CN114477214B - Method for removing alkali metal from molecular sieve - Google Patents
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- CN114477214B CN114477214B CN202011144472.6A CN202011144472A CN114477214B CN 114477214 B CN114477214 B CN 114477214B CN 202011144472 A CN202011144472 A CN 202011144472A CN 114477214 B CN114477214 B CN 114477214B
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
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Abstract
The invention discloses a method for removing alkali metal from a molecular sieve, which is characterized by comprising the following steps: the method comprises the steps of carrying out hydrothermal roasting treatment on an alkali metal-containing molecular sieve under the atmosphere environment of externally applying pressure and externally adding water containing an acidic substance or an alkaline substance, and then carrying out 1-2 times of rinsing with deionized water containing acidity and drying treatment to obtain the alkali metal-containing molecular sieve, wherein the atmosphere environment has the apparent pressure of 0.01-1 Mpa and contains 1-100% of water vapor, and the hydrothermal roasting treatment temperature is 200-800 ℃. The method adopts a simpler method to reduce the alkali metal content of the molecular sieve to below 10 weight percent.
Description
Technical Field
The invention relates to a method for removing alkali metal from a molecular sieve.
Background
With the progress of industrial development, molecular sieves are more and more widely used in production. Taking the Y-type molecular sieve as an example, the Y-type molecular sieve has large usage amount in industrial application, the annual production capacity in China exceeds 7 million tons, the prepared catalyst is close to 20 million tons, and nearly 1.5 million tons of oil products per year are processed by the catalyst to produce fuels and chemicals, and the Y-type molecular sieve is widely applied to processes of catalytic cracking (FCC), catalytic cracking, hydrogenation, alkylation, transalkylation, conversion of heavy aromatics, modification of Light Cycle Oil (LCO), acylation and the like.
The Y-type molecular sieve is synthesized in a sodium-containing aluminosilicate crystallization system, and the initial state of the Y-type molecular sieve is in a stable NaY form. Because the alundum tetrahedron is completely charged with negative charges by Na + The positive charges are neutralized, so the NaY molecular sieve has no acidity. In order to obtain the acidity required for the catalytic reaction, the molecular sieve must be freed from sodium. Another reason for sodium removal is that sodium has a large toxic side effect on the activity and hydrothermal stability of the molecular sieve. In the traditional preparation method, the commonly adopted molecular sieve sodium removal technology is a solution ion exchange method, and the specific method comprises the following steps: mixing NaY molecular sieve, ammonium salt and water according to a certain proportion, pulping, adjusting pH value to acidity, controlling temperature at 65-95 ℃, exchanging for 0.5-2 hours, and then roasting at high temperature (550-580 ℃). The exchange and roasting process is repeated for 2-4 times as required, and excessive ammonium salt needs to be added, so that a large amount of high-concentration ammonia nitrogen wastewater is discharged, and the environment is polluted. Therefore, how to adopt a new technology to shorten the process flow for rapid sodium removal of NaY becomes a great technical problem to be solved in industry.
CN1911513A discloses a method of mixing and pulping NaY molecular sieve, water and inorganic ammonium salt, and using alkaline solution to adjust the pH value of the system to 9-12,65-90 ℃ for exchange, wherein the sodium content is reduced to below 5% after one-time exchange. The method can repeatedly adjust the acidity and alkalinity of the system, but the sodium removal effect is not ideal.
CN101633507a discloses a solid phase ammonium exchange method, i.e. according to molecular sieve: mixing the NaY molecular sieve and ammonium salt according to the weight ratio of (0.1-1.0), heating and keeping for 1 hour, and washing once to obtain the ammonium-exchanged molecular sieve. Although the method reduces the dosage of ammonium salt and water, the content of sodium in the product is still more than 2 percent.
CN10570334A discloses a method for modifying NaY molecular sieve by using ion exchange resin, wherein the ion exchange reaction is carried out in two adjacent reaction chambers, the slurry of the molecular sieve and the resin are separated by a screen and are respectively placed in the two reaction chambers, so that the NaY molecular sieve is not in direct contact with the ion resin, and hydrogen ions and sodium ions can be exchanged under the pushing of the concentration difference of the hydrogen ions and the sodium ions through the screen, but the method has limited sodium removal effect.
According to the prior art, the sodium removal treatment of the NaY molecular sieve needs the high-temperature roasting and ammonium exchange steps, and a large amount of ammonia nitrogen wastewater is generated in the ammonium exchange process, so that the wastewater treatment pressure of enterprises is higher. Therefore, how to adopt a sodium removal technology for reducing the discharge of ammonia nitrogen wastewater is a problem to be solved urgently. There is also a problem with structural formulas such as MOR, MFI, how to remove alkali metals while meeting environmental requirements.
