CN108408967B - Waste alkali liquid treatment method in molecular sieve production process - Google Patents
Waste alkali liquid treatment method in molecular sieve production process Download PDFInfo
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- CN108408967B CN108408967B CN201810257023.9A CN201810257023A CN108408967B CN 108408967 B CN108408967 B CN 108408967B CN 201810257023 A CN201810257023 A CN 201810257023A CN 108408967 B CN108408967 B CN 108408967B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—Organic compounds containing oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for treating waste alkali liquor in a molecular sieve production process, which comprises the following steps: (1) firstly, collecting and standing waste alkali liquor generated in the production process of the molecular sieve to obtain supernatant of the waste alkali liquor; (2) stirring and heating fatty acid, adding supernatant of waste alkali liquor into the fatty acid for multiple times, and fully saponifying to obtain a fatty acid salt mixed solution; (3) and adding a surfactant into the fatty acid salt mixed solution, and stirring to obtain a fatty acid mixture. The invention also provides an application of the fatty acid mixture, and the fatty acid mixture is applied to flotation separation of scheelite. The waste alkali liquid treatment method is easy to implement, strong in operability and environment-friendly; the invention avoids using sulfuric acid to treat the waste alkali liquor, reduces the waste water treatment cost, changes the waste alkali liquor into valuables, and the obtained fatty acid mixture can be applied to the flotation separation of scheelite; the method has simple process, has important significance for reducing the production cost, and has practical popularization value.
Description
Technical Field
The invention belongs to the field of resource recycling, and particularly relates to a method for treating waste alkali liquor in a molecular sieve production process.
Background
The molecular sieve is an artificially synthesized one with the function of screening moleculesThe hydrated aluminosilicate or natural zeolite of the general formula (M' 2M) O.Al2O3·xSiO2·yH2O, M', M are respectively monovalent and divalent cations such as K+、Na+And Ca2+、Ba2+The molecular sieves with different apertures separate molecules with different sizes and shapes, and have high adsorption capacity, high selectivity and high temperature resistance, and are widely applied in various industrial fields such as fine chemical industry, petrochemical industry, medical health, environmental protection and the like. The 13X type molecular sieve, also called Na X type molecular sieve, is an alkali metal aluminosilicate, belongs to a class of solid alkali, is usually synthesized by a hydrothermal method, takes water as a solvent, mixes a silicon source and an aluminum source, and is heated in an alkaline system to synthesize the zeolite molecular sieve, and the method is the most mature and widely applied zeolite molecular sieve synthesis method.
However, when the hydrothermal method is used for preparing the molecular sieve, the crystallization mother liquor needs to be replaced along with the reduction of the system alkalinity, so a large amount of waste alkali liquor is generated, and because the waste alkali liquor has complex components and high alkali content and is difficult to utilize, the waste alkali liquor is usually neutralized by sulfuric acid and then directly discharged outside in the prior art, a large amount of sulfuric acid is consumed in the treatment process, the cost of sewage treatment is increased, and simultaneously, the resource is greatly wasted.
Disclosure of Invention
The invention aims to provide a method for treating waste alkali liquor in a molecular sieve production process, which is used for treating the waste alkali liquor in the molecular sieve production process and then recycling the treated waste alkali liquor.
The invention provides a method for treating waste lye in the production process of a molecular sieve, which comprises the following steps:
(1) firstly, collecting and standing waste alkali liquor generated in the production process of the molecular sieve to obtain supernatant of the waste alkali liquor;
(2) stirring and heating fatty acid, adding the supernatant of the waste alkali liquor obtained in the step (1) into the fatty acid for multiple times, and fully saponifying to obtain a fatty acid salt mixed solution;
(3) and (3) adding a surfactant into the fatty acid salt mixed solution obtained in the step (2), and stirring to obtain a fatty acid mixture.
Preferably, the waste alkali liquor is waste alkali liquor in the 13X type molecular sieve production process, and OH in the waste alkali liquor-The concentration of (b) is 60-80 g/L.
