CN111320178B - Metal modified silica sol for synthesizing SAPO-34 molecular sieve and preparation method thereof - Google Patents

Metal modified silica sol for synthesizing SAPO-34 molecular sieve and preparation method thereof Download PDF

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CN111320178B
CN111320178B CN202010134980.XA CN202010134980A CN111320178B CN 111320178 B CN111320178 B CN 111320178B CN 202010134980 A CN202010134980 A CN 202010134980A CN 111320178 B CN111320178 B CN 111320178B
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周君梦
徐双
刘禹
王凤
王闯
袁龙
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Chia Tai Energy Materials Dalian Co ltd
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Abstract

The invention discloses a metal modified silica sol for synthesizing SAPO-34 molecular sieve and a preparation method thereof. And (2) activating the silicon powder, adding an alkaline catalyst, reacting for a period of time to obtain a silica sol seed solution, continuously reacting with a metal salt solution and the alkaline catalyst under stirring conditions at a certain temperature, standing, precipitating and filtering to finally obtain the metal modified silica sol product. The metal modified silica sol for synthesizing the SAPO-34 molecular sieve prepared by the invention has the advantages of simple operation method, short reaction time and mild conditions, and the obtained silica sol product has the characteristics of small particle size, large specific surface area, high activity and adjustable proportion of loaded metal. Meanwhile, the SAPO-34 molecular sieve prepared by using the silica sol product obtained by the invention has excellent performance in the reaction of preparing olefin from methanol.

Description

Metal modified silica sol for synthesizing SAPO-34 molecular sieve and preparation method thereof
Technical Field
The invention relates to a metal modified silica sol, in particular to a metal modified silica sol for synthesizing a SAPO-34 molecular sieve and a preparation method thereof, belonging to the technical field of small-particle-size metal modified silica sol.
Background
SAPO-34 molecular sieves are receiving increasing attention from the industry in terms of their desirable acid sites, good hydrothermal stability, excellent ethylene and propylene selectivity, and long life. With the continuous demand for improving the performance of SAPO-34 molecular sieves, more optimization schemes are proposed, which include metal modification of the molecular sieves, reduction of the particle size of the molecular sieves, and the like.
The traditional SAPO-34 molecular sieve metal modification is carried out by molecular sieve impregnation, in-situ synthesis and other methods, but the methods can cause that metal ions can not enter a molecular sieve framework and are only adsorbed on the surface of the molecular sieve, or the metal ions are unevenly distributed in the framework, so that the molecular sieve is quickly inactivated.
At present, there are few solutions for metal modification of silica sol and modified metal species, among them, the solutions of aluminum modified silica sol provided by patents CN20140673957, CN 154418A and CN 105586004A, etc.; CN102344761 provides a method for preparing cerium-doped silica sol; CN1259238 provides a preparation method of boron modified particle silica sol;
in the prior art, the preparation process of a plurality of metal ion modified silica sol products is not disclosed, and the SAPO-34 molecular sieve prepared by using the silica sol product synthesized by the method has the advantages of reduced particle size, correspondingly increased specific surface area and obviously improved performance and service life; the invention discloses a silica sol product which has simple and easy process, mild condition, short reaction time, small particle size, uniform dispersion of metal ions and adjustable proportion. Therefore, the invention has wide demand in the SAPO-34 molecular sieve market.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a metal modified silica sol for synthesizing a SAPO-34 molecular sieve and a preparation method thereof.
In order to achieve the above object, the present invention adopts the following technical solutions:
a method for preparing metal modified silica sol comprises the following steps:
s1, activating silicon powder and deionized water in a certain proportion under stirring conditions at a certain temperature to obtain an activated silicon powder-water mixture;
s2, adding an alkaline catalyst into the activated silicon powder-water mixture, and reacting for a certain time under a stirring condition and a certain temperature to obtain a silica sol seed solution;
and S3, mixing the silica sol seed solution, the metal salt solution with a certain concentration and the heated alkaline catalyst solution according to a certain proportion, and continuously reacting for a certain time under the stirring condition and a certain temperature to obtain the modified silica sol solution.
