CN114477236A - Calcium halide purification method and pH value adjustment method - Google Patents
Calcium halide purification method and pH value adjustment method Download PDFInfo
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- CN114477236A CN114477236A CN202210104146.5A CN202210104146A CN114477236A CN 114477236 A CN114477236 A CN 114477236A CN 202210104146 A CN202210104146 A CN 202210104146A CN 114477236 A CN114477236 A CN 114477236A
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- calcium
- brine
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- halide
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- 239000011575 calcium Substances 0.000 title claims abstract description 157
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 157
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000000746 purification Methods 0.000 title claims abstract description 29
- -1 Calcium halide Chemical class 0.000 title claims description 80
- 239000012267 brine Substances 0.000 claims abstract description 145
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 142
- 239000004571 lime Substances 0.000 claims abstract description 119
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 117
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 117
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000000843 powder Substances 0.000 claims abstract description 57
- 239000008267 milk Substances 0.000 claims abstract description 53
- 210000004080 milk Anatomy 0.000 claims abstract description 53
- 235000013336 milk Nutrition 0.000 claims abstract description 53
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 34
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 23
- 241001131796 Botaurus stellaris Species 0.000 claims abstract description 21
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011780 sodium chloride Substances 0.000 claims abstract description 17
- 239000001110 calcium chloride Substances 0.000 claims abstract description 16
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 16
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 238000012360 testing method Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 93
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 58
- 239000007788 liquid Substances 0.000 claims description 54
- 238000002360 preparation method Methods 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 45
- 229910052736 halogen Inorganic materials 0.000 claims description 41
- 239000000292 calcium oxide Substances 0.000 claims description 36
- 235000012255 calcium oxide Nutrition 0.000 claims description 36
- 150000002367 halogens Chemical class 0.000 claims description 30
- 239000011777 magnesium Substances 0.000 claims description 25
- 229910052749 magnesium Inorganic materials 0.000 claims description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 18
- 239000008394 flocculating agent Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 9
- 238000012546 transfer Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 159000000007 calcium salts Chemical class 0.000 claims description 5
- 238000010979 pH adjustment Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 4
- 239000007832 Na2SO4 Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims 1
- 238000001704 evaporation Methods 0.000 abstract description 5
- 230000008020 evaporation Effects 0.000 abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
- C01D3/16—Purification by precipitation or adsorption
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
- C01F11/32—Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a calcium brine purification method and a pH value adjustment method, wherein the purification method S1 comprises the steps of taking single-well calcium brine, detecting the calcium brine, including the steps of detecting NaCl and CaCl2(ii) a Let in the original brine bucket with calcium bittern, detect the original brine bucket in calcium bittern brine, the test item includes: NaCl, CaCl2、Mg2+Content and pH value. S2, determining the weight of the lime powder according to the data detected in the original brine barrel in the step S1; mixing lime powder and refined brine to obtain lime milk, the problem that the lime milk calcium brine is purified and the pH value is controlled before brine enters an evaporation system is solved through the lime milk calcium brine purification and control method.
Description
Technical Field
The invention relates to the field of inorganic chemical industry, in particular to a calcium halide purification method and a pH value adjustment method.
Background
In the production of the calcium salt, the pH value of the calcium halide is 10.5-11, no or trace magnesium ions are contained, while the existing calcium halide is generally alkalescent, the pH value is far lower than the value, and the content of the magnesium ions is higher. In order to reduce the adverse effect of low pH value of calcium halide on corrosion of equipment pipelines in the production of calcium chloride, the pH value is required to be adjusted to 10.5-11 so as to improve the alkalinity of the calcium halide, and in order to prevent magnesium ions in the production of the calcium chloride from separating out to be scale layers attached to the equipment pipelines to influence heat transfer or reduce the pipe diameter, the calcium halide brine is required to be purified to remove magnesium.
