minable bittern of underground all places containing potassium.Main component in subsurface brine is Na
+, K
+, Br
-, I
-, Ca
2+, Cl
-.The feature of potassium-rich brine under base area, this technique is extracted product to underground bittern comprehensive utilization and is: NaCl, KCl, I
2, Br
2, CaCl
22H
2o.
Technical scheme of the present invention is as follows:
A kind of underground comprehensive utilization production method that is rich in Repone K bittern, its step is as follows:
1) at first subsurface brine is entered into after purifying to the sodium chloride extraction device and extract the sodium-chlor product;
2) mother liquor after extraction sodium-chlor enters into Repone K device continuation evaporation concentration to obtain sylvite, and sylvite obtains Potassium Chloride Product after decomposing washing;
3) the evaporation concentration liquid of Repone K device enters into storage tank as blowing the iodine raw material, and raw material is acidified, chlorine oxidation and Air blowing, sulfurous gas absorb enrichment, the free operation of iodine and iodinating and refining operation and prepares iodine;
4) iodine waste liquid processed enters into bromine device processed, at the bromide anion in bromine device Raw processed, after the oxidation of chlorine becomes simple substance bromine, through steam distillation, condensation separation and rectification working process, has finally made the bromine product;
5) from steaming the Zhongdao calcium chloride device of bromine mother liquor out, in the calcium chloride device, through evaporation concentration and film-making, finally obtain the Calcium dichloride dihydrate product.
Sodium chloride extraction of the present invention adopts multiple-effect evaporation or MVR method.
The method that described multiple-effect evaporation technique is extracted sodium-chlor is: bittern is delivered to evaporation unit through being preheated to 40-50 ℃, and the first effect of multi-effect evaporation system adopts the living steam that pressure is 0.2-0.5Mpa, and end effect evaporating pot working pressure absolute pressure is 2-20Kpa.
The method that described MVR technique is extracted sodium-chlor is: bittern is delivered to evaporation unit through being preheated to 40-50 ℃, adopts the living steam of 0.07-0.14Mpa, and end effect secondary steam pressure is 71.5-140Kpa.
Repone K of the present invention extracts multiple-effect evaporation or the MVR method of adopting.
Multiple-effect evaporation extracts the Repone K method: the mother liquor that sodium-chlor production is discharged enters into the Repone K evaporation unit and carries out shwoot and evaporation, in the evaporation unit of Repone K, the first effect of multi-effect evaporation system adopts the living steam that pressure is 0-0.4Mpa, and end effect evaporating pot working pressure absolute pressure is 2-20Kpa; Sylvite is eluriated leg from the evaporator room bottom and is discharged, and the sylvite after discharge is through washing and separating preparing potassium chloride.
MVR technique is extracted the Repone K method: the mother liquor that sodium-chlor production is discharged enters into the Repone K evaporation unit and carries out shwoot and evaporation, in the evaporation unit of Repone K, adopts the living steam of 0.07-0.14Mpa, and end effect secondary steam pressure is 71.5-140Kpa.
The present invention prepares elemental iodine and adopts the Air blowing method: the bittern acidifying is controlled at pH=1.0-3.5; It is 105～120% that chlorine oxidation is joined the chlorine rate; Refining iodine temperature is controlled at 120-160 ℃.
Steam of the present invention blows out method and extracts bromine: the mother liquor after over-blowing iodine enters into steamed bromine device and produces bromine, chlorine oxidation joins that the chlorine rate is 115～125%, steam distillation goes out 80～100 ℃ of bromine mouth temperature, distillation tower adopt vapor pressure 0.05～0.20Mpa, condensation and separate, thick bromine rectifying and tail gas recycle, 40～60 ℃ of thick bromine rectification temperatures, the rectifying vapor pressure is 0.05～0.20Mpa.