Preferably, the mass percentages of the supernatant of the waste alkali liquor, the fatty acid and the surfactant are (49-57%): (38-50%): (1% to 5%).
Preferably, the fatty acid is one or two of soybean fatty acid and palm oil fatty acid.
Preferably, the surfactant is one or two of fatty acid methyl ester sodium sulfonate (MES) and fatty alcohol-polyoxyethylene ether sodium sulfate (AES).
Preferably, the standing time in the step (1) is 1-2 h.
Preferably, the heating temperature in the step (2) is 40-60 ℃.
Preferably, in the step (2), the supernatant of the waste alkali liquor is added into the fatty acid for 2-6 times, and the interval time is 20-30 min.
Preferably, in the step (3), the stirring time is 20-60 min.
The invention also provides an application of the fatty acid mixture, and the fatty acid mixture is applied to flotation separation of scheelite.
Compared with the prior art, the invention has the beneficial technical effects that:
according to the method for treating the waste alkali liquor in the molecular sieve production process, fatty acid and the waste alkali liquor generated in the molecular sieve production process are subjected to saponification reaction, then the surfactant is added to obtain a fatty acid mixture, and the obtained fatty acid mixture can be applied to flotation separation of scheelite, so that the waste alkali liquor in the molecular sieve production process is recycled, and great economic benefits are created; the method for treating the waste alkali liquor is easy to implement, simple in process and strong in operability, saves resources and is environment-friendly; and the waste alkali liquor is not treated by using sulfuric acid, so that the waste water treatment cost is reduced, the waste alkali liquor is changed into valuable, the method has an important significance for reducing the production cost, and has an actual popularization value.
Drawings
FIG. 1 is a process flow diagram of the spent lye treatment method of the molecular sieve production process of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
The waste alkali liquor in the embodiment of the invention is waste alkali liquor produced by 13X type molecular sieve produced by Luoyang balance molecular sieve company Limited, and the main component (g L)-1)：Na+100～120、K+40～60、OH-60～80、Ca2+0.1～0.2、Mg2+0.3～0.5、Al3+1～1.2。
Example 1
The method for treating the waste alkali liquor in the production process of the molecular sieve comprises the following steps:
(1) collecting and standing the waste alkali liquor generated in the production process of the 13X-type molecular sieve for 2 hours to obtain supernatant of the waste alkali liquor;
(2) adding soybean fatty acid into a reaction kettle, stirring and heating to 60 ℃, adding the supernatant of the waste alkali liquor obtained in the step (1) into the fatty acid for 3 times at intervals of 20min, continuously stirring in the whole process, and fully saponifying to obtain a fatty acid salt mixed solution;
(3) and (3) adding 2.5 wt% of fatty acid methyl ester sodium sulfonate and 2.5 wt% of fatty alcohol-polyoxyethylene ether sodium sulfate into the fatty acid salt mixed solution obtained in the step (2), and stirring for 30min to obtain a fatty acid mixture which can be used as a collector for scheelite flotation separation.
OH in the supernatant of the spent lye in this example-The concentration is 60g/L, and the mass percent of supernatant liquor of the waste alkali liquor, the soybean fatty acid and the surfactant is 57%: 38%: 5% of the spent caustic produced by the company monthlyThe liquid is about 100 cubic meters, and the cost of the waste alkali liquid treatment method of the invention is compared with the cost of the traditional acid-base neutralization treatment, and the result is shown in the table 1:
TABLE 1 comparison of the costs of the spent lye treatment process of example 1 with the conventional acid and base neutralization treatment
As shown in Table 1, according to the traditional sulfuric acid neutralization treatment scheme, the treatment cost per cubic meter is 30 yuan, and the treatment cost per month of waste alkali liquor is 3000 yuan, but by adopting the waste alkali liquor treatment method disclosed by the invention, the obtained fatty acid mixture can be directly applied to flotation separation of scheelite as a collector, the value is 30000 yuan, the waste alkali liquor is completely recycled, the direct value generated reaches 33000 yuan per month, and the method has important significance for waste water utilization, environmental protection, energy conservation, emission reduction and production cost reduction.