Common raw materials for purifying calcium halide to remove magnesium and improving the pH value of the calcium halide are as follows: liquid caustic soda or quicklime. Liquid caustic soda calcium halide is directly used for purifying and adjusting the pH value, a liquid caustic soda storage tank, a caustic soda pump, a matched pipeline, an electrical instrument, civil engineering and other equipment are required to be additionally arranged, most of the rest of the liquid caustic soda with the content of 32 percent is water, namely, the liquid caustic soda is used as a raw material, a large amount of clear water enters an evaporation system of a calcium salt device, the calcium halide is easy to scale and influence heat transfer after being not purified and pretreated, and the liquid caustic soda is higher in price than quicklime, so that the production cost is very high; the pH value is adjusted by the quicklime and the quicklime can only be used in calcium brine in front of an evaporation system, the addition amount of the poor stability of the active ingredients of the quicklime is difficult to control, more impurities of water insoluble substances enter the evaporation system to influence the product quality, the calcium brine is easy to scale and influence heat transfer in the unpurified pretreatment, the facility investment is more, a lime storage barrel, a lime slaking barrel, a lime milk pump, a matched pipeline, an electric instrument and civil engineering need to be newly added or utilized, and the cost of equipment is higher.
Disclosure of Invention
Based on the above, the invention aims to provide a calcium brine purification method and a pH value adjustment method in the production of calcium chloride, which solve the problems caused by the fact that more raw water enters an evaporation system, more water-insoluble impurities enter a production device to influence the product quality, the operation difficulty is high and the like in the existing calcium brine unpurified and pH value adjustment;
in order to achieve the purpose, the invention provides the following technical scheme:
on one hand, the invention provides a method for purifying calcium halide in the production of salt calcium,
the method comprises the following steps:
s1, taking single-well calcium bittern, detecting the calcium bittern including NaCl and CaCl2(ii) a Let in the original brine bucket with calcium bittern, detect the original brine bucket in calcium bittern brine, the test item includes: NaCl, CaCl2、Mg2+Content and pH value;
s2, according to the data detected in the original halogen barrel in the step S1,
determining the weight of lime powder; mixing the lime powder and the refined brine to obtain lime milk;
and S3, mixing the calcium-halogen brine in the raw brine barrel in the step S1 and the lime milk obtained in the step S2 in a reaction barrel, and adding a flocculating agent after the reaction is finished.
Preferably, the S1 includes the steps of:
s11, taking single-well calcium halide samples, analyzing and detecting NaCl and CaCl of each single-well calcium halide2；
S12, feeding the calcium-halogen single-well brine into a calcium-halogen raw brine barrel, and calculating the total flow of raw brine in hours, wherein if the flow of raw brine is more than 560m3H; starting the stirring device when the liquid level reaches 3 m;
s13, if the flow rate of the original halogen is lower than 560m3H, by calcium-halogenating CaCl2And sodium nitrate halide Na2SO4The difference of the amount of the supplementary calcium and the amount of the supplementary brine is adopted;
s14, when the liquid level of the raw brine barrel reaches 14 m, starting a raw brine pump to transfer materials to the reaction barrel until the liquid level reaches 19.5 m, stopping transferring the materials, and recording the liquid level of the reaction barrel; starting a stirring device matched with the reaction barrel when the feed liquid is 3 m;
s15, taking the original brine barrel calcium brine sample to analyze and detect NaCl and CaCl of the calcium brine2pH value, Mg2+And (4) content.
Preferably, the lime milk preparation comprises the following steps:
and S1, automatically flowing the lime powder to a lime scale, and weighing the weight of the lime powder required by calcium halide purification.
And S2, making the refined brine automatically flow to a lime milk preparation barrel, adding the lime powder into the lime milk preparation barrel, stirring, and continuously stirring to dissolve and emulsify the lime powder into lime milk for later use.
Preferably, step S3 specifically includes the following steps:
s31, adding lime milk into the reaction barrel, and mixing and stirring the lime milk and the calcium halide in the reaction barrel;
s32, carrying out brine purification reaction;
and S33, stirring the reaction barrel to react for 3 hours, and detecting the pH value of the calcium halide.