In some embodiments, the method for preparing a metal-modified silica sol further comprises: and standing the modified silica sol solution for precipitation, and performing suction filtration to remove impurities to obtain a metal modified silica sol product.
More specifically, in the above preparation process, the added silicon powder: deionized water: basic catalyst: metal salt: the molar ratio of the heated basic catalyst is 1: (4-15): (0.005-0.1): (0.01-0.2): (0.01-0.05).
In some embodiments, the basic catalyst is one or more of tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and ammonia.
In some embodiments, the metal salt is one or more of zinc salt, manganese salt, nickel salt, copper salt and cobalt salt;
the zinc salt comprises zinc nitrate, zinc sulfate, zinc acetate and zinc chloride;
the manganese salt comprises manganese nitrate, manganese acetate and manganese sulfate;
the nickel salt comprises nickel nitrate and nickel sulfate;
the copper salt comprises copper nitrate, copper sulfate and copper acetate;
the cobalt salt comprises cobalt nitrate, cobalt acetate and cobalt sulfate.
In some embodiments, in step S1, the particle size of the silicon powder is not higher than 50 μm, and the purity is not lower than 99%; the molar ratio of the deionized water to the silicon powder is 4-15;
the activation temperature is 45-65 ℃, and the activation time is 15 min-1 h.
In some embodiments, in the step S2, the adding amount of the basic catalyst is 0.005-0.1 times mole number of the silicon powder, and the feeding temperature is 50-65 ℃;
the reaction temperature is 70-95 ℃, and the reaction time is 3-8 h.
In some embodiments, in step S3, the metal salt is added in an amount of 0.01 to 0.2 times by mole of the silicon powder, the basic catalyst is added in an amount of 0.01 to 0.05 times by mole of the silicon powder, and the temperature of the heated basic catalyst is 65 to 90 ℃.
In some embodiments, in the step S3, the stirring reaction is performed at a temperature of 70 to 95 ℃ for 1 to 5 hours.
In a second aspect, a metal modified silica sol for synthesizing the SAPO-34 molecular sieve is provided, which is prepared by the preparation method of the metal modified silica sol. The particle size of the metal modified silica sol is 4-10 nm.
Has the advantages that: the invention has the advantages that: the SAPO-34 molecular sieve prepared by using the silica sol product synthesized by the method has small particle size and large specific surface area, and the performance and the service life of the molecular sieve are obviously improved; the method has the advantages of simple process, easy operation, mild condition and short reaction time. Has the following advantages:
(1) according to the method, after being activated under certain conditions, metal silicon powder and an alkaline catalyst undergo hydrolysis reaction, and a silica sol seed solution is obtained after the reaction is carried out for a period of time; and continuously reacting the silica sol seed solution with metal salt and the alkaline catalyst after supplementary heating to obtain the metal modified silica sol product.
In the invention, metal ions can be bonded into siloxane bonds (-Si-O-Si-) through hydrolysis reaction with silanol (-Si-OH) on the surface of silica sol seed colloidal particles under the action of an alkaline catalyst, so that the metal ions are uniformly dispersed in the silica sol particles, and the metal ion ratio is adjustable;
the silica sol prepared by the method has small particle size, does not need to add other reagents to prevent the growth of the silica sol particle size, can reach 4nm at least, and has large specific surface area; the SAPO-34 molecular sieve synthesized by the small-particle-size metal modified silica sol product prepared by the method can detect that metal ions enter a molecular sieve framework through characterization and analysis, the particle size of the molecular sieve is reduced, the specific surface area is correspondingly increased, and the catalytic performance and the service life of the molecular sieve for preparing olefin from methanol are obviously improved;
(2) the production process has the advantages of simple operation, short production period, mild conditions, low requirement on equipment, no wastewater generation and repeated use of residual trace raw material metal silicon powder.
