CN111377459A - Method for extracting boric acid from calcium chloride type brine - Google Patents
Method for extracting boric acid from calcium chloride type brine Download PDFInfo
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- CN111377459A CN111377459A CN202010253174.4A CN202010253174A CN111377459A CN 111377459 A CN111377459 A CN 111377459A CN 202010253174 A CN202010253174 A CN 202010253174A CN 111377459 A CN111377459 A CN 111377459A
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- boric acid
- calcium chloride
- mother liquor
- temperature
- brine
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1045—Oxyacids
- C01B35/1054—Orthoboric acid
- C01B35/1081—Preparation by working up other natural sources, e.g. seawater
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1045—Oxyacids
- C01B35/1054—Orthoboric acid
- C01B35/109—Purification; Separation; Concentration
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- 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
- C01F11/30—Concentrating; Dehydrating; Preventing the adsorption of moisture or caking
Abstract
A method for extracting boric acid from calcium chloride type brine comprises the following steps: the method comprises the following steps: acidifying the oil field brine after extracting lithium and potassium by adding hydrochloric acid to convert boron into boric acid to obtain original brine A; step two: carrying out constant-temperature evaporation operation on the original halogen A at the temperature of 20-30 ℃, precipitating boric acid crystals, and filtering to obtain a mother solution B; step three: mixing the mother liquor B with the original halogen A to obtain mother liquor C, carrying out constant-temperature cooling crystallization operation on the mother liquor C at the temperature of 0-10 ℃, precipitating boric acid crystals, and filtering to obtain mother liquor D; step four: and (3) carrying out constant-temperature evaporation operation on the mother liquor D at the temperature of 20-30 ℃, separating out calcium chloride hexahydrate crystals, and filtering to obtain a mother liquor B. After potassium and lithium elements are extracted from the oilfield brine in the south wing mountain area, the brine system can be regarded as a calcium chloride-boric acid-water system, so that the boric acid and calcium chloride are separated by adopting phase diagrams of the ternary system at 0 ℃ and 25 ℃.
Description
Technical Field
The invention belongs to the field of brine treatment, and particularly relates to a method for extracting boric acid from calcium chloride type brine.
Background
The brine is liquid mineral with salt content more than 5%, and is called surface brine or lake brine which is gathered on the surface. The underground brine is called as the underground brine collected below the ground. Since the brine resource is often associated with oil and gas and comes to the ground together with petroleum and natural gas, the brine is often called oil (gas) field brine. The brine contains considerable elements and contains abundant potassium, lithium, boron and other elements, but the brine in different regions has different element contents, and if a unified method is selected for treatment, the treatment efficiency of the oil field brine in part of regions is low, so that the oil field brine treatment in different regions needs to be researched in a targeted manner.
Disclosure of Invention
The invention provides a method for extracting boric acid from calcium chloride type brine, which is used for overcoming the defects in the prior art.
The invention is realized by the following technical scheme:
a method for extracting boric acid from calcium chloride type brine comprises the following steps:
the method comprises the following steps: acidifying the oil field brine after extracting lithium and potassium by adding hydrochloric acid to convert boron into boric acid to obtain original brine A;
step two: carrying out constant-temperature evaporation operation on the original halogen A at the temperature of 20-30 ℃, precipitating boric acid crystals, and filtering to obtain a mother solution B;
step three: mixing the mother liquor B with the original halogen A to obtain mother liquor C, carrying out constant-temperature cooling crystallization operation on the mother liquor C at the temperature of 0-10 ℃, precipitating boric acid crystals, and filtering to obtain mother liquor D;
step four: and (4) carrying out constant-temperature evaporation operation on the mother liquor D at the temperature of 20-30 ℃, precipitating calcium chloride hexahydrate crystals, filtering to obtain a mother liquor B, and mixing the mother liquor B with the original halogen A and the mother liquor B obtained in the step two for recycling.
The method for extracting the boric acid from the calcium chloride type brine is characterized in that the concentration of the hydrochloric acid added in the step one is 36-38%.
According to the method for extracting boric acid from calcium chloride type brine, hydrochloric acid is added to the oil field brine after lithium and potassium are extracted in the first step in a fed-batch manner, the mixture is stirred for 5-10min after each addition, the pH value is detected, and the hydrochloric acid addition is stopped when the pH value is reduced to 1.8-2.2.
In the method for extracting boric acid from calcium chloride type brine, the constant-temperature evaporation temperature in the second step and the fourth step is 25 ℃.
In the method for extracting boric acid from calcium chloride type brine, the cooling crystallization temperature in the third step is 0 ℃.
In the method for extracting boric acid from calcium chloride type brine, the constant-temperature evaporation in the second step and the constant-temperature evaporation in the fourth step are carried out in a closed container connected with a negative pressure pump.
In the method for extracting boric acid from calcium chloride type brine, the constant-temperature evaporation operation time in the second step is 18-24 h.
In the method for extracting boric acid from calcium chloride type brine, the cooling crystallization operation time of the third step is 4-6 h.