The method of described step 5) is to utilize single-effect evaporation to produce Calcium dichloride dihydrate to be: utilize steam in evaporation equipment, mother liquor to be carried out to evaporation concentration as thermal source, vapor pressure is 0.30～0.50Mpa, treat that mother liquor is concentrated into to 40% to 50% of original volume just can discharge mother liquor, through the overcooling film-making, obtain the Calcium dichloride dihydrate product.
The underground comprehensive utilization production method that is rich in Repone K bittern because be comprehensive utilization, consider product and environmental protection etc. factor, the method adopted is carried out simultaneously; The raw material that the mother liquor of last operation is subsequent handling.
Adopting multiple-effect evaporation or MVR(is the abbreviation of steam mechanical recompression mechanical vapor recompression) technique extracts sodium-chlor, but in implementation process, selects good in economic efficiency a kind of; Because the scale difference, benefit is different.So depend on the circumstances.MVR is the energy that re-uses the secondary steam that it self produces, thereby reduces a power-saving technology of the demand of the energy to external world; Multiple-effect evaporation or MVR technique are extracted Repone K; The Air blowing method is extracted elemental iodine; Steam blows out method and extracts bromine; Utilize single-effect evaporation to produce Calcium dichloride dihydrate.
The present invention extracts and calcium chloride extraction technique through sodium chloride extraction, Repone K extraction, iodine extraction, simple substance bromine.Extracting product from the subsurface brine comprehensive utilization is: NaCl, KCl, I
2, Br
2, CaCl
22H
2o.Whole production process is discharged without waste liquid, has finally realized the zero release of underground potassium-rich brine.
The accompanying drawing explanation
Fig. 1: underground potassium-rich brine comprehensive utilization schema of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The present invention is by subsurface brine (wherein main component: NaCl, KCl, I as shown in Figure 1
2, Br
2, CaCl
2) process through bittern purifying impurity such as removing iron ion, at first the bittern after purification enter into the extraction element of sodium-chlor, through operations such as preheating, evaporation, washing, centrifuge dehydration and dryings, obtains the sodium-chlor product, discharges mother liquor by evaporation section simultaneously.The higher evaporation section that enters into the Repone K device of mother liquor temperature of being discharged by the sodium-chlor device, adopt multiple-effect evaporation or MVR technique in the Repone K evaporative process, temperature in evaporating pot is lower, so it is at first concentrated through shwoot to enter into the Repone K evaporation section from the mother liquor of sodium-chlor device, then heat and carry out evaporation concentration by evaporation, in evaporating concentration process, evaporation along with moisture, sylvite is constantly separated out from solution, the separating, washing workshop section that final sylvite has entered into the Repone K device produces Repone K, the evaporation waste liquid is discharged in the storage tank of iodine device.Repone K evaporation waste liquid absorbs enrichment, the free operation of iodine and iodinating and refining operation through bittern acidifying, chlorine oxidation and Air blowing, sulfurous gas and finally produces iodine, and it is as follows that iodine is produced the main chemical reactions occurred in process:
(1) Air blowing operation chlorine oxidation reaction
2I
－+Cl
2→2Cl
-+I
2
(2) sulfurous gas absorbs the enrichment operation
I
2＋SO
2+2H
2O→2HI+H
2SO
4
(3) free operation
2HI＋NaClO→I
2+NaCl+H
2O
The waste liquid that iodine device processed is discharged enters and steams the bromine device, in steaming the bromine device, iodine waste liquid processed through the condensation of chlorine oxidation, wet distillation, bromine with separate, thick bromine rectifying and tail gas recycle operation finally produce simple substance bromine, the main chemical reactions occurred in the bromine preparation process (chlorine oxidation) is as follows:
2Br
-+2Cl
2→Br
2+2Cl
-+91.84KJ
The mother liquor that steams the discharge of bromine device wet distillation workshop section enters into final calcium chloride device, mainly contain evaporation and two workshop sections of film-making in the calcium chloride device, adopt evaporation concentration at evaporation section, the mother liquor after concentrated enters into pelleter and carries out film-making, finally obtains the product Calcium dichloride dihydrate.