These methods can cause that metal ions can not enter the molecular sieve framework and only are adsorbed on the surface of the molecular sieve, or the metal ions are unevenly distributed in the framework, so that the molecular sieve is quickly deactivated. The SAPO-34 molecular sieve prepared by using the small-particle-size metal modified silica sol product can avoid the problems, the particle size of the molecular sieve is reduced, the specific surface area is correspondingly increased, and the performance and the service life of the molecular sieve are obviously improved.
Drawings
FIG. 1 is an SEM electron micrograph of the SAPO-34 molecular sieve synthesized in example 3.
FIG. 2 is a schematic EDS spectrum of a SAPO-34 molecular sieve as synthesized in example 6.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments.
A metal modified silica sol for synthesizing SAPO-34 molecular sieve is prepared by the following steps:
s1, mixing silicon powder with the mole number of 3.5-6.5, the particle size of not more than 50 mu m and the purity of not less than 99% with deionized water with the mole number of 14-52, stirring, and activating at 45-65 ℃ for 15 min-1 h;
s2, adding 0.025-0.30 mole number of alkaline catalysts, feeding at 50-65 ℃, and reacting at 70-95 ℃ for 5-8 hours to obtain a silica sol seed solution;
s3, mixing and stirring a silica sol seed solution, deionized water, a metal salt solution with the mole number of 0.025-0.05 and an alkaline catalyst with the mole number of 0.025-0.05 and the temperature of 65-90 ℃ for reaction for 2-5 hours at the temperature of 70-95 ℃ to obtain a modified silica sol solution;
and S4, standing, precipitating and filtering to obtain the metal modified silica sol product with the particle size of 4-10 nm.
In the preparation process, the added silicon powder: deionized water: basic catalyst: metal salt: the molar ratio of the heated basic catalyst is 1: (4-15): (0.005-0.1): (0.01-0.2): (0.01-0.05).
The alkaline catalyst is selected from one or more of tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide, sodium hydroxide, potassium hydroxide and ammonia water.
The metal salt is selected from the following components: one or more of zinc salt, manganese salt, nickel salt, copper salt and cobalt salt; wherein the zinc salt comprises one or more of zinc nitrate, zinc sulfate, zinc acetate and zinc chloride; the manganese salt comprises one or more of manganese nitrate, manganese acetate and manganese sulfate; the nickel salt comprises one or more of nickel nitrate and nickel sulfate; the copper salt comprises one or more of copper nitrate, copper sulfate and copper acetate; the cobalt salt comprises one or more of cobalt nitrate, cobalt acetate and cobalt sulfate.
Example 1
500ml of deionized water was added to a 2L round bottom flask, and 100g of silicon metal powder was added with stirring and activated at 45 ℃ for 15min in a water bath. And slowly and gradually adding an alkaline catalyst solution prepared from 1g of sodium hydroxide and 100ml of deionized water into the activated solution when the temperature is increased to 65 ℃, and increasing to 80 ℃ for reaction for 5 hours after the reaction is stable in heat release to prepare the silica sol seed solution.
1g of sodium hydroxide was dissolved in 100ml of deionized water to prepare a basic catalyst solution, which was heated to 80 ℃ and 15g of Zn (NO) was added3)·6H2Dissolving O in 100ml deionized water to prepare a metal salt solution; mixing the two solutions with the silica sol seed solution prepared in the previous step, and reacting for 2 hours at 80 ℃ in a stirring state.
After standing, precipitating and filtering to remove trace unreacted metal silicon powder, obtaining the small-particle-size metal modified silica sol product.
Example 2
700ml of deionized water was added to a 2L round bottom flask, and 120g of silicon metal powder was added with stirring and activated at 50 ℃ for 15min in a water bath. And slowly and gradually adding an alkaline catalyst solution prepared from 2g of sodium hydroxide and 100ml of deionized water into the activated solution when the temperature is increased to 65 ℃, and increasing to 85 ℃ for reaction for 5 hours after the reaction is stable in heat release to prepare the silica sol seed solution.
