CN114477214A - Method for removing alkali metal from molecular sieve - Google Patents
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- CN114477214A CN114477214A CN202011144472.6A CN202011144472A CN114477214A CN 114477214 A CN114477214 A CN 114477214A CN 202011144472 A CN202011144472 A CN 202011144472A CN 114477214 A CN114477214 A CN 114477214A
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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 is 0.01-1 Mpa and contains 1-100% of water vapor, and the hydrothermal roasting treatment temperature is 200-800 ℃. The method can reduce the alkali metal content of the molecular sieve to below 10 wt% by adopting a simpler method.
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 is charged with negative charges completelyNa+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 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 and pulping the NaY molecular sieve, ammonium salt and water according to a certain proportion, adjusting the pH value to be acidic, controlling the temperature to be 65-95 ℃, exchanging for 0.5-2 hours, and then performing high-temperature roasting (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.
In CN1911513A, a method of mixing and pulping NaY molecular sieve, water and inorganic ammonium salt, adjusting the pH value of a system to 9-12 by using an alkaline solution, and exchanging at 65-90 ℃ is disclosed, wherein the sodium content is reduced to below 5% after primary exchange. The method can repeatedly adjust the acidity and alkalinity of the system, but the sodium removal effect is not ideal.
In CN101633507A, a solid phase ammonium exchange method is disclosed, i.e. according to molecular sieve: mixing the NaY molecular sieve and the ammonium salt according to the weight ratio of (0.1-1.0) to 1, 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 performed in two adjacent reaction chambers, the slurry of molecular sieve and resin are separated by a screen and placed in the two reaction chambers, so that no direct contact is generated between NaY molecular sieve and ion resin, and hydrogen ions and sodium ions can be exchanged by the screen under the push of the concentration difference, 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 high. 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, and 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 preparation method, the apparent pressure is 0.01-1 MPa, preferably 0.05-0.6 MPa, more preferably 0.1-0.5 MPa, preferably 30-100% of water vapor, and more preferably 60-100% of water vapor.
In the preparation method, the acidic substance is selected from 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, the weight ratio of the acidic deionized water to the molecular sieve is 1-20, preferably 6-15, and further preferably 8-12.
In the preparation method, the acidic deionized water is deionized water which is diluted by nitric acid and other acids and is adjusted to have a pH value of 3-7, preferably a pH value of 2-6, and more preferably a pH value of 3-5.
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 method4The content of sodium oxide in the NaY molecular sieve is reduced to below 10 weight percent, and 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 250mA), 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 50 mA.
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 at 500 deg.C and external pressure to obtain 0.3Mpa apparent pressure under 100% steam atmosphere for 2 hr, and then using the molecular sieve according to its dry weight10 times of acidic deionized water with pH value of 4, performing 1 time of acidic water leaching at water temperature of 60 deg.C, filtering, and oven drying to obtain NH4A sample of NaY molecular sieve, noted JNY-1. The physical properties are shown in Table 1.
Comparative example 1
Comparative example 1 illustrates NH obtained by hydrothermal calcination at atmospheric pressure4NaY 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.
Taking 100g of NaY molecular sieve, applying pressure to the outside, adding 8g of ammonia water and 15g of ammonium carbonate, carrying out hydrothermal roasting treatment for 2 hours at 400 ℃ under the condition that the apparent pressure is 0.5Mpa and the 100% water vapor atmosphere is adopted, then carrying out 1-time acid water leaching according to the dry basis weight ratio of the molecular sieve to acid-containing water with the pH value of 6 according to the water temperature of 70 ℃, filtering and drying to obtain NH4A sample of NaY molecular sieve, noted JNY-2. The physical properties are shown in Table 1.
Comparative example 2
Comparative example 2 illustrates NH obtained by hydrothermal calcination at atmospheric pressure4NaY molecular sieve control sample.
The difference from example 1 is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). To obtain NH4A 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, externally applying pressure, adding 16g of ammonium carbonate, carrying out hydrothermal roasting treatment for 2 hours in an atmosphere of 90% water vapor at 300 ℃, apparent pressure of 0.6Mpa, then carrying out 2 times of acidic water leaching according to a dry basis weight ratio of the molecular sieve to acidic water with pH value of 5 of 1:12, filtering and drying treatment at 90 ℃, and obtaining NH4Sample NaY molecular sieve, noted JNY-3. The physical properties are shown in Table 1.
Comparative example 3
Comparative example 3 illustrates NH obtained by hydrothermal calcination at atmospheric pressure4NaY molecular sieve control sample.
The difference from example 1 is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). To obtain NH4A 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.