The method that multiple-effect evaporation technique is extracted sodium-chlor is: bittern is delivered to evaporation unit through being preheated to 40-50 ℃, and the first effect of multi-effect evaporation system adopts the living steam that pressure is 0.2-0.5Mpa, and end effect evaporating pot working pressure absolute pressure is 2-20Kpa.
The method that MVR technique is extracted sodium-chlor is: bittern is delivered to evaporation unit through being preheated to 40-50 ℃, adopts the living steam of 0.07-0.14Mpa, and end effect secondary steam pressure is 71.5-140Kpa.
Multiple-effect evaporation extracts the Repone K method: the mother liquor that sodium-chlor production is discharged enters into the Repone K evaporation unit and carries out shwoot and evaporation, in the evaporation unit of Repone K, the first effect of multi-effect evaporation system adopts the living steam that pressure is 0-0.4Mpa, and end effect evaporating pot working pressure absolute pressure is 2-20Kpa; Sylvite is eluriated leg from the evaporator room bottom and is discharged, and the sylvite after discharge is through washing and separating preparing potassium chloride.
MVR technique is extracted the Repone K method: the mother liquor that sodium-chlor production is discharged enters into the Repone K evaporation unit and carries out shwoot and evaporation, in the evaporation unit of Repone K, adopts the living steam of 0.07-0.14Mpa, and end effect secondary steam pressure is 71.5-140Kpa.
The method that the Air blowing method is extracted elemental iodine is: at first the mother liquor that the Repone K device is discharged enters dashpot, then enter into air through pump delivery and blow iodine device production iodine, the preparation method of iodine comprises that bittern acidifying (the bittern potential of hydrogen is controlled at PH=1.0-3.5), chlorine oxidation (it is 105～120% that chlorine oxidation is joined the chlorine rate) and Air blowing, sulfurous gas absorb the operations such as enrichment, the free operation of iodine and iodinating and refining, and refining iodine temperature is controlled at 120-160 ℃.
The method that steam blows out method extraction bromine is: the mother liquor after over-blowing iodine enters into steamed bromine device and produces bromine, the production of bromine comprises that (distillation tower adopts vapor pressure 0.05～0.20Mpa for chlorine oxidation (it is 115～125% that chlorine oxidation is joined the chlorine rate), steam distillation, distill out 80～100 ℃ of bromine mouth temperature), condensation with separate, thick bromine rectifying (40～60 ℃ of thick bromine rectification temperatures, the rectifying vapor pressure is 0.05～0.20Mpa) and tail gas recycle.
The method of utilizing single-effect evaporation to produce Calcium dichloride dihydrate is: utilize steam in evaporation equipment, mother liquor to be carried out to evaporation concentration as thermal source, vapor pressure is 0.30～0.50Mpa, treat that mother liquor is concentrated into to 40% to 50% of original volume just can discharge mother liquor, through the overcooling film-making, obtain the Calcium dichloride dihydrate product.
The actually operating that adopts above-mentioned technical process to carry out is as follows:
In example below, step 1 adopts multiple-effect evaporation, and step 2 can adopt multiple-effect also can adopt MVR; Step 1 adopts MVR, and step 2 can adopt multiple-effect also can adopt MVR; It is the relation of a permutation and combination.
The sodium-chlor production process
Example 1:
Multi-effect evaporating device: by after the raw material preheating to 40 after purifying ℃, enter the end effect evaporation unit, end effect evaporating pot working pressure is (absolute pressure) 2KPa, in tank, complete evaporation of liquid is entered the evaporating pot of front by the end effect evaporating pot through transfering material pump, finally forwards in first effect evaporating pot.The pressure that first effect evaporating pot enters living steam is 0.2MPa.And imitate evaporating pot from head and discharged liquid and enter the Repone K evaporation section.At this, the sodium-chlor product is eluriated leg and is discharged from the evaporator room bottom of each evaporating pot, is pooled in the salt stock tank; Enter the operations such as dehydration, drying via brine pump.
