CN110894073B - Process for producing sodium silicate - Google Patents
Process for producing sodium silicate Download PDFInfo
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- CN110894073B CN110894073B CN201911338263.2A CN201911338263A CN110894073B CN 110894073 B CN110894073 B CN 110894073B CN 201911338263 A CN201911338263 A CN 201911338263A CN 110894073 B CN110894073 B CN 110894073B
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/32—Alkali metal silicates
Abstract
The invention provides a method for producing sodium silicate, which uses waste alkali solution produced in the process of producing cyclohexanone by a cyclohexane oxidation method or concentrated solution produced in the process of refining caprolactam as a sodium source, quartz sand provides a silicon source, and sodium silicate is obtained by burning. The method avoids the generation of dangerous wastes such as sodium carbonate and sodium sulfate in the incineration treatment process of the waste alkali liquor or the concentrated solution, changes waste into valuable, reduces the environmental protection treatment cost of enterprises, and simultaneously provides energy required by the production of sodium silicate by the incineration of the waste alkali liquor or the concentrated solution, thereby reducing the consumption of fuel, further reducing the production cost of the sodium silicate, reducing the energy consumption and the emission of carbon dioxide, and reducing the environmental pollution.
Description
Technical Field
The invention relates to the field of sodium silicate production, in particular to a production method of sodium silicate.
Background
The cyclohexane oxidation method for producing cyclohexanone is an important ring for producing caprolactam, but in the production process, the selectivity is only about 85%, oxidation byproducts mainly comprise dicarboxylic acid, hydroxycarboxylic acid, caprolactone and other substances, and the substances are washed by alkali to form a waste liquid solution (commonly called 'saponification liquid') containing a large amount of sodium carboxylate and sodium hydroxide. Meanwhile, in the ion exchange refining process of caprolactam, an aqueous solution (commonly called as a concentrated solution) containing caprolactam, sodium sulfate, ammonium sulfate and sodium nitrate is generated. At present, the main treatment method for the above-mentioned waste alkali liquor and concentrated solution in the industry is a mixed burning method, which uses fuel oil or natural gas as fuel and burns the waste alkali liquor and concentrated solution at high temperature to convert into water vapor, carbon dioxide, sodium carbonate and sodium sulfate; the treatment method not only needs to consume a large amount of energy, but also generates a large amount of carbon dioxide in the incineration process, and finally generates solids mainly comprising sodium carbonate and sodium sulfate, and because the solubility of the two sodium salts in water is almost similar, the two sodium salts cannot be effectively separated, so that the two sodium salts can only be used as 'dangerous waste' for landfill treatment in industry, a plurality of environmental hidden dangers are brought, and the environmental protection treatment cost of caprolactam enterprises is increased.
The traditional sodium silicate production process comprises the following steps: mixing coal powder, quartz sand (silicon dioxide) and sodium carbonate, burning at high temperature, and cooling with air to obtain sodium silicate solid, wherein the reaction equation is as follows:
Na2CO3+SiO2→Na2O·SiO2+CO2↑
the main functions of the coal powder are to provide heat, sodium carbonate provides a sodium source, and quartz sand provides a silicon source. The production process needs to consume a large amount of energy, and simultaneously, the combustion of the fuel can release a large amount of carbon dioxide to cause environmental pollution.
Disclosure of Invention
Therefore, the method for producing sodium silicate comprehensively utilizes the waste liquid generated in the process of producing cyclohexanone by a cyclohexane oxidation method or the waste liquid generated in the process of refining caprolactam to produce sodium silicate, can reduce energy consumption and discharge of carbon dioxide, and reduces environmental pollution.
The technical scheme of the invention is as follows.
The invention provides a production method of sodium silicate, which comprises the following steps:
providing a sodium source and a silicon source, wherein the sodium source is waste liquid generated in the process of producing cyclohexanone by a cyclohexane oxidation method or waste liquid generated in the refining process of caprolactam, and the silicon source is quartz sand;
and mixing and burning the sodium source, the silicon source and the fuel to obtain the sodium silicate.
The above production method further comprises the steps of:
the mass of the Na element in the sodium source and the mass of the Si element in the silicon source were measured.
The ratio of the mass of the Na element in the sodium source to the mass of the Si element in the silicon source is 23 (12 to 16).
The ratio of the mass of the Na element in the sodium source to the mass of the Si element in the silicon source is 23: 14.