Example 2
The method for treating the waste alkali liquor in the production process of the molecular sieve comprises the following steps:
(1) collecting and standing the waste alkali liquor generated in the production process of the 13X-type molecular sieve for 2 hours to obtain supernatant of the waste alkali liquor;
(2) adding 25 wt% of soybean fatty acid and 25 wt% of palm oil fatty acid into a reaction kettle, stirring and heating to 60 ℃, adding the supernatant of the waste alkali liquor obtained in the step (1) into the fatty acid for 3 times at an interval of 20min every time, continuously stirring in the whole process, and fully saponifying to obtain a fatty acid salt mixed solution;
(3) and (3) adding 1 wt% of fatty acid methyl ester sodium sulfonate into the fatty acid salt mixed solution obtained in the step (2), and stirring for 50min to obtain a fatty acid mixture which can be used as a collector for scheelite flotation separation.
OH in the supernatant of the spent lye in this example-The concentration is 80g/L, and the mass percent of supernatant liquor, fatty acid and surfactant of the waste alkali liquor is 49%: 50%: 1% of waste lye produced by the company about 100 cubic meters per monthThe cost of the waste alkali liquid treatment method is compared with the cost of the traditional acid-base neutralization treatment, and the result is shown in the table 2:
table 2 cost comparison of spent lye treatment method with conventional acid and base neutralization treatment in example 2
As shown in Table 2, according to the traditional sulfuric acid neutralization treatment scheme, the treatment cost per cubic meter is 40 yuan, and the treatment cost per month of waste alkali liquor is 4000 yuan, but by adopting the waste alkali liquor treatment method disclosed by the invention, the obtained fatty acid mixture can be directly applied to flotation separation of scheelite as a collector, the value is 40000 yuan, the waste alkali liquor is completely recycled, and meanwhile, the generated direct value reaches 44000 yuan per month.
Example 3
The fatty acid mixture obtained in example 1 is used as a collector for scheelite flotation separation, a comparison test is carried out with the existing flotation reagent (sodium fatty acid), the grade of scheelite in a selected ore sample is 0.102%, the scheelite is taken from the area of Luoyang goldenland, the pH value of ore pulp is adjusted by sodium carbonate, water glass is used as a gangue inhibitor, the scheelite is subjected to one-time rough concentration and two-time scavenging, rough concentrate is heated to remove the chemical, and then the rough concentrate is subjected to one-time rough concentration and two-time fine concentration and two-time scavenging, and the flotation indexes of the two are compared as follows:
table 3 comparison of flotation indexes of fatty acid mixture obtained in example 1 and existing flotation agents
As can be seen from table 3: the fatty acid mixture provided in example 1 of the present invention is directed to LuanThe low-grade scheelite in Sichuan area obtains the final tungsten concentrate WO3The grade is 31.04 percent, the recovery rate is 81.12 percent, and the indexes are the same as those of the tungsten concentrate WO finally obtained by the existing flotation reagent3The grade is 30.12%, and the recovery rate is 82.56%, so the fatty acid mixture provided by the invention can replace the existing flotation reagent (sodium fatty acid).