The MVR device: enter evaporation unit by after the raw material preheating to 40 after purifying ℃, while starting to start the MVR device, use external steam to be heated, the working pressure of heating chamber is that 0.07MPa gives birth to steam.After indoor generation secondary steam to be evaporated, through washing, enter vapour compressor; At this vapour compressor, low-grade secondary steam is compressed into to the higher-grade steam needed, through eliminating after overheated to enter in heating chamber, substitutes the living steam from boiler.In operating process, the secondary steam pressure of end effect evaporating pot is controlled at 71.5KPa.The sodium-chlor product is eluriated leg and is discharged in the salt stock tank from the evaporator room bottom of evaporating pot; Enter the operations such as dehydration, drying via brine pump.Complete evaporation of liquid enters the Repone K evaporization process as the raw material of preparing potassium chloride.
Example 2:
Multi-effect evaporating device: by after the raw material preheating to 45 after purifying ℃, enter the end effect evaporation unit, end effect evaporating pot working pressure is (absolute pressure) 10KPa, in tank, complete evaporation of liquid is entered the evaporating pot of front by the end effect evaporating pot through transfering material pump, finally forwards in first effect evaporating pot.The pressure that first effect evaporating pot enters living steam is 0.3MPa.And imitate evaporating pot from head and discharged liquid and enter the Repone K evaporation section.At this, the sodium-chlor product is eluriated leg and is discharged from the evaporator room bottom of each evaporating pot, is pooled in the salt stock tank; Enter the operations such as dehydration, drying via brine pump.
The MVR device: enter evaporation unit by after the raw material preheating to 45 after purifying ℃, while starting to start the MVR device, use external steam to be heated, the working pressure of heating chamber is that 0.10MPa gives birth to steam.After indoor generation secondary steam to be evaporated, through washing, enter vapour compressor; At this vapour compressor, low-grade secondary steam is compressed into to the higher-grade steam needed, through eliminating after overheated to enter in heating chamber, substitutes the living steam from boiler.In operating process, the secondary steam pressure of end effect evaporating pot is controlled at 100KPa.The sodium-chlor product is eluriated leg and is discharged in the salt stock tank from the evaporator room bottom of evaporating pot; Enter the operations such as dehydration, drying via brine pump.Complete evaporation of liquid enters the Repone K evaporization process as the raw material of preparing potassium chloride.
Example 3:
Multi-effect evaporating device: by after the raw material preheating to 50 after purifying ℃, enter the end effect evaporation unit, end effect evaporating pot working pressure is (absolute pressure) 20KPa, in tank, complete evaporation of liquid is entered the evaporating pot of front by the end effect evaporating pot through transfering material pump, finally forwards in first effect evaporating pot.The pressure that first effect evaporating pot enters living steam is 0.5MPa.And imitate evaporating pot from head and discharged liquid and enter the Repone K evaporation section.At this, the sodium-chlor product is eluriated leg and is discharged from the evaporator room bottom of each evaporating pot, is pooled in the salt stock tank; Enter the operations such as dehydration, drying via brine pump.
The MVR device: enter evaporation unit by after the raw material preheating to 50 after purifying ℃, while starting to start the MVR device, use external steam to be heated, the working pressure of heating chamber is that 0.14MPa gives birth to steam.After indoor generation secondary steam to be evaporated, through washing, enter vapour compressor; At this vapour compressor, low-grade secondary steam is compressed into to the higher-grade steam needed, through eliminating after overheated to enter in heating chamber, substitutes the living steam from boiler.In operating process, the secondary steam pressure of end effect evaporating pot is controlled at 140KPa.The sodium-chlor product is eluriated leg and is discharged in the salt stock tank from the evaporator room bottom of evaporating pot; Enter the operations such as dehydration, drying via brine pump.Complete evaporation of liquid enters the Repone K evaporization process as the raw material of preparing potassium chloride.