Disclosure of Invention
The invention aims to provide a simpler method for dealkalizing molecular sieves, which can reduce the content of alkali metal oxides of the molecular sieves to below 10 weight percent, different from the conventional method for dealkalizing molecular sieves by ammonium exchange.
The invention provides a method for removing alkali metal from a molecular sieve, which is characterized by comprising the following steps: the method comprises the steps of carrying out hydrothermal roasting treatment on an alkali metal-containing molecular sieve under the atmosphere environment of externally applying pressure and externally adding water containing an acidic substance or an alkaline substance, then carrying out leaching and drying treatment on the molecular sieve by using acidic deionized water, wherein the atmosphere environment is 0.01-1 Mpa and contains 1-100% of water vapor, and the hydrothermal roasting treatment temperature is 200-800 ℃.
In the production method of the present invention, the apparent pressure is 0.01 to 1MPa, preferably 0.05 to 0.6MPa, more preferably 0.1 to 0.5MPa, preferably 30 to 100% water vapor, more preferably 60 to 100% water vapor.
In the preparation method of the invention, the acidic substance is one or a mixture of more of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, hydrochloric acid, sulfuric acid and nitric acid.
In the preparation method, the alkaline substance comprises one or more of ammonia water, ammonia water and ammonium chloride buffer solution.
In the preparation method of the invention, the weight ratio of the acid-containing deionized water to the molecular sieve is 1-20, preferably 6-15, and more preferably 8-12.
In the preparation method of the present invention, the acidic deionized water refers to deionized water diluted with an acid such as nitric acid to adjust the pH to 3 to 7, preferably to 2 to 6, more preferably to 3 to 5.
In the preparation method, the leaching of the acid-containing deionized water is carried out at the temperature of 30-100 ℃, preferably 60-80 ℃.
The preparation process of the present invention can be applied to various alkali metal-containing molecular sieves, for example, one or more selected from FAU, MOR, MFI molecular sieves. In the alkali metal-containing molecular sieve, the alkali metal is selected from one or more of Na, K, rb and Cs, and the content of the alkali metal is 0.1-20% by weight of the alkali metal-containing molecular sieve.
The method for removing alkali metal by using the molecular sieve provided by the invention is different from the conventional method. For example, taking NaY molecular sieve as an example, the NH obtained can be obtained by adopting a simpler method 4 The content of sodium oxide in the NaY molecular sieve is reduced to below 10 percent by weightAnd a large amount of ammonia nitrogen wastewater generated in the ammonium exchange process is avoided to a certain extent.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
The X-ray diffraction spectrum is measured on a Nippon science TTR-3 powder X-ray diffractometer, and the instrument parameters are as follows: copper target (tube voltage 40kV, tube current 250 mA), scintillation counter, step width 0.02 degree, scanning speed 0.4 (degree)/min.
The chemical composition was analyzed on an X-ray fluorescence spectrometer model 3013, manufactured by Mooney corporation, japan (XRF), using a tungsten target, an excitation voltage of 40kV, and an excitation current of 50mA.
The NaY molecular sieve raw material used in the comparative examples and examples was produced by long distance division of petrochemical catalyst corporation, china, and had a sodium oxide content of 13.4 wt%, a unit cell constant of 2.465nm, and a crystallinity of 84.1%.
Example 1
Example 1 illustrates the sodium removal process for NaY molecular sieves of the present invention.
Adding 10g ammonia water into 100g NaY molecular sieve, performing hydrothermal roasting treatment for 2h under 100% water vapor atmosphere at 500 ℃ and external pressure to make apparent pressure 0.3Mpa, performing acidic water leaching with 10 times of acidic deionized water with pH value of 4 according to molecular sieve dry basis weight for 1 time at water temperature of 60 ℃, filtering, and drying to obtain NH 4 A sample of NaY molecular sieve, designated JNY-1. The physical properties are shown in Table 1.
Comparative example 1
Comparative example 1 illustrates NH obtained by hydrothermal calcination at atmospheric pressure 4 NaY molecular sieve control sample.
The difference from example 1 is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A NH4NaY molecular sieve comparison sample is obtained and is marked as DBNY-1. The physical properties are shown in Table 1.
Example 2
Example 2 illustrates the NaY molecular sieve sodium removal process of the present invention.