1g of sodium hydroxide was dissolved in 100ml of deionized water to prepare a basic catalyst solution, which was heated to 85 ℃ and 15g of Zn (NO)3)·6H2Dissolving O in 100ml deionized water to prepare a metal salt solution; mixing the two solutions with the silica sol seed solution prepared in the previous step, and reacting for 3 hours at 85 ℃ in a stirring state.
After standing, precipitating and filtering to remove trace unreacted metal silicon powder, obtaining the small-particle-size metal modified silica sol product.
Example 3
700ml of deionized water was added to a 2L round bottom flask, and 130g of silicon metal powder was added with stirring and activated at 50 ℃ for 15min in a water bath. And slowly and gradually adding an alkaline catalyst solution prepared from 2g of sodium hydroxide and 100ml of deionized water into the activated solution when the temperature is raised to 60 ℃, raising the temperature to 85 ℃ after the reaction is stable, and reacting for 4 hours to obtain the silica sol seed solution.
1g of sodium hydroxide was dissolved in 100ml of deionized water to prepare a basic catalyst solution, which was heated to 85 ℃ and 20g of Zn (NO)3)·6H2Dissolving O in 100ml deionized water to prepare a metal salt solution; mixing the two solutions with the silica sol seed solution prepared in the previous step, and reacting for 5 hours at 85 ℃ in a stirring state.
And removing trace unreacted metal silicon powder through standing, precipitating and suction filtering to obtain the small-particle-size metal modified silica sol product. FIG. 1 is an SEM electron micrograph of the SAPO-34 molecular sieve synthesized in example 3.
Example 4
700ml of deionized water was added to a 2L round bottom flask, 130g of silicon metal powder was added with stirring, and activation was carried out for 15min at 60 ℃ in a water bath. Slowly and gradually adding an alkaline catalyst solution prepared from 2g of sodium hydroxide and 100ml of deionized water into the activated solution at the same temperature, heating to 90 ℃ after the reaction is stable and releasing heat, and reacting for 4 hours to obtain a silica sol seed solution.
2g sodium hydroxide was dissolved in 100ml deionized water to make a basic catalyst solution, and heated to 90 deg.C, 20g Zn (NO)3)·6H2Dissolving O in 100ml deionized water to prepare a metal salt solution; mixing the two solutions with the silica sol seed solution prepared in the previous step, and reacting for 4 hours at 90 ℃ in a stirring state.
And removing trace unreacted metal silicon powder through standing, precipitating and suction filtering to obtain the small-particle-size metal modified silica sol product.
Example 5
700ml of deionized water was added to a 2L round bottom flask, 145g of silicon metal powder was added with stirring, and activation was carried out for 15min at 55 ℃ in a water bath. When the temperature is raised to 65 ℃, slowly and gradually adding an alkaline catalyst solution prepared from 2.8g of potassium hydroxide and 100ml of deionized water into the activated solution, raising the temperature to 90 ℃ after the reaction is stable, and reacting for 4 hours to obtain a silica sol seed solution.
2.8g of potassium hydroxide was dissolved in 100ml of deionized water to prepare a basic catalyst solution, which was heated to 90 ℃ with 20g of Mn (NO)3)2Mixing the 50% solution and the silica sol seed solution prepared in the previous step, and reacting for 4 hours at 90 ℃ in a stirring state.
And removing trace unreacted metal silicon powder through standing, precipitating and suction filtering to obtain the small-particle-size metal modified silica sol product.
Example 6
700ml of deionized water was added to a 2L round bottom flask, 145g of silicon metal powder was added with stirring, and activation was carried out for 15min at 55 ℃ in a water bath. And slowly and gradually adding an alkaline catalyst solution prepared from 4g of sodium hydroxide and 100ml of deionized water into the activated solution when the temperature is increased to 65 ℃, and increasing to 90 ℃ for reaction for 4 hours after the reaction is stable in heat release to prepare the silica sol seed solution.