The KCl production operation
Example 1:
Multi-effect evaporating device: enter first effect evaporating pot from 130 ℃ of materials of sodium-chlor production workshop section and carry out shwoot and heating evaporation, first effect heating chamber vapor temperature is 100 ℃ (being 0MPa), complete evaporation of liquid enters next effect and carries out heating evaporation, and thermal source is from the secondary steam of a upper effect; Finally enter the end effect evaporation unit, end effect evaporating pot working pressure is (absolute pressure) 2KPa.Sylvite is eluriated leg from the evaporator room bottom and is discharged, and the sylvite after discharge is through washing and separating preparing potassium chloride.
The MVR device: enter evaporating pot from 130 ℃ of materials of sodium-chlor production workshop section and carry out shwoot and heating evaporation, while starting to start the MVR device, use external steam to be heated, the working pressure of heating chamber is that 0.07MPa gives birth to steam.After indoor generation secondary steam to be evaporated, through washing, enter vapour compressor; At this vapour compressor, low-grade secondary steam is compressed into to the higher-grade steam needed, through eliminating after overheated to enter in heating chamber, substitutes the living steam from boiler.In operating process, the secondary steam pressure of end effect evaporating pot is controlled at 71.5KPa.The sylvite product is eluriated leg from the evaporator room bottom of evaporating pot and is discharged to the salt stock tank; Enter the operations such as dehydration, packing via brine pump.
Example 2:
Multi-effect evaporating device: enter first effect evaporating pot from 130 ℃ of materials of sodium-chlor production workshop section and carry out shwoot and heating evaporation, first effect heating chamber vapor temperature is 0.2MPa, complete evaporation of liquid enters next effect and carries out heating evaporation, and thermal source is from the secondary steam of a upper effect; Finally enter the end effect evaporation unit, end effect evaporating pot working pressure is (absolute pressure) 10KPa.Sylvite is eluriated leg from the evaporator room bottom and is discharged, and the sylvite after discharge is through washing and separating preparing potassium chloride.
The MVR device: enter evaporating pot from 130 ℃ of materials of sodium-chlor production workshop section and carry out shwoot and heating evaporation, while starting to start the MVR device, use external steam to be heated, the working pressure of heating chamber is that 0.10MPa gives birth to steam.After indoor generation secondary steam to be evaporated, through washing, enter vapour compressor; At this vapour compressor, low-grade secondary steam is compressed into to the higher-grade steam needed, through eliminating after overheated to enter in heating chamber, substitutes the living steam from boiler.In operating process, the secondary steam pressure of end effect evaporating pot is controlled at 100KPa.The sylvite product is eluriated leg from the evaporator room bottom of evaporating pot and is discharged to the salt stock tank; Enter the operations such as dehydration, packing via brine pump.
Example 3:
Multi-effect evaporating device: enter first effect evaporating pot from 130 ℃ of materials of sodium-chlor production workshop section and carry out shwoot and heating evaporation, first effect heating chamber vapor temperature is 0.4MPa, complete evaporation of liquid enters next effect and carries out heating evaporation, and thermal source is from the secondary steam of a upper effect; Finally enter the end effect evaporation unit, end effect evaporating pot working pressure is (absolute pressure) 20KPa.Sylvite is eluriated leg from the evaporator room bottom and is discharged, and the sylvite after discharge is through washing and separating preparing potassium chloride.
The MVR device: enter evaporating pot from 130 ℃ of materials of sodium-chlor production workshop section and carry out shwoot and heating evaporation, while starting to start the MVR device, use external steam to be heated, the working pressure of heating chamber is that 0.14MPa gives birth to steam.After indoor generation secondary steam to be evaporated, through washing, enter vapour compressor; At this vapour compressor, low-grade secondary steam is compressed into to the higher-grade steam needed, through eliminating after overheated to enter in heating chamber, substitutes the living steam from boiler.In operating process, the secondary steam pressure of end effect evaporating pot is controlled at 140KPa.The sylvite product is eluriated leg from the evaporator room bottom of evaporating pot and is discharged to the salt stock tank; Enter the operations such as dehydration, packing via brine pump.