And S34, if the pH value of the calcium halide is detected to be not less than 10.5, adding the prepared flocculating agent into the reaction barrel, stopping stirring the stirring device of the flocculating agent preparation barrel, and stopping stirring after the stirring device in the reaction barrel continuously stirs for 5 minutes.
S35, after the reaction barrel stops the stirring device and is clarified for 3 hours, detecting calcium halide in the reaction barrel, wherein the detection items comprise: NaCl, CaCl2pH, solids.
Preferably, after step S3, the adjusting method further includes:
s4, detecting whether the reaction barrel is clear and qualified in halogen clearing, and transferring the clear halogen in the reaction barrel to a refined halogen barrel;
and S5, conveying the clear brine in the refined brine barrel in the step S4 to a calcium brine barrel of a brine purification workshop to be used as a raw material of a calcium salt production device.
Preferably, after the clear bittern in the reaction barrel is transferred to the refined bittern barrel, the method further comprises the following steps:
s41, after the completion of the brine removal and material transfer of the reaction barrel, starting stirring, and stirring the reaction magnesium mud into a suspension state;
and S42, when the reacted magnesium mud is uniformly stirred, conveying the mud to a light calcium liquid barrel, and injecting the light calcium liquid into a well to recover brine.
In yet another aspect, the present application provides a method of pH adjustment, the method comprising the steps of:
s21, according to the liquid level of calcium and brine in the reaction barrel, Mg2+Calculating the weight of lime powder required by calcium halide magnesium removal according to the content of CaO and MgO of the lime powder;
s22, calculating the weight of lime powder required by the pH value adjustment of the calcium halide according to the liquid level and the pH value of the calcium halide in the reaction barrel and the pH value adjustment not less than 10.5; the sum of the weight of the lime powder required by the magnesium removal of the calcium halide and the pH value adjustment of the calcium halide is the weight of the lime powder required by the purification of the batch of calcium halide.
S23 calculating the weight of lime powder
The weight of the lime powder is calculated as follows:
m(CaO)＝(230.73×c(Mg2+)+8.8666)×h÷ω(CaO)
in the formula: m is(CaO)Purifying and adjusting pH with lime powder in unit/(Kg)
c(Mg2+)- - -magnesium content in calcium halide in unit/(g/L)
V- - -reaction barrel (T-1181B/C) calcium halide volume, unit/(m)3)
ω(CaO)- -determination of the effective calcium oxide content of the lime powder, unit/(%)
In yet another aspect, the present application provides a method for adjusting the pH of a calcium brine in the production of calcium chloride, comprising: a calcium brine raw brine barrel, a reaction barrel, a refined brine barrel, a flocculating agent preparation barrel, a lime milk preparation barrel and a light calcium liquid barrel;
the calcium halide raw halogen barrel is used for collecting and storing calcium halide raw halogen, the calcium halide raw halogen enters the calcium halide raw halogen barrel from a halogen well through a pipeline, and the total flow of the raw halogen in hours is calculated (T-1181A);
the reaction barrel is used for calcium halide raw halogen purification reaction and pH adjustment, the reaction barrel and the calcium halide raw halogen barrel are connected through a pipeline, and a raw halogen pump is arranged on the pipeline between the reaction barrel and the calcium halide raw halogen barrel;
the refined brine barrel is used for storing refined brine, the refined brine barrel is connected with the reaction barrel through a pipeline, and a brine cleaning pump is arranged on the pipeline between the refined brine barrel and the reaction barrel;
the flocculant preparation barrel is used for preparing and storing a flocculant, the flocculant preparation barrel is connected with the reaction barrel through a pipeline, a flocculant pump is arranged on the pipeline between the flocculant preparation barrel and the reaction barrel, and a denitration calcium brine pump is arranged on the pipeline between the flocculant preparation barrel and the refined brine barrel;
the lime milk preparation barrel is used for preparing and storing lime milk, and a denitration calcium brine pump is arranged on a pipeline between the lime milk preparation barrel and the refined brine barrel through the pipeline; a lime milk pump is arranged on a pipeline between the lime milk preparation barrel and the reaction barrel through a pipeline;
the fresh calcium liquid barrel is used for storing fresh calcium liquid, the fresh calcium liquid barrel is connected with the reaction barrel through a pipeline, and a slurry pump is arranged on the pipeline between the fresh calcium liquid barrel and the reaction barrel.