2g sodium hydroxide was dissolved in 100ml deionized water to make a basic catalyst solution, and heated to 90 deg.C with 20g Mn (NO)3)2Mixing the 50% solution and the silica sol seed solution prepared in the previous step, and reacting for 4 hours at 90 ℃ in a stirring state.
And removing trace unreacted metal silicon powder through standing, precipitating and suction filtering to obtain the small-particle-size metal modified silica sol product. FIG. 2 is a schematic EDS spectrum of a SAPO-34 molecular sieve as synthesized in example 6.
Example 7
In the same manner as in example 1, the reaction temperature in step S1 was changed to 75 ℃ and the reaction time was changed to 8 hours; in step S2, the number of moles of each substance was changed to 9.5g of Cu (NO) instead of the metal salt3)2And dissolving in 100ml deionized water to prepare a metal salt solution, wherein the reaction temperature is unchanged, but the time is prolonged to 5 hours. And removing trace unreacted metal silicon powder through standing, precipitating and suction filtering to obtain the small-particle-size metal modified silica sol product.
Example 8
In the same manner as in example 1, the reaction temperature in step S1 was changed to 75 ℃ and the reaction time was changed to 8 hours; in step S2, the number of moles of each substance was changed to 9.1g of Ni (NO) instead of the metal salt3)2And dissolving the mixture in 100ml of deionized water to prepare a metal salt solution, wherein the reaction temperature is constant, but the reaction time is prolonged to 4 hours.
And removing trace unreacted metal silicon powder through standing, precipitating and suction filtering to obtain the small-particle-size metal modified silica sol product.
Example 9
In the same manner as in example 2, the number of moles of each substance in step S1 was changed except that 1g of sodium hydroxide and 1.4g of potassium hydroxide as the basic catalyst were dissolved in 100ml of deionized water to prepare a basic catalyst solution; step S2 reaction time was 4 h.
And removing trace unreacted metal silicon powder through standing, precipitating and suction filtering to obtain the small-particle-size metal modified silica sol product.
Example 10
In the same manner as in example 4, the number of moles of each of the substances in step S2 was changed except that 20.3g of 25% tetrapropylammonium hydroxide and 10.5g of 35% tetraethylammonium hydroxide as basic catalysts were dissolved in 100ml of deionized water to prepare a basic catalyst solution, 100ml of deionized water was supplemented, and the basic catalyst solution was added to the mixed solution for 5 hours.
And removing trace unreacted metal silicon powder through standing, precipitating and suction filtering to obtain the small-particle-size metal modified silica sol product.
Table 1 shows the results of performance test analysis of the small particle size metal-modified silica sol products prepared in examples 1 to 10.
TABLE 1
Figure BDA0002396638460000101
Figure BDA0002396638460000111
Example 11
Using the zinc metal modified silica sol product synthesized in example 4, the following 1Al2O3:1P2O5:0.3SiO2:3.5 TEA: synthesizing the SAPO-34 molecular sieve by using the molar ratio of 55H2O, wherein the aluminum source used in the method is pseudo-boehmite, the phosphorus source used in the method is phosphoric acid, the organic template agent used in the method is triethylamine, the reaction temperature is 200 ℃, and the reaction time is 48 hours. After the reaction is finished, cooling the materials to room temperature, centrifugally separating the crystallized product from the mother liquor, washing the solid product to be neutral by using deionized water, and finally drying at 120 ℃ for 4 hours to obtain the SPSO-34 molecular sieve raw powder
Roasting the molecular sieve raw powder for 6 hours at 650 ℃, tabletting and granulating, sieving particles of 20-40 meshes, weighing 2.5g, placing in a fixed bed reactor, activating for 1 hour at 550 ℃, then cooling to 450 ℃, feeding by using a micro pump, wherein the raw material is 40% methanol aqueous solution, and the airspeed is 2 hours-1The reaction product was subjected to on-line chromatographic analysis for the fixed bed activity evaluation of methanol to low carbon olefins (MTO), and the selectivity and lifetime of ethylene, propylene and butene were shown in table 2.