The above production method further comprises the steps of:
measuring the calorific value of the sodium source and the calorific value of the fuel;
the amount of addition of the fuel is adjusted so that the amount of heat released per kg of the sodium source and the fuel during the incineration is controlled to 1000 to 30000kcal on average, based on the measured calorific values of the sodium source and the fuel.
The sodium source is waste alkali solution generated in alkali washing in the process of producing cyclohexanone by a cyclohexane oxidation method or concentrated solution generated in a caprolactam refining process.
The waste alkali solution contains sodium carboxylate and sodium hydroxide; the concentrate contains caprolactam, sodium sulfate, ammonium sulfate and sodium nitrate.
The fuel is natural gas or fuel oil.
The above incineration was performed in an air atmosphere.
The conditions of the incineration are as follows: incinerating for 2-10 h at 1400-1700 ℃.
In the method, the waste liquid generated in the process of producing cyclohexanone by a cyclohexane oxidation method or the waste liquid generated in the refining process of caprolactam is used as a sodium source, quartz sand provides a silicon source, and sodium silicate is prepared by high-temperature incineration. The main component of the waste alkali solution generated in the process of alkali washing in the process of producing cyclohexanone by a cyclohexane oxidation method is sodium carboxylate, and sodium carbonate is mainly formed in the process of high-temperature incineration treatment; sodium sulfate is formed in the concentrated solution generated in the refining process of caprolactam during high-temperature incineration treatment, and simultaneously, sodium silicate is generated by quartz sand (silicon dioxide) and formed sodium carbonate or sodium sulfate during high-temperature incineration. On one hand, the waste liquid in the method provides a sodium source required for producing sodium silicate, avoids 'dangerous wastes' such as sodium carbonate and sodium sulfate generated in the traditional mixed burning method, changes waste into valuable, and simultaneously reduces the environmental protection treatment cost of enterprises.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
One embodiment of the present invention provides a method for producing sodium silicate, comprising the following steps S1 to S2.
S1, providing a sodium source and a silicon source, wherein the sodium source is waste liquid generated in the process of producing cyclohexanone by a cyclohexane oxidation method or waste liquid generated in the refining process of caprolactam, and the silicon source is quartz sand;
in one embodiment, the sodium source is a waste alkali solution generated in alkali washing in the process of producing cyclohexanone by a cyclohexane oxidation method or a concentrated solution generated in a caprolactam refining process. Further, the waste alkali solution contains sodium carboxylate and sodium hydroxide, and the concentrated solution contains caprolactam, sodium sulfate, ammonium sulfate and sodium nitrate.
In the process of producing cyclohexanone by cyclohexane oxidation, alkali washing is carried out in the post-treatment process to form waste alkali aqueous solution containing 30-90% of sodium carboxylate and 10-30% of sodium hydroxide; meanwhile, in the ion exchange refining process of caprolactam, an aqueous solution (commonly called as a concentrated solution) containing 5-15% of caprolactam, 3-6% of sodium sulfate, 5-15% of ammonium sulfate and 5-15% of sodium nitrate is generated; at present, the main treatment method for waste alkali liquor and concentrated solution in the industry is a mixed burning method, the solid phase mainly formed after oxygen-containing high-temperature burning is sodium carbonate, the solid phase mainly formed after high-temperature burning of concentrated solution is sodium sulfate, and the finally generated solid is mainly sodium carbonate and sodium sulfate.
The technicians try to recover dicarboxylic acid from waste alkali liquor, but new acid-containing waste water is generated, and a large part of carboxylic acid cannot be recovered, so that how to treat waste liquor generated in the production process in a green and efficient manner is a great challenge for the technicians in the field.
In one embodiment, step S1 further includes step S11.
And S11, measuring the mass of the Na element in the waste liquid and the mass of the Si element in the quartz sand.
In order to treat the waste liquid generated in the production process in a green and efficient way, a great deal of research and analysis finds that: the mass fraction of Na element in the waste liquid and the mass fraction of Si element in the quartz sand are obtained through elemental analysis and measurement, then the mass of Na element contained in the waste liquid to be treated is calculated, the addition amount of the quartz sand is adjusted according to the calculated result, and the mass of the Si element in the added quartz sand and the mass of the Na element contained in the waste liquid to be treated are controlled in a proper proportion, so that the sodium ions in the waste liquid can be recovered to the maximum extent, and the quartz sand is fully utilized.