Applying pressure to 100g of NaY molecular sieve, adding 6g of hydrochloric acid, performing hydrothermal roasting treatment for 2h at 450 ℃, apparent pressure of 0.3Mpa and 60% of water vapor atmosphere, performing 1-time acid leaching on the molecular sieve and acidic water with pH value of 4 according to a dry basis weight ratio of 1:10, wherein the water temperature is 100 ℃, and performing filtration and drying treatment to obtain NH4Sample NaY molecular sieve, noted JNY-4. The physical properties are shown in Table 1.
Comparative example 4
Comparative example 4 illustrates NH obtained by hydrothermal calcination at atmospheric pressure4NaY molecular sieve control sample.
The difference from example 1 is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). To obtain NH4A 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, carrying out hydrothermal roasting treatment for 2h in an atmosphere of 80% water vapor at 350 ℃, with the apparent pressure of 0.5Mpa, then carrying out 1-time acid leaching on the molecular sieve and acidic water with the pH value of 3 according to the dry basis weight ratio of 1:15, with the water temperature of 80 ℃, filtering and drying to obtain NH4Sample NaY molecular sieve, noted JNY-5. The physical properties are shown in Table 1.
Comparative example 5
Comparative example 5 illustrates NH obtained by hydrothermal calcination at atmospheric pressure4NaY molecular sieve control sample.
The difference from example 1 is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). To obtain NH4Pair of NaY molecular sievesThe sample 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 ℃ and under the apparent pressure of 0.4Mpa in the atmosphere of 50% of water vapor, then performing acid water leaching for 2 times according to the dry basis weight ratio of the molecular sieve to acidic water with the pH value of 5 according to the dry basis weight ratio of 1:8, wherein the water temperature is 90 ℃, and performing filtration and drying treatment to obtain NH4Sample NaY molecular sieve, noted JNY-6. The physical properties are shown in Table 1.
Comparative example 6
Comparative example 6 illustrates NH obtained by atmospheric hydrothermal calcination4Comparative sample of NaY molecular sieve.
The difference from example 1 is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). To obtain NH4A comparative sample of NaY molecular sieve was designated DBNY-6. The physical properties are shown in Table 1.
TABLE 1
| Sample name | Na2O content,% (w) | Unit 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 examples2Content of OThe percentage point is reduced by 2.4 to 3.4, namely the method has better technical effect of dealkalizing metal on the basis of keeping the crystal structure more complete.
Claims (11)
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, and 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 ℃.
2. The process according to claim 1, wherein the apparent pressure is 0.05 to 0.6MPa, preferably 0.1 to 0.5MPa, preferably 30 to 100% water vapor, more preferably 60 to 100% water vapor.
3. The method according to claim 1, wherein the hydrothermal calcination treatment is carried out at 350 to 500 ℃ for 1.0 to 4.0 hours.
4. 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.
5. The method of claim 1, wherein the basic substance comprises one or more of ammonia, ammonia and ammonium chloride buffer solution.
6. The preparation method according to claim 1, wherein the weight ratio of the acid-containing deionized water to the molecular sieve is 1-20, preferably 6-15, and more preferably 8-12.
7. The method according to claim 1, wherein the acidic deionized water has a pH of preferably 2 to 6, more preferably 3 to 5.
8. The preparation method according to claim 3, wherein the leaching with the acid-containing deionized water is carried out at a temperature of 30-100 ℃, preferably 60-80 ℃; and the deionized water containing the acidity is leached for 1-2 times.
9. 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.
10. The process according to claim 1, wherein the alkali metal is one or more selected from the group consisting of Na, K, Rb and Cs.
11. The process according to claim 1, wherein the alkali metal-containing molecular sieve contains 0.1 to 20% by weight of the alkali metal-containing molecular sieve.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20150209767A1 (en) * | 2012-06-01 | 2015-07-30 | Petrochina Company Limited | Phosphorus-containing ultrastable y-type rare earth molecular sieve and preparation method therefor |
| US20210395100A1 (en) * | 2018-10-26 | 2021-12-23 | China Petroleum & Chemical Corporation | Phosphorus-containing high-silica molecular sieve, its preparation and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150209767A1 (en) * | 2012-06-01 | 2015-07-30 | Petrochina Company Limited | Phosphorus-containing ultrastable y-type rare earth molecular sieve and preparation method therefor |
| 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 |
| US20210395100A1 (en) * | 2018-10-26 | 2021-12-23 | China Petroleum & Chemical Corporation | Phosphorus-containing high-silica molecular sieve, its preparation and application thereof |
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