Compared with the prior art, the invention has the beneficial effects that:
the device has the advantages that the pipeline of the device is changed less, and the utilization rate of part of the existing devices can be improved; the device is placed together with saltpeter brine purification and the like, has strong integrity, is convenient for centralized management and is beneficial to operation and running;
the application solves the problems of purifying and adjusting the pH on the well through lime milk calcium halide and stably adjusting the pH.
Drawings
FIG. 1: is a schematic diagram of the equipment of the method for purifying calcium halide in the production of salt calcium in the specific embodiment of the application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
The application relates to a method for purifying calcium bittern in salt calcium production and a method for adjusting pH value, and the equipment connection relation is shown in figure 1
The device shown in figure 1 comprises a calcium brine raw brine barrel, a reaction barrel, a refined brine barrel, a flocculating agent preparation barrel, a lime milk preparation barrel and a light calcium liquid barrel;
the calcium-brine raw brine barrel obtains raw brine from a brine well, and the raw brine enters the reaction barrel through a pipeline; the reaction barrel not only receives the original halogen, but also is communicated with the flocculating agent preparation barrel and the lime milk preparation barrel, the lime milk and the original halogen react to purify the calcium halogen, the pH value is adjusted to a standard value, and then the flocculating agent is added to separate impurities; the reaction barrel is also communicated with a refined brine barrel, brine with the pH value of the brine to a standard value and impurities removed is introduced into the refined brine barrel from the reaction barrel, the refined brine barrel is also communicated with a lime milk preparation barrel and a flocculant preparation barrel, and the refined brine is introduced into the lime milk preparation barrel and the flocculant preparation barrel to be used for preparing lime milk and a flocculant; then the reaction barrel is connected with a light calcium liquid barrel, the precipitated impurities are introduced into the light calcium liquid barrel, the main components of the impurities are magnesium hydroxide precipitate and water insoluble substances in quicklime, and the impurities and the light calcium liquid can be directly used for exploiting the original brine after being mixed.
All buckets are connected through pipelines, corresponding valves and corresponding pumps are arranged, and stirring devices matched with each other are arranged in the buckets.
A comparison of the methods for increasing the pH of calcium halide is given in Table 1 below
TABLE 1
Example 1
In example 1, the room temperature of the reaction environment is 25 ℃, and the specifications of all the barrels such as the original brine barrel, the reaction barrel, the refined brine barrel and the like are phi 20000 multiplied by 22000.
1.1 preparation of crude bittern
1) Taking single-well calcium bittern samples, analyzing and monitoring NaCl and CaCl of each single-well calcium bittern2。
2) Blending the raw brine quality and the brine well quantity of the calcium brine well, feeding the calcium brine single-well brine into a calcium brine raw brine barrel (T-1181A), calculating the total flow of the raw brine in hours, and keeping the raw brine yield to be more than 560m3H; when the liquid level reaches 3 m, the stirring device (AG-1181A) is started.
3) E.g. with a flow of raw halogen of less than 560m3H, according to calcium-halogen CaCl2And sodium nitrate halide Na2SO4The difference of the calcium halide quantity is supplemented.
4) When the liquid level of a raw brine barrel A (T-1181A) reaches 14 meters, starting a raw brine pump (P-1181) according to a rule, transferring materials to a reaction barrel (T-1181B/C) until the liquid level reaches 19.5 meters, stopping transferring the materials, stopping the pump according to the rule, and recording the liquid level of the reaction barrel; and starting a stirring device (AG-1181B/C) matched with the reaction barrel when the feed liquid is 3 meters.