It is understood that other methods in the art for measuring the mass of Na element in the waste liquid and the mass of Si element in the silica sand can be used.
In one embodiment, the mass ratio of Na element in the waste liquid to Si element in the quartz sand is 23 (12-16).
In one embodiment, the mass ratio of the Na element in the waste liquid to the Si element in the quartz sand is 23: 14.
In one embodiment, step S1 further includes step S12.
And S21, measuring the heat value of the sodium source and the heat value of the fuel.
In one embodiment, the amount of fuel added is adjusted to control the amount of heat released per kg of the sodium source and the fuel during the incineration to 1000kcal to 30000kcal on average, based on the measured calorific value of the sodium source and the measured calorific value of the fuel.
In one embodiment, the amount of fuel added is adjusted to control the amount of heat released per kg of the sodium source and the fuel upon the incineration to 10000kcal to 30000kcal on average, based on the measured calorific value of the sodium source and the calorific value of the fuel.
It is understood that the heating value of the sodium source and the heating value of the fuel can be measured using a calorimeter, and other methods of measuring the heating value known in the art can be used.
The method for calculating the heat quantity includes: the total heat given off by the waste liquid and the fuel during incineration is divided by the total mass of the waste liquid and the fuel.
It should be noted that step S21 and step S11 have no specific sequence.
And S2, mixing and burning the sodium source, the silicon source and the fuel to obtain the sodium silicate.
The waste liquid produced in the process of producing cyclohexanone by using a cyclohexane oxidation method or the waste liquid produced in the refining process of caprolactam is used as a sodium source, and through a large amount of research and analysis, the addition amount of fuel is adjusted, so that the heat produced during the incineration of the waste liquid can just meet the energy required by the production of sodium silicate, the use of the fuel is reduced, the waste of energy is avoided, and then the production cost of sodium silicate is reduced, the energy consumption and the carbon dioxide emission are reduced, and the environmental pollution is reduced.
Meanwhile, sodium carbonate or sodium sulfate generated by quartz sand (silicon dioxide) and waste alkali liquor or concentrated solution generates sodium silicate when incinerated at high temperature. The method avoids the dangerous wastes such as sodium carbonate, sodium sulfate and the like generated in the traditional mixed burning method, changes waste into valuable, and reduces the environmental protection treatment cost of enterprises.
In one embodiment, the fuel is natural gas or fuel oil.
In one of the embodiments, the incineration is performed in an air atmosphere.
In one embodiment, the conditions of incineration are: incinerating for 2-10 h at 1400-1700 ℃.
While the present invention will be described with respect to particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover by the appended claims the scope of the invention, and that certain changes in the embodiments of the invention will be suggested to those skilled in the art and are intended to be covered by the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The method for producing sodium silicate according to the present invention is exemplified herein, but the present invention is not limited to the following examples.
Example 1
1) Provides waste alkali solution, quartz sand and fuel oil produced during alkali washing in the process of producing cyclohexanone by a cyclohexane oxidation method for later use.
2) The content of Na element in the waste alkali solution is 8.3 percent and the content of Si element in the quartz sand is 46.1 percent through element analysis; the calorific value of the waste alkali solution is 1789kcal/kg and the calorific value of the fuel oil is 10980kcal/kg measured by a calorimeter.
3) And mixing 1t of waste alkali solution and 0.1095t of quartz sand to obtain a mixed solution for later use.
4) Adding 0.3615t of fuel oil into the mixture prepared in the step 3), burning in a burning furnace, burning for 8h at 1410-1520 ℃, and cooling to obtain 0.221t of sodium silicate solid, wherein the purity of the sodium silicate solid is 98.4%.
Wherein t represents the unit: ton.
Example 2
1) Provides waste alkali solution, quartz sand and fuel oil produced during alkali washing in the process of producing cyclohexanone by a cyclohexane oxidation method for later use.
2) The content of Na element in the waste alkali solution is 16.5 percent and the content of Si element in the quartz sand is 43.5 percent through element analysis; the calorific value of the waste alkali solution is 3421kcal/kg and the calorific value of the fuel oil is 10980kcal/kg measured by a calorimeter.
3) And mixing 1t of waste alkali solution and 0.1004t of quartz sand to obtain a mixed solution for later use.
4) 0.4362t of fuel oil is added into the mixture prepared in the step 3), the mixture is burned in an incinerator, the burning is carried out for 8h at the temperature of 1410-1520 ℃, and 0.439t of sodium silicate solid is obtained after the mixture is cooled, wherein the purity of the sodium silicate solid is 95.1%.