In the method for extracting boric acid from calcium chloride type brine, the constant-temperature evaporation operation time in the fourth step is 9-16 h.
The invention has the advantages that:
1. after potassium and lithium elements are extracted from the oilfield brine in the southern wing mountain area, a brine system can be regarded as a calcium chloride-boric acid-water system, and as the average temperature in summer and night in the southern wing mountain area is close to 0 ℃ and the temperature in the day can reach 25 ℃, the invention adopts phase diagrams of 0 ℃ and 25 ℃ of the ternary system to separate boric acid and calcium chloride.
2. By utilizing the basic principle of the solubility characteristics of calcium chloride salt and boric acid at different temperatures, a closed circulating system is designed, and calcium chloride hexahydrate and boric acid are respectively crystallized and separated out.
3. The method can adapt to the actual situation of large change of the proportion of the brine calcium chloride and the boric acid in the production process, designs a similar separation route, and is favorable for the stability of production and the product quality.
4. The process has the advantages of short flow, low energy consumption and obvious improvement of the utilization rate of brine boron resources.
5. Multiple-effect evaporation can be adopted, which is beneficial to improving the heat economy of an evaporation system.
6. Under the technological condition of brine purification, the boric acid product has high quality and low comprehensive energy consumption.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a phase diagram separation scheme of the ternary system calcium chloride-boric acid-water of the present invention at 0 ℃ and 25 ℃, with the inner line at 273.15K and the outer line at 298.15K.
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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples
The method comprises the following steps: adding 37% hydrochloric acid solution in batches in an oil field brine flow adding mode after extracting lithium and potassium, stirring for 5-10min after each addition, detecting the pH value, and stopping adding hydrochloric acid when the pH value is reduced to 1.95 to obtain original brine A;
step two: taking 100kg of original halogen A, carrying out constant-temperature evaporation operation in a closed container connected with a negative pressure pump at the temperature of 25 ℃, continuously operating the negative pressure pump to timely extract evaporated water vapor, accelerating the evaporation of the water vapor, carrying out constant-temperature evaporation operation for 18h, evaporating part of 62.42kg of aqueous solution, precipitating 0.89kg of boric acid crystals, and filtering to obtain 36.69kg of mother liquor B;
step three: mixing 31.92kg of mother liquor B and 35.38kg of original halogen A to obtain 68.30kg of mother liquor C, carrying out constant-temperature cooling crystallization operation on the mother liquor C at the temperature of 0 ℃, carrying out constant-temperature cooling crystallization operation for 5 hours, precipitating 0.5kg of boric acid crystals, and filtering to obtain 67.80kg of mother liquor D;
step four: and (3) carrying out constant-temperature evaporation operation on the mother liquor D in a closed container connected with a negative pressure pump at the temperature of 25 ℃, continuously working the negative pressure pump to timely extract evaporated water vapor, accelerating the evaporation of the water vapor, carrying out constant-temperature evaporation operation for 12 hours, evaporating 27.09kg of water solution, separating out 5.33kg of calcium chloride hexahydrate crystals, filtering to obtain 35.38kg of mother liquor B, and mixing the mother liquor B with the original brine A for repeated operation.
The content of each substance in the brine of the oilfield in the south wing mountain area after potassium and lithium elements are extracted is shown in the table I, and the material balance in the operation process of the invention is shown in the table II.
| Ca2+（g/L） | B3+（mg/L） | Cl-（g/L） | ρ（g/cm3） |
| 69.10 | 3341.7 | 237.9 | 1.260 |
Watch 1
Watch two
The embodiment proves that the preparation method disclosed by the invention has low energy consumption and higher precipitation efficiency of the boric acid and the calcium chloride hexahydrate, and can be used for efficiently treating the calcium chloride type oilfield brine in the southern wing mountains.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (9)
1. A method for extracting boric acid from calcium chloride type brine is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: acidifying the oil field brine after extracting lithium and potassium by adding hydrochloric acid to convert boron into boric acid to obtain original brine A;
step two: carrying out constant-temperature evaporation operation on the original halogen A at the temperature of 20-30 ℃, precipitating boric acid crystals, and filtering to obtain a mother solution B;
step three: mixing the mother liquor B with the original halogen A to obtain mother liquor C, carrying out constant-temperature cooling crystallization operation on the mother liquor C at the temperature of 0-10 ℃, precipitating boric acid crystals, and filtering to obtain mother liquor D;
step four: and (4) carrying out constant-temperature evaporation operation on the mother liquor D at the temperature of 20-30 ℃, precipitating calcium chloride hexahydrate crystals, filtering to obtain a mother liquor B, and mixing the mother liquor B with the original halogen A and the mother liquor B obtained in the step two for recycling.
2. The method for extracting boric acid from calcium chloride type brine according to claim 1, wherein the method comprises the following steps: the concentration of the hydrochloric acid added in the step one is 36-38%.