100g of NaY molecular sieve is externally pressurized, 8g of ammonia water and 15g of ammonium carbonate are added, the temperature is 400 ℃, and the apparent pressure is 0.5MpaCarrying out hydrothermal roasting treatment for 2h in the atmosphere of 100% water vapor, then carrying out acid water leaching for 1 time according to the dry weight ratio of the molecular sieve to acidic water with the pH value of 6 to 1:8, wherein the water temperature is 70 ℃, and carrying out filtering and drying treatment to obtain NH 4 A sample of NaY molecular sieve, designated JNY-2. The physical properties are shown in Table 1.
Comparative example 2
Comparative example 2 illustrates NH obtained by hydrothermal calcination at atmospheric pressure 4 NaY molecular sieve control sample.
The difference from example 1 is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). To obtain NH 4 A comparative sample of NaY molecular sieve was designated DBNY-2. The physical properties are shown in Table 1.
Example 3
Example 3 illustrates the sodium removal process for NaY molecular sieves of the present invention.
Taking 100g of NaY molecular sieve, applying pressure to the outside, adding 16g of ammonium carbonate, performing hydrothermal roasting treatment for 2 hours at 300 ℃ under the apparent pressure of 0.6Mpa and the water vapor atmosphere of 90%, then performing 2-time acid water leaching according to the dry basis weight ratio of the molecular sieve to acidic water with the pH value of 5 according to 1 4 A sample of NaY molecular sieve, designated JNY-3. The physical properties are shown in Table 1.
Comparative example 3
Comparative example 3 illustrates NH obtained by hydrothermal calcination at atmospheric pressure 4 NaY molecular sieve control sample.
The difference from example 1 is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). To obtain NH 4 A comparative sample of NaY molecular sieve was designated DBNY-3. The physical properties are shown in Table 1.
Example 4
Example 4 illustrates the sodium removal process for NaY molecular sieves of the present invention.
Taking 100g of NaY molecular sieve, applying pressure to the outside, adding 6g of hydrochloric acid, performing hydrothermal roasting treatment for 2h under the atmosphere of 60% water vapor at 450 ℃, the apparent pressure of 0.3Mpa, and then performing 1-time acid leaching on the molecular sieve and acidic water with the pH value of 4 according to the dry weight ratio of 1 4 A sample of NaY molecular sieve, designated JNY-4. It is composed ofThe physical properties are shown in Table 1.
Comparative example 4
Comparative example 4 illustrates NH obtained by hydrothermal calcination at atmospheric pressure 4 NaY molecular sieve control sample.
The difference from example 1 is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). To obtain NH 4 A comparative sample of NaY molecular sieve was designated DBNY-4. The physical properties are shown in Table 1.
Example 5
Example 5 illustrates the sodium removal process for NaY molecular sieves of the present invention.
Taking 100g of NaY molecular sieve, applying pressure to the outside, adding 16g of ammonium bicarbonate, performing hydrothermal roasting treatment for 2 hours at 350 ℃, under the apparent pressure of 0.5Mpa and in the atmosphere of 80% of water vapor, then performing 1-time acid leaching on the molecular sieve and acidic water with the pH value of 3 according to the dry weight ratio of 1 4 A sample of NaY molecular sieve, designated JNY-5. The physical properties are shown in Table 1.
Comparative example 5
Comparative example 5 illustrates NH obtained by hydrothermal calcination at atmospheric pressure 4 NaY molecular sieve control sample.
The difference from example 1 is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). To obtain NH 4 A comparative sample of NaY molecular sieve was designated DBNY-5. The physical properties are shown in Table 1.
Example 6
Example 6 illustrates the NaY molecular sieve sodium removal process of the present invention.
Applying pressure to the outside of 100g of NaY molecular sieve, adding 12g of ammonia water and 10g of ammonium bicarbonate, performing hydrothermal roasting treatment for 2 hours at 430 ℃ under the condition of apparent pressure of 0.4Mpa and 50% of water vapor atmosphere, then performing 2-time acid water leaching according to the dry weight ratio of the molecular sieve to acidic water with the pH value of 5 according to 1:8, wherein the water temperature is 90 ℃, and performing filtration and drying treatment to obtain NH 4 A sample of NaY molecular sieve designated JNY-6. The physical properties are shown in Table 1.
Comparative example 6
Comparative example 6 illustrates NH obtained by hydrothermal calcination at atmospheric pressure 4 Comparative sample of NaY molecular sieve.
Simultaneous consolidationExample 1, except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). To obtain NH 4 A comparative sample of NaY molecular sieve was designated DBNY-6. The physical properties are shown in Table 1.