Comparative example 1
According to the traditional sodium silicate production method: mixing fuel oil (with a calorific value of 10980kcal/kg), quartz sand (silicon dioxide, the content of Si element is 46.1%) and sodium carbonate, then burning at high temperature, and cooling by air to obtain sodium silicate solid.
The results show that 0.5244t of fuel oil, 0.201t of sodium carbonate and 0.107t of quartz sand are consumed to produce 0.221t of sodium silicate solid.
The results show that the method for producing sodium silicate comprehensively utilizes the waste liquid generated in the process of producing cyclohexanone by a cyclohexane oxidation method or the waste liquid generated in the process of refining caprolactam to produce sodium silicate, can reduce energy consumption and discharge of carbon dioxide, and reduce environmental pollution.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The production method of sodium silicate is characterized by comprising the following steps:
providing a sodium source and a silicon source, wherein the sodium source is waste liquid generated in the process of producing cyclohexanone by a cyclohexane oxidation method or waste liquid generated in the refining process of caprolactam, and the silicon source is quartz sand;
mixing and burning the sodium source, the silicon source and the fuel to obtain sodium silicate;
wherein, before the step of mixedly incinerating the sodium source, the silicon source and the fuel, the calorific value of the sodium source and the calorific value of the fuel are measured; adjusting the addition amount of the fuel so as to control the heat amount emitted by the waste liquid and the fuel during the incineration to 1000-30000 kcal on average per kilogram according to the measured heat values of the sodium source and the fuel;
the mass ratio of Na element in the sodium source to Si element in the silicon source is 23 (12-16);
the fuel is natural gas or fuel oil; the incineration conditions are as follows: incinerating for 2-10 h at 1400-1700 ℃.
2. The method of claim 1, further comprising the steps of:
and measuring the mass of the Na element in the sodium source and the mass of the Si element in the silicon source.
3. The production method according to claim 1 or 2, wherein a ratio of a mass of Na element in the sodium source to a mass of Si element in the silicon source is 23: 14.
4. The production process according to claim 1 or 2, wherein the sodium source is a waste alkali solution produced in the alkali washing in the process of producing cyclohexanone by the cyclohexane oxidation method or a concentrated solution produced in the refining process of caprolactam.
5. The production method according to claim 4, wherein the spent caustic solution contains a sodium carboxylate and sodium hydroxide; the concentrate contains caprolactam, sodium sulfate, ammonium sulfate and sodium nitrate.
6. The production method according to claim 1 or 2, characterized in that the amount of addition of the fuel is adjusted so as to control the amount of heat given off at the time of the incineration to 10000kcal to 30000kcal per kg of the sodium source and the fuel on average, based on the measured calorific value of the sodium source and the calorific value of the fuel.
7. The production method according to claim 5, wherein the waste lye is an aqueous solution containing 30 to 90% by mass of the sodium carboxylate and 10 to 30% by mass of the sodium hydroxide.
8. The method of claim 5, wherein the concentrated solution is an aqueous solution containing 5 to 15% caprolactam, 3 to 6% sodium sulfate, 5 to 15% ammonium sulfate, and 5 to 15% sodium nitrate, in terms of mass percentage.
9. The production method according to claim 1 or 2, wherein the incineration is performed in an air atmosphere.
10. The production method according to claim 1 or 2, wherein the conditions for the incineration are: incinerating at 1410-1520 deg.c for 8 hr.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342603A (en) * | 2001-10-29 | 2002-04-03 | 江苏德邦化学工业集团有限公司 | Process for preparing sodium silicate |
| CN108870413A (en) * | 2017-05-15 | 2018-11-23 | 中国石油化工股份有限公司 | A method of petrochemical industry waste liquid is burned based on gas and oil-based liquid fuel combination |
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| SU519269A1 (en) * | 1975-03-21 | 1976-06-30 | Всесоюзный научно-исследовательский и конструкторско-технологический институт компрессорного машиностроения | Mix for making cores and molds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1342603A (en) * | 2001-10-29 | 2002-04-03 | 江苏德邦化学工业集团有限公司 | Process for preparing sodium silicate |
| CN108870413A (en) * | 2017-05-15 | 2018-11-23 | 中国石油化工股份有限公司 | A method of petrochemical industry waste liquid is burned based on gas and oil-based liquid fuel combination |
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