Example 4
The fatty acid mixture obtained in example 2 is used as a collector for scheelite flotation separation, a comparison test is carried out with the existing flotation reagent (sodium fatty acid), the grade of the scheelite in the selected ore sample is 0.420%, the scheelite is taken from the Xixiang furnance region of Jiangxi, the pH value of ore pulp is adjusted by sodium carbonate, water glass is used as a gangue inhibitor, and a closed flotation process of once rough flotation, five times fine flotation and three times scavenging is carried out, wherein the flotation indexes of the two are compared as follows:
table 4 comparison of flotation indexes of fatty acid mixture obtained in example 2 and existing flotation agents
| Species of collector | Dosage of collecting agent/(g/t) | WO3Percent recovery% | WO3Grade/% |
| Fatty acid sodium salt | 350 | 84.46 | 55.87 |
| Fatty acid mixtures | 350 | 85.86 | 56.02 |
As can be seen from table 4: the fatty acid mixture provided by the embodiment 2 of the invention aims at scheelite in the Xixiang Mount Jiang region to obtain the final tungsten concentrate WO3The grade is 56.02 percent, and the recovery rate is 85.86 percent, compared with the prior flotation reagent, the final tungsten concentrate WO3The grade is 55.87%, and the index of recovery rate 84.46% is better, so the fatty acid mixture provided by the invention can replace the existing flotation reagent.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (5)
1. A method for treating waste lye in the production process of a molecular sieve comprises the following steps:
(1) firstly, collecting and standing waste alkali liquor generated in the production process of the molecular sieve to obtain supernatant of the waste alkali liquor;
(2) stirring and heating fatty acid, adding the supernatant of the waste alkali liquor obtained in the step (1) into the fatty acid for multiple times, and fully saponifying to obtain a fatty acid salt mixed solution;
(3) adding a surfactant into the fatty acid salt mixed solution obtained in the step (2), and stirring to obtain a fatty acid mixture;
the mass percentages of the supernatant of the waste alkali liquor, the fatty acid and the surfactant are (49-57%): (38% -50%): (1% -5%);
the fatty acid is one or two of soybean fatty acid and palm oil fatty acid;
applying the fatty acid mixture to flotation separation of scheelite;
the waste alkali liquor is waste alkali liquor in the production process of the 13X-type molecular sieve, and OH in the waste alkali liquor-The concentration of (A) is 60-80 g/L;
the surfactant is one or two of fatty acid methyl ester sodium sulfonate and fatty alcohol-polyoxyethylene ether sodium sulfate.
2. The method for treating waste alkali liquor generated in the production process of the molecular sieve according to claim 1, wherein the standing time in the step (1) is 1-2 h.
3. The method for treating waste alkali liquor generated in the production process of the molecular sieve according to claim 1, wherein the heating temperature in the step (2) is 40-60 ℃.
4. The method for treating waste alkali liquor generated in the molecular sieve production process according to claim 1, wherein in the step (2), the supernatant of the waste alkali liquor is added to the fatty acid in 2-6 times at intervals of 20 min.
5. The method for treating waste alkali liquor generated in the molecular sieve production process according to claim 1, wherein in the step (3), the stirring time is 20-60 min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102139246A (en) * | 2010-12-01 | 2011-08-03 | 中钢集团马鞍山矿山研究院有限公司 | Method for preparing feldspar iron removal floatation collecting agent |
| CN105855063A (en) * | 2016-04-01 | 2016-08-17 | 河北舜嘉矿产品科技有限公司 | Anionic collector and preparation method thereof |
| CN107377231A (en) * | 2017-06-19 | 2017-11-24 | 湖北富邦科技股份有限公司 | A kind of collecting agent for alleviating phosphoric acid extraction bubbling and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102139246A (en) * | 2010-12-01 | 2011-08-03 | 中钢集团马鞍山矿山研究院有限公司 | Method for preparing feldspar iron removal floatation collecting agent |
| CN105855063A (en) * | 2016-04-01 | 2016-08-17 | 河北舜嘉矿产品科技有限公司 | Anionic collector and preparation method thereof |
| CN107377231A (en) * | 2017-06-19 | 2017-11-24 | 湖北富邦科技股份有限公司 | A kind of collecting agent for alleviating phosphoric acid extraction bubbling and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 铝基材碱洗废液除油净化研究;申明乐等;《工业水处理》;20130320;第33卷(第3期);第55-56页第1节、第2.2节、第2.3节 * |
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