5) The laboratory test personnel takes the original bittern barrel (T-1181A) calcium bittern sample according to the regulations to analyze and monitor NaCl and CaCl of the calcium bittern2pH value, Mg2 +And (4) content.
1.2 lime milk preparation
1.2.1 calculation of lime powder weight
1) According to the liquid level of calcium bittern in the reaction barrel and Mg2+And calculating the weight of the lime powder required by the calcium halide for removing magnesium according to the contents of CaO and MgO of the lime powder.
2) And calculating the weight of the lime powder required by the pH value adjustment of the calcium halide according to the liquid level and the pH value of the calcium halide in the reaction barrel and the pH value up-to-standard value of the refined halide of 10.5.
3) The sum of the weight of the lime powder required by the magnesium removal of the calcium halide and the pH value adjustment of the calcium halide is the weight of the lime powder required by the purification of the batch of calcium halide.
4) Calculation of lime powder weight
The calculation formula of the weight of the lime powder which needs to be added for purifying the calcium halide and adjusting the pH value in each reaction barrel is as follows:
m(CaO)＝(72447×c(Mg2+)+2784.11)×h÷ω(CaO)
in the formula: m is(CaO)Purifying and adjusting pH with lime powder in unit/(Kg)
c(Mg2+)- - -magnesium content in calcium halide in unit/(g/L)
h- - -reaction barrel (T-1181B/C) calcium halogen material level, unit/(m)
ω(CaO)- -determination of the effective calcium oxide content of the lime powder, unit/(%)
1.2.2 lime milk preparation
1) And (3) automatically flowing lime powder to a lime weighing scale from a lime bin, and weighing the weight of the lime powder required by calcium halide purification in batches.
2) Opening a valve from a refined brine barrel (T-1181D) to a lime milk preparation barrel pipeline, wherein refined brine automatically flows to the lime milk preparation barrel (T-1184), or when the liquid level of the refined brine barrel is low, adding refined brine into the lime milk preparation barrel by a denitration calcium brine pump (P-1184A/B), and stopping adding refined brine when the liquid level reaches 3.5 m; when the feed liquid is 1 m, the stirring device (AG-1184) of the lime milk preparation barrel is started.
3) When the refined brine is added into a lime milk preparation barrel (T-1184) to the liquid level of 1.5 m, a screw conveyor is started to add the lime powder weighed in the weighing scale into the lime milk preparation barrel (T-1184), and the lime powder is dissolved and emulsified into lime milk for later use by continuous stirring.
The main reaction: CaO + H2O→Ca(OH)2
13 preparation of flocculating agent
1) Weighing 1.5Kg of solid flocculant.
2) Opening a valve from a refined brine barrel (T-1181D) to a lime milk preparation barrel pipeline, enabling refined brine to automatically flow to a flocculant preparation barrel (T-1185), or adding refined brine into the flocculant preparation barrel by a denitration calcium brine pump (P-1184A/B) when the liquid level of the refined brine barrel is low, and stopping adding the refined brine when the liquid level reaches 2 m; when the feed liquid reaches 1 m, a stirring device (AG-1185) of a flocculant preparation barrel is started.
3) When refined brine is added into a flocculant preparation barrel (T-1185) to the liquid level of 1.8 m, the weighed solid flocculant is slowly added into the flocculant preparation barrel (T-1185), and the mixture is continuously stirred for 4 hours to dissolve the flocculant for later use.