The iodine production process
Example 1:
The mother liquor that the Repone K device is discharged, acid adding is regulated the pH value to 1.0 of bittern, then passes into chlorine.It is 105% that chlorine is joined the chlorine rate, pass into the iodide ion in mother liquor after chlorine and be oxidized to free molecular iodine, the free-iodine that enters stripping tower enters absorption tower from top, top adds sulfur dioxide gas and fresh fresh water simultaneously, absorb into the hydroiodic acid HI mother liquor, the hydroiodic acid HI mother liquor is oxidized to thick iodine with NaClO again, after thick iodine adds the vitriol oil, passes into steam, refining iodine temperature is controlled at 120 ℃, makes finished product.
Example 2:
The mother liquor that the Repone K device is discharged, acid adding is regulated the pH value to 2.0 of bittern, then passes into chlorine.It is 115% that chlorine is joined the chlorine rate, pass into the iodide ion in mother liquor after chlorine and be oxidized to free molecular iodine, the free-iodine that enters stripping tower enters absorption tower from top, top adds sulfur dioxide gas and fresh fresh water simultaneously, absorb into the hydroiodic acid HI mother liquor, the hydroiodic acid HI mother liquor is oxidized to thick iodine with NaClO again, after thick iodine adds the vitriol oil, passes into steam, refining iodine temperature is controlled at 140 ℃, makes finished product.
Example 3:
The mother liquor that the Repone K device is discharged, acid adding is regulated the pH value to 3.5 of bittern, then passes into chlorine.It is 120% that chlorine is joined the chlorine rate, pass into the iodide ion in mother liquor after chlorine and be oxidized to free molecular iodine, the free-iodine that enters stripping tower enters absorption tower from top, top adds sulfur dioxide gas and fresh fresh water simultaneously, absorb into the hydroiodic acid HI mother liquor, the hydroiodic acid HI mother liquor is oxidized to thick iodine with NaClO again, after thick iodine adds the vitriol oil, passes into steam, refining iodine temperature is controlled at 160 ℃, makes finished product.
The bromine production process
Example 1:
After iodine production, mother liquor enters the bromine production equipment, carries out the oxidizing reaction of chlorine and the still-process of free bromine in distillation tower, carries waste liquid after bromine and discharges at the bottom of by tower, and it is 115% that chlorine oxidation is joined the chlorine rate; Distill out 80 ℃ of bromine mouth temperature, distillation tower adopts vapor pressure 0.05Mpa.The bromine vapor distilled out enters condenser.Carry out separating of liquid bromine and bromine water after condensation, the bromine water after separation is returned in distillation tower; Thick bromine enters in rectifying tower to be made with extra care.40 ℃ of thick bromine rectification temperatures, the rectifying vapor pressure is 0.05Mpa.The smart bromine of being discharged by rectifying still is put into storage bromine bottle after entering the water cooler cooling, through being packaged into product.
Example 2:
After iodine production, mother liquor enters the bromine production equipment, carries out the oxidizing reaction of chlorine and the still-process of free bromine in distillation tower, carries waste liquid after bromine and discharges at the bottom of by tower, and it is 120% that chlorine oxidation is joined the chlorine rate; Distill out 90 ℃ of bromine mouth temperature, distillation tower adopts vapor pressure 0.10Mpa.The bromine vapor distilled out enters condenser.Carry out separating of liquid bromine and bromine water after condensation, the bromine water after separation is returned in distillation tower; Thick bromine enters in rectifying tower to be made with extra care.50 ℃ of thick bromine rectification temperatures, the rectifying vapor pressure is 0.10Mpa.The smart bromine of being discharged by rectifying still is put into storage bromine bottle after entering the water cooler cooling, through being packaged into product.