TABLE 1
| Sample name | Na 2 O content,% (w) | Cell constant, nm | Degree of crystallinity,% (w) | |
| Example 1 | JNY-1 | 9.2 | 2.458 | 82.6 |
| Comparative example 1 | DBNY-1 | 11.8 | 2.455 | 78.1 |
| Example 2 | JNY-2 | 8.0 | 2.463 | 84.5 |
| Comparative example 2 | DBNY-2 | 11.2 | 2.461 | 80.1 |
| Example 3 | JNY-3 | 7.4 | 2.464 | 86.4 |
| Comparative example 3 | DBNY-3 | 10.8 | 2.462 | 81.2 |
| Example 4 | JNY-4 | 9.2 | 2.463 | 82.3 |
| Comparative example 4 | DBNY-4 | 11.6 | 2.461 | 76.9 |
| Example 5 | JNY-5 | 9.5 | 2.464 | 85.6 |
| Comparative example 5 | DBNY-5 | 11.8 | 2.463 | 82.1 |
| Example 6 | JNY-6 | 8.7 | 2.463 | 81.7 |
| Comparative example 6 | DBNY-6 | 11.2 | 2.461 | 80.3 |
As can be seen from the results in Table 1, the method for removing alkali metals from molecular sieves provided by the invention has the advantages that the crystallinity is improved by 1.4-5.4 percentage points and Na is added in comparison with the comparative samples obtained by the corresponding comparative examples 2 The content of O is reduced by 2.4-3.4 percentage points, namely the method has better technical effect of dealkalizing metal on the basis of keeping the crystal structure more complete.
Claims (17)
1. A method for dealkalizing molecular sieves, characterized in that the method comprises: the method comprises the steps of carrying out hydrothermal roasting treatment on an alkali metal-containing molecular sieve under the atmosphere environment of externally applying pressure and externally adding water containing an acidic substance or an alkaline substance, then carrying out rinsing and drying treatment by using acid-containing deionized water, wherein the atmosphere environment has the apparent pressure of 0.01-1 MPa and contains 1-100% of water vapor, and the hydrothermal roasting treatment temperature is 200-800 ℃.
2. The process according to claim 1, wherein the pressure is 0.05 to 0.6MPa and 30 to 100% water vapor.
3. The process according to claim 1, wherein the pressure is 0.1 to 0.5MPa and contains 30 to 100% of water vapor.
4. The process according to claim 1, wherein the pressure is 0.1 to 0.5MPa and 60 to 100% water vapor.
5. The method according to claim 1, wherein the hydrothermal calcination treatment temperature is 350 to 500 ℃ and the treatment time is 1.0 to 4.0 hours.
6. The method of claim 1, wherein the acidic material is selected from the group consisting of ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium bicarbonate, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, hydrochloric acid, sulfuric acid, and nitric acid.
7. The method of claim 1, wherein the basic substance comprises one or more of aqueous ammonia, a mixture of aqueous ammonia and a buffered solution of ammonium chloride.
8. The process of claim 1 wherein the weight ratio of acid-containing deionized water to molecular sieve is from 1 to 20.
9. The process of claim 1 wherein the weight ratio of acid-containing deionized water to molecular sieve is from 6 to 15.
10. The process of claim 1 wherein the weight ratio of acid-containing deionized water to molecular sieve is from 8 to 12.
11. The method of claim 1 wherein said acidic deionized water has a pH of 2 to 6.
12. The method of claim 1 wherein said acidic deionized water has a pH of 3 to 5.
13. The method according to claim 1, wherein the leaching with the acid-containing deionized water is carried out at a temperature of 30-100 ℃; and the deionized water containing the acidity is leached for 1-2 times.
14. The method of claim 13, wherein said rinsing with acidic deionized water is carried out at a temperature of 60 to 80 ℃.
15. The process of claim 1 wherein said alkali metal containing molecular sieve is selected from one or more of FAU, MOR, MFI structure molecular sieves.
16. The method of claim 1 wherein said alkali metal is selected from one or more of Na, K, rb and Cs.
17. The process of claim 1 wherein the alkali metal-containing molecular sieve has an alkali metal content of from 0.1 to 20% by weight based on the weight of the alkali metal-containing molecular sieve.
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| CN104261426A (en) * | 2014-10-08 | 2015-01-07 | 山东齐鲁华信高科有限公司 | Preparation method for low-sodium high-silicon Y type molecular sieve |
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| WO2020082880A1 (en) * | 2018-10-26 | 2020-04-30 | 中国石油化工股份有限公司 | Phosphorus-containing high-silicon molecular sieve, preparation method therefor and application thereof |
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