1.4 purification of calcium halide and pH adjustment
Calcium brine purification is to remove magnesium by using insoluble magnesium hydroxide generated by hydroxide radicals of lime dissolved in water and magnesium in calcium brine, and add hydroxide radicals generated by excessive lime to improve the pH value of the calcium brine, and the main reaction formula is as follows: A) lime hydrolysis: CaO + H2O→Ca(OH)2(ii) a B) Calcium hydroxide ionization: ca (OH)2→Ca2++2OH－(ii) a C) Generation of insoluble matter: 2OH－+Mg2+→Mg(OH)2↓. The specific operation is as follows:
1) when the feed liquid in the reaction barrel (T-1181B/C) reaches 16 m, a lime milk pump is started to add the prepared lime milk into the reaction barrel (T-1181B/C), and the lime milk pump and a lime milk preparation barrel stirring device (AG-1184) are stopped according to regulations after the lime milk is transferred.
2) When the feed liquid in the reaction barrel (T-1181B/C) reaches 19.5 m, the original halogen pump is stopped, and the stirring device continues to stir for reaction for 3 hours.
3) When the feed liquid in the reaction barrel (T-1181B/C) reaches 16 m, a brine circulating pump (P-1188/1189) is started, and the pH value of the calcium brine is observed.
4) After stirring and reacting for 3 hours, an analyst takes a calcium halide sample in a reaction barrel (T-1181B/C) to detect the pH value of the calcium halide.
5) And (3) when the pH value of the calcium halide reaches 10.5, starting a flocculant pump, adding the prepared flocculant into a reaction barrel (T-1181B/C), stopping the flocculant pump according to rules after the flocculant is transferred, stopping a flocculant preparation barrel stirring device (AG-1185), continuously stirring the reaction barrel stirring device (AG-1181B/C) for 5 minutes, and stopping the stirring device (AG-1181B/C).
6) After the reaction barrel (T-1181B/C) stops the stirring device and is clarified for 3 hours, an inspector takes a calcium halide sample of the reaction barrel (T-1181B/C) to monitor NaCl and CaCl2pH value, solid content and the like.
1.5 calcium brine storage and transportation
1) After the laboratory technician monitors that the reaction barrel (T-1181B/C) is clarified and qualified in clear halogen, a halogen clearing pump (P-1182) is started according to the regulations to transfer the clear halogen of the reaction barrel (T-1181B/C) to a refined halogen barrel (T-1181D).
2) And (3) starting a calcium brine conveying pump (P-1183A/B) according to the regulation, and conveying the refined brine in the refined brine barrel (T-1181D) to a calcium brine barrel in a brine purification workshop through a calcium brine pipe to be used as a raw material of a calcium salt production device.
1.6 reaction magnesium sludge cleaning
1) After the reaction barrel (T-1181B/C) completes the brine removal and material transfer, a stirring device (AG-1181B/C) is started to stir the reaction magnesium mud into a suspension state.
2) After the reaction magnesium mud is uniformly stirred, a mud pump (P-1185) is started according to the regulations to convey the mud in the reaction barrel (T-1181B/C) to a light calcium liquid barrel (T-1121B) through a mud pipe, and the mud is mixed with the light calcium liquid and then injected into a well along with the light calcium liquid to recover the brine.
Example 1 the results of the tests are given in Table 2 below
TABLE 2
(1) Original halogen (before pH adjustment): NaCl greater than or equal to 270g/L, MgSO4 0.2～0.3g/L、CaCl250g/L、pH 8.02。
2) Refined brine control indexes are as follows: NaCl more than or equal to 270g/L, CaCl 250 g/L, pH value of 10.5, solid content less than or equal to 20ppm, Mg2+Less than or equal to 6ppm or none.
As can be seen from Table 2, by the method of example 1, the pH was adjusted to 10.5 and the solid content was 20ppm or less, and Mg was cut off2+。
Example 2
Example 2 differs from example 1 in that the room temperature was 30 c,
the calculation formula of the weight of the lime powder which needs to be added for purifying the calcium halide and adjusting the pH value in each reaction barrel is as follows:
m(CaO)＝C×(72447×c(Mg2+)+2784.11)×h÷ω(CaO)
in the formula: m is(CaO)Purifying and adjusting pH with lime powder in unit/(Kg)
c(Mg2+)- - -magnesium content in calcium halide in unit/(g/L)
h- - -reaction barrel (T-1181B/C) calcium halogen material level, unit/(m)
ω(CaO)- -determination of the effective calcium oxide content of the lime powder, unit/(%)
C- -lime powder addition adjustment coefficient.