Example 3:
After iodine production, mother liquor enters the bromine production equipment, carries out the oxidizing reaction of chlorine and the still-process of free bromine in distillation tower, carries waste liquid after bromine and discharges at the bottom of by tower, and it is 125% that chlorine oxidation is joined the chlorine rate; Distill out 100 ℃ of bromine mouth temperature, distillation tower adopts vapor pressure 0.20Mpa.The bromine vapor distilled out enters condenser.Carry out separating of liquid bromine and bromine water after condensation, the bromine water after separation is returned in distillation tower; Thick bromine enters in rectifying tower to be made with extra care.60 ℃ of thick bromine rectification temperatures, the rectifying vapor pressure is 0.20Mpa.The smart bromine of being discharged by rectifying still is put into storage bromine bottle after entering the water cooler cooling, through being packaged into product.
The Calcium dichloride dihydrate production process
Example 1:
Enter the calcium chloride evaporation concentration device from 80 ℃, the mother liquor of the chloride containing calcium that steams the bromine device, chloride containing calcium 210g/l Repone K 90g/l sodium-chlor 60g/l in mother liquor, mother liquor is evaporated in the calcium chloride concentrating unit, 140 ℃ of vapor temperatures, proportion until feed liquid is increased at 1.37 o'clock, stop evaporation, separate sodium-chlor and solid potassium chloride mixture in feed liquid, mixture returns to the KCl production device, clear liquid after separation enters the cooling moviemaking system of calcium chloride, finally obtains sheet Calcium dichloride dihydrate product.
Example 2:
Enter the calcium chloride evaporation concentration device from 85 ℃, the mother liquor of the chloride containing calcium that steams the bromine device, chloride containing calcium 195g/l Repone K 105g/l, sodium-chlor 75g/l in mother liquor, mother liquor is evaporated in the calcium chloride concentrating unit, 140 ℃ of vapor temperatures, proportion until feed liquid is increased at 1.37 o'clock, stop evaporation, separate sodium-chlor and solid potassium chloride mixture in feed liquid, mixture returns to the KCl production device, clear liquid after separation enters the cooling moviemaking system of calcium chloride, finally obtains sheet Calcium dichloride dihydrate product.
Example 3:
Enter the calcium chloride evaporation concentration device from 90 ℃, the mother liquor of the chloride containing calcium that steams the bromine device, chloride containing calcium 250g/l, Repone K 80g/l, sodium-chlor 65g/l in mother liquor, mother liquor is evaporated in the calcium chloride concentrating unit, 140 ℃ of vapor temperatures, proportion until feed liquid is increased at 1.37 o'clock, stop evaporation, separate sodium-chlor and solid potassium chloride mixture in feed liquid, mixture returns to the KCl production device, clear liquid after separation enters the cooling moviemaking system of calcium chloride, finally obtains sheet Calcium dichloride dihydrate product.
Claims (10)
1. the underground comprehensive utilization production method that is rich in Repone K bittern is characterized in that step is as follows:
1) at first subsurface brine is entered into after purifying to the sodium chloride extraction device and extract the sodium-chlor product;
2) mother liquor after extraction sodium-chlor enters into Repone K device continuation evaporation concentration to obtain sylvite, and sylvite obtains Potassium Chloride Product after washing separates;
3) the evaporation concentration liquid of Repone K device enters into storage tank as blowing the iodine raw material, and raw material is acidified, chlorine oxidation and Air blowing, sulfurous gas absorb enrichment, the free operation of iodine and iodinating and refining operation and prepares iodine;
4) iodine waste liquid processed enters into bromine device processed, at the bromide anion in bromine device Raw processed, after the oxidation of chlorine becomes simple substance bromine, through steam distillation, condensation separation and rectification working process, finally makes the bromine product;
5) from steaming the Zhongdao calcium chloride device of bromine mother liquor out, in the calcium chloride device, through evaporation concentration and film-making, finally obtain the Calcium dichloride dihydrate product.