3. The method for extracting boric acid from calcium chloride type brine according to claim 1, wherein the method comprises the following steps: and (3) adding hydrochloric acid in batches in a fed-batch manner in the oil field brine after extracting lithium and potassium in the step one, stirring for 5-10min after adding each time, detecting the pH value, and stopping adding hydrochloric acid when the pH value is reduced to 1.8-2.2.
4. The method for extracting boric acid from calcium chloride type brine according to claim 1, wherein the method comprises the following steps: the constant-temperature evaporation temperature of the second step and the fourth step is 25 ℃.
5. The method for extracting boric acid from calcium chloride type brine according to claim 1, wherein the method comprises the following steps: and the cooling crystallization temperature of the third step is 0 ℃.
6. The method for extracting boric acid from calcium chloride type brine according to claim 1, wherein the method comprises the following steps: and the constant-temperature evaporation in the second step and the fourth step is carried out in a closed container connected with a negative pressure pump.
7. The method for extracting boric acid from calcium chloride type brine according to claim 1, wherein the method comprises the following steps: the constant-temperature evaporation operation time of the second step is 18-24 h.
8. The method for extracting boric acid from calcium chloride type brine according to claim 1, wherein the method comprises the following steps: and the cooling crystallization operation time of the third step is 4-6 h.
9. The method for extracting boric acid from calcium chloride type brine according to claim 1, wherein the method comprises the following steps: and the constant-temperature evaporation operation time of the fourth step is 9-16 h.
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| CN202010253174.4A CN111377459A (en) | 2020-04-02 | 2020-04-02 | Method for extracting boric acid from calcium chloride type brine |
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| CN202010253174.4A CN111377459A (en) | 2020-04-02 | 2020-04-02 | Method for extracting boric acid from calcium chloride type brine |
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Citations (7)
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|---|---|---|---|---|
| CN102336418A (en) * | 2011-08-09 | 2012-02-01 | 天津科技大学 | Method for extracting potassium salt from potassium-ion-containing brine |
| CN102491379A (en) * | 2011-12-10 | 2012-06-13 | 中南大学 | Method for preparing high-purity magnesium oxide with high boron salt lake brine |
| CN103074502A (en) * | 2013-01-29 | 2013-05-01 | 中国科学院青海盐湖研究所 | Salt lake brine treatment method for separating lithium from high-magnesium-lithium-ratio salt lake brine |
| CN103896312A (en) * | 2012-12-31 | 2014-07-02 | 江西江锂科技有限公司 | Method for preparing high-purity magnesium oxide by adopting seawater and salt lake brine as raw materials |
| CN109592829A (en) * | 2017-09-30 | 2019-04-09 | 成都明道食品有限公司 | Oil field wastewater treatment technique |
| CN209853741U (en) * | 2019-04-30 | 2019-12-27 | 临沂大学 | Device for comprehensively extracting lithium and boron from oil field brine |
| WO2021026498A1 (en) * | 2019-08-07 | 2021-02-11 | Enviro Water Minerals Company, Inc. | Boron and bromine recovery system |
-
2020
- 2020-04-02 CN CN202010253174.4A patent/CN111377459A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336418A (en) * | 2011-08-09 | 2012-02-01 | 天津科技大学 | Method for extracting potassium salt from potassium-ion-containing brine |
| CN102491379A (en) * | 2011-12-10 | 2012-06-13 | 中南大学 | Method for preparing high-purity magnesium oxide with high boron salt lake brine |
| CN103896312A (en) * | 2012-12-31 | 2014-07-02 | 江西江锂科技有限公司 | Method for preparing high-purity magnesium oxide by adopting seawater and salt lake brine as raw materials |
| CN103074502A (en) * | 2013-01-29 | 2013-05-01 | 中国科学院青海盐湖研究所 | Salt lake brine treatment method for separating lithium from high-magnesium-lithium-ratio salt lake brine |
| CN109592829A (en) * | 2017-09-30 | 2019-04-09 | 成都明道食品有限公司 | Oil field wastewater treatment technique |
| CN209853741U (en) * | 2019-04-30 | 2019-12-27 | 临沂大学 | Device for comprehensively extracting lithium and boron from oil field brine |
| WO2021026498A1 (en) * | 2019-08-07 | 2021-02-11 | Enviro Water Minerals Company, Inc. | Boron and bromine recovery system |
Non-Patent Citations (4)
| Title |
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| JIAOYU PENG ET AL: ""Solubility, Metastable Zone Width, and Nucleation Kinetics of Boric Acid in the NaCl−KCl−CaCl"", 《J. CHEM. ENG. DATA》 * |
| 孔凡志 等: ""不同浓度CaCl2溶液中H3BO3介稳区性质研究"", 《盐湖研究》 * |
| 孟令宗 等: ""三元体系H3BO3－MgCl2－H2O在308.15K和323.15K稳定相平衡研究"", 《广东微量元素科学》 * |
| 田立楠等: "《盐化工概论》", 30 June 1992, 华中理工大学出版社 * |
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