The C value is 1.00 to 1.05.
Other preparation methods and preparation conditions were the same as in example 1.
Example 3
Example 3 differs from example 1 in that the room temperature was 10 c,
the calculation formula of the weight of the lime powder which needs to be added for purifying the calcium halide and adjusting the pH value in each reaction barrel is as follows:
m(CaO)＝C×(72447×c(Mg2+)+2784.11)×h÷ω(CaO)
in the formula: m is(CaO)Purifying and adjusting pH with lime powder in unit/(Kg)
c(Mg2+)- - -magnesium content in calcium halide in unit/(g/L)
h- - -reaction barrel (T-1181B/C) calcium halogen material level, unit/(m)
ω(CaO)- -determination of the effective calcium oxide content of the lime powder, unit/(%)
C- -lime powder addition adjustment coefficient.
The C value is 1.00 to 1.05.
The other preparation methods and preparation conditions were the same as in example 1.
Comparative example 1
Comparative example 1 differs from example 1 in that
Calculating the weight of lime powder according to the raw brine barrel, directly adding the calculated lime milk into a calcium brine raw brine barrel, then adding the calcium brine into a reaction barrel from the raw brine barrel, and adding a flocculating agent, wherein other preparation methods and preparation conditions are consistent with those of the example 1.
Comparative example 2
Comparative example 2 differs from example 1 in that
The weight of the lime powder is calculated according to the refined brine tank, the calculated lime milk and the flocculating agent are directly added into the refined brine tank, and other preparation methods and preparation conditions are consistent with those of the example 1.
Examples 2 to 3 and comparative examples 1 to 2
The results of the measurements are shown in Table 3 below
TABLE 3
As can be seen from table 3, in examples 2 and 3, the weight of the lime powder is increased by 1.02 times when the temperature is higher or lower, and the pH value can be ensured to reach 10.5; according to the comparative example 1, if the pH is adjusted by lime milk in the original brine tank, the pH does not reach the standard, and more solid matters are contained, and according to the comparative example 2, the lime milk is directly added into the refined brine tank, so that the pH value reaches the standard, the pH value is higher, but the content of the solid matters is more; in contrast, in examples 1 to 3 and comparative examples 1 to 2, the content of Mg was well controlled by adjusting with lime milk.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention are equivalent to or changed within the scope of the present invention.
Claims (7)
1. A calcium halide purification process, characterized in that it comprises the following steps:
s1, taking single-well calcium bittern, and detecting the calcium bittern including NaCl and CaCl2(ii) a Let in the original brine bucket with calcium bittern, detect the original brine bucket in calcium bittern brine, the test item includes: NaCl, CaCl2、Mg2+Content and pH value;
s2, determining the weight of the lime powder according to the data detected in the original halogen barrel in the step S1, and mixing and emulsifying the lime powder and the refined halogen to obtain lime milk;
and S3, mixing the calcium-halogen brine in the raw brine barrel in the step S1 and the lime milk obtained in the step S2 in a reaction barrel, and adding a flocculating agent after the reaction is finished.
2. The calcium halide purification method according to claim 1, wherein the S1 comprises the steps of:
s11, taking single-well calcium halide samples, analyzing and detecting NaCl and CaCl of each single-well calcium halide2；
S12, feeding the calcium-halogen single-well brine into a calcium-halogen raw brine barrel, and calculating the total flow of raw brine in hours, wherein if the flow of raw brine is more than 560m3H; starting the stirring device when the liquid level reaches 3 m;
s13, if the flow rate of the original halogen is lower than 560m3H, by calcium-halogenating CaCl2And sodium nitrate halide Na2SO4The difference of the amount of the supplementary calcium and the amount of the supplementary brine is adopted;
s14, when the liquid level of the raw brine barrel reaches 14 m, starting a raw brine pump to transfer materials to the reaction barrel until the liquid level reaches 19.5 m, stopping transferring the materials, and recording the liquid level of the reaction barrel; starting a stirring device matched with the reaction barrel when the feed liquid is 3 m;
s15, taking the original brine barrel calcium brine sample to analyze and detect NaCl and CaCl of the calcium brine2pH value, Mg2+And (4) content.