Example 12
The same as example 11, wherein the silica sol used was changed to the manganese metal-modified silica sol product synthesized in example 5.
Comparative example 1
In the same manner as in example 11, the silica sol used was changed to a silica sol product which had not been metal-modified.
The detection instrument used by the invention comprises:
an S8 Tiger X-ray fluorescence spectrometer, a 7890B Agilent gas chromatograph, a Hitachi S3400 scanning electron microscope and an X-max Horiba energy spectrometer.
Table 2 shows the results of fixed bed evaluation of methanol-to-light olefins for SAPO-34 molecular sieves synthesized in examples 11 and 12 and comparative example 1.
TABLE 2
Figure BDA0002396638460000121
Wherein the service life is the time for maintaining the conversion rate of the methanol to be more than 99.95 percent, and the index of the service life is selected.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.

Claims (7)

1. A preparation method of metal modified silica sol is characterized by comprising the following steps:
s1, activating silicon powder and deionized water in a certain proportion under stirring conditions at a certain temperature to obtain an activated silicon powder-water mixture;
s2, adding an alkaline catalyst into the activated silicon powder-water mixture, and reacting for a certain time under a stirring condition and a certain temperature to obtain a silica sol seed solution;
s3, mixing the silica sol seed solution, the metal salt solution with a certain concentration and the heated alkaline catalyst solution according to a certain proportion, and continuously reacting for a certain time under the stirring condition and a certain temperature to obtain a modified silica sol solution; the adding amount of the metal salt is 0.01-0.2 time of the mole number of the silicon powder, the adding amount of the alkaline catalyst is 0.01-0.05 time of the mole number of the silicon powder, the temperature of the heated alkaline catalyst is 65-90 ℃, the stirring reaction temperature is 70-95 ℃, and the reaction time is 1-5 hours; the metal salt is one or more of zinc salt, manganese salt, nickel salt, copper salt and cobalt salt;
the particle size of the metal modified silica sol is 4-10 nm.
2. The method for preparing a metal-modified silica sol according to claim 1, further comprising: and standing the modified silica sol solution for precipitation, and performing suction filtration to remove impurities to obtain a metal modified silica sol product.
3. The method for preparing metal-modified silica sol according to claim 1, wherein the basic catalyst is one or more of tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide, sodium hydroxide, potassium hydroxide, and ammonia water.
4. The method for producing a metal-modified silica sol according to claim 1,
the zinc salt comprises zinc nitrate, zinc sulfate, zinc acetate and zinc chloride;
the manganese salt comprises manganese nitrate, manganese acetate and manganese sulfate;
the nickel salt comprises nickel nitrate and nickel sulfate;
the copper salt comprises copper nitrate, copper sulfate and copper acetate;
the cobalt salt comprises cobalt nitrate, cobalt acetate and cobalt sulfate.
5. The method for preparing the metal modified silica sol according to claim 1, wherein in the step S1, the particle size of the silicon powder is not higher than 50 μm, and the purity is not lower than 99%; the molar ratio of the deionized water to the silicon powder is 4-15;
the activation temperature is 45-65 ℃, and the activation time is 15 min-1 h.
6. The method for preparing the metal-modified silica sol according to claim 1, wherein in the step S2, the addition amount of the basic catalyst is 0.005-0.1 times of the mole number of the silicon powder, and the feeding temperature is 50-65 ℃;
the reaction temperature is 70-95 ℃, and the reaction time is 3-8 h.
7. A metal modified silica sol for use in the synthesis of SAPO-34 molecular sieves, prepared by the process of any one of claims 1 to 6.
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CN102040868A (en) * 2010-11-24 2011-05-04 上海迪升防腐新材料科技有限公司 Method for preparation and surface modification of alkaline silicon sol
CN102344761A (en) * 2011-08-03 2012-02-08 南通海迅天恒纳米科技有限公司 Preparation method of cerium-doped silica sol
CN103213995A (en) * 2013-04-01 2013-07-24 神华集团有限责任公司 Preparation method of silica sol containing potassium with controllable particle size
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