2. the method for claim 1, is characterized in that sodium chloride extraction adopts multiple-effect evaporation or MVR method.
3. method as claimed in claim 2, the method that it is characterized in that multiple-effect evaporation technique extraction sodium-chlor is: bittern is delivered to evaporation unit through being preheated to 40-50 ℃, the first effect of multi-effect evaporation system adopts the living steam that pressure is 0.2-0.5Mpa, and end effect evaporating pot working pressure absolute pressure is 2-20Kpa.
4. method as claimed in claim 2, it is characterized in that MVR technique extracts the method for sodium-chlor and be: bittern is delivered to evaporation unit through being preheated to 40-50 ℃, adopts the living steam of 0.07-0.14Mpa, and end effect secondary steam pressure is 71.5-140Kpa.
5. the method for claim 1, is characterized in that Repone K extracts multiple-effect evaporation or the MVR method of adopting.
6. method as claimed in claim 5, it is characterized in that multiple-effect evaporation extracts the Repone K method and is: the mother liquor that sodium-chlor production is discharged enters into the Repone K evaporation unit and carries out shwoot and evaporation, in the evaporation unit of Repone K, the first effect of multi-effect evaporation system adopts the living steam that pressure is 0-0.4Mpa, and end effect evaporating pot working pressure absolute pressure is 2-20Kpa; Sylvite is eluriated leg from the evaporator room bottom and is discharged, and the sylvite after discharge is through washing and separating preparing potassium chloride.
7. method as claimed in claim 5, it is characterized in that MVR technique extraction Repone K method is: the mother liquor that sodium-chlor production is discharged enters into the Repone K evaporation unit and carries out shwoot and evaporation, in the evaporation unit of Repone K, adopt the living steam of 0.07-0.14Mpa, end effect secondary steam pressure is 71.5-140Kpa.
8. the method for claim 1, it is characterized in that preparing elemental iodine and adopt the Air blowing method: the bittern acidifying is controlled at pH=1.0-3.5; It is 105～120% that chlorine oxidation is joined the chlorine rate; Refining iodine temperature is controlled at 120-160 ℃.
9. the method for claim 1, the method that it is characterized in that step 4) is that steam blows out method extraction bromine: the mother liquor after over-blowing iodine enters into steamed bromine device and produces bromine, chlorine oxidation joins that the chlorine rate is 115～125%, steam distillation goes out 80～100 ℃ of bromine mouth temperature, distillation tower adopt vapor pressure 0.05～0.20Mpa, condensation and separate, thick bromine rectifying and tail gas recycle, 40～60 ℃ of thick bromine rectification temperatures, the rectifying vapor pressure is 0.05～0.20Mpa.
10. the method for claim 1, the method that it is characterized in that step 5) is to utilize single-effect evaporation to produce Calcium dichloride dihydrate to be: utilize steam in evaporation equipment, mother liquor to be carried out to evaporation concentration as thermal source, vapor pressure is 0.30～0.50Mpa, treat that mother liquor is concentrated into to 40% to 50% of original volume just can discharge mother liquor, through the overcooling film-making, obtain the Calcium dichloride dihydrate product.
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| CN104229737A (en) * | 2014-09-18 | 2014-12-24 | 中盐工程技术研究院有限公司 | Method and device for producing bromine from brominated butyl rubber wastewater through steam distillation |
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| CN115304083A (en) * | 2022-08-25 | 2022-11-08 | 湖北振华化学股份有限公司 | Method for circularly extracting bromine from glaserite mother liquor in production process of preparing potassium sulfate from glauber salt |
| CN115304083B (en) * | 2022-08-25 | 2023-07-07 | 湖北振华化学股份有限公司 | Method for circularly extracting bromine from glaserite mother liquor in production process of preparing potassium sulfate from mirabilite |
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