3. The calcium halide purification method according to claim 1, wherein the lime milk is prepared by the following steps:
s1, automatically flowing lime powder to a lime scale, and weighing the weight of the lime powder required by calcium halide purification;
and S2, making the refined brine automatically flow to a lime milk preparation barrel, adding the lime powder into the lime milk preparation barrel, stirring, and continuously stirring to dissolve and emulsify the lime powder into lime milk for later use.
4. The calcium halide purification method according to claim 1, wherein the step S3 specifically comprises the steps of:
s31, adding lime milk into the reaction barrel, and mixing and stirring the lime milk and the calcium halide in the reaction barrel;
s32, carrying out brine purification reaction;
s33, stirring the reaction barrel to react for 3 hours, and detecting the pH value of the calcium halide;
s34, if the pH value of the calcium halide is detected to be not less than 10.5, adding the prepared flocculating agent into a reaction barrel, stopping stirring the stirring device of the flocculating agent preparation barrel, and stopping stirring after the stirring device in the reaction barrel continuously stirs for 5 minutes;
s35, after the reaction barrel stops the stirring device and is clarified for 3 hours, detecting calcium halide in the reaction barrel, wherein the detection items comprise: NaCl, CaCl2pH, solids.
5. The calcium halide purification method according to claim 1, wherein the adjustment method further comprises, after step S3:
s4, detecting whether the reaction barrel is clear and qualified in halogen clearing, and transferring the clear halogen in the reaction barrel to a refined halogen barrel;
and S5, conveying the clear brine in the refined brine barrel in the step S41 to a calcium brine barrel of a brine purification workshop to be used as a raw material of a calcium salt production device.
6. The calcium bittern purification method as claimed in claim 5, further comprising after transferring the clean bittern in the reaction barrel to the refined bittern barrel:
s41, after the completion of the brine removal and material transfer of the reaction barrel, starting stirring, and stirring the reaction magnesium mud into a suspension state;
and S42, when the reacted magnesium mud is uniformly stirred, conveying the mud to a light calcium liquid barrel, and injecting the light calcium liquid into a well to recover brine.
7. A pH adjustment method for the calcium halide purification method according to any one of claims 1 to 6, characterized in that the method comprises the steps of:
s21, according to the liquid level of calcium and brine in the reaction barrel, Mg2+Calculating the weight of lime powder required by calcium halide magnesium removal according to the content of CaO and MgO of the lime powder;
s22, calculating the weight of lime powder required by the pH value adjustment of the calcium halide according to the liquid level and the pH value of the calcium halide in the reaction barrel and the pH value adjustment not less than 10.5; the sum of the weight of the lime powder required by the magnesium removal of the calcium halide and the pH value adjustment of the calcium halide is the weight of the lime powder required by the purification of the calcium halide of the batch;
s23 calculating the weight of lime powder
The weight of the lime powder is calculated as follows:
m(CaO)＝(230.73×c(Mg2+)+8.8666)×h÷ω(CaO)
in the formula: m is a unit of(CaO)Purifying and adjusting pH with lime powder in unit/(Kg)
c(Mg2+)- -the magnesium content in the calcium halide in units/(g/L)
V- - -reaction barrel (T-1181B/C) calcium halide volume, unit/(m)3)
ω(CaO)The effective calcium oxide content of the lime powder is determined in units/(%).
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| CN117243360A (en) * | 2023-10-17 | 2023-12-19 | 重庆合川盐化工业有限公司 | Brine treatment method and table salt preparation method for inhibiting yellowing of iodized salt |
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