CN111298831B - Preparation method of SSZ-13 molecular sieve for MTO catalytic reaction - Google Patents
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Abstract
The invention relates to a preparation method of an SSZ-13 molecular sieve for MTO catalytic reaction, which comprises the steps of firstly preparing a Cu-SSZ-13 molecular sieve by using a cheap copper-amine complex as a template agent, and then removing Cu in the Cu-SSZ-13 molecular sieve for catalyzing the MTO reaction. Compared with the existing MTO catalyst, the SSZ-13 molecular sieve for catalyzing the MTO reaction is obtained by removing the copper in the Cu-SSZ-13 molecular sieve, so that the expensive N, N, N-trimethyl-1-adamantane ammonium hydroxide (TMADAOH) template agent is avoided being used in large quantity, the cost is reduced, the energy consumption is reduced, and the operation cost is reduced by reducing the MTO reaction temperature.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a preparation method of an SSZ-13 molecular sieve for an MTO catalytic reaction.
Background
With the rapid development of chemical industry in China, ethylene and propylene which are used as basic raw materials of the chemical industry occupy important positions in the chemical industry and are leading products in the petrochemical industry. The technology of methanol to olefin (MTO for short) is a new way to prepare olefin from non-petroleum resources. The MTO process can lead the chemical utilization of coal or natural gas to obtain a new development space, and particularly creates the opportunity of utilizing natural gas or coal to develop methanol, low-carbon olefin and downstream industries in a large scale for remote areas with rich natural gas resources or coal resources. Therefore, the research and development of the MTO catalyst have important significance for reducing the dependence of petroleum import in China.
The patent document US4544538 discloses a method for synthesizing SSZ-13 molecular sieve for the first time. The method adopts N, N, N-trimethyl-1-amantadine cation as a template agent to synthesize the SSZ-13 molecular sieve.
In recent years, SSZ-13 molecular sieves have evolved to exhibit corner-cut behavior in the reaction of MTO catalysts. Especially better catalytic activity and selectivity of low-temperature MTO reaction, and has wide prospect in industrial application. CN110182826 discloses a method for synthesizing a hollow SSZ-13 molecular sieve, which adopts a method of adding seed crystals into a synthetic solution, and the finally obtained product is the hollow SSZ-13 molecular sieve, which has great application potential in the aspect of MTO catalysis. CN106830007B discloses a hierarchical pore SSZ-13 molecular sieve catalyst, a synthesis method and an application thereof, and the hierarchical pore SSZ-13 molecular sieve catalyst prepared by the invention has an airspeed of 4.0h in an MTO reaction -1 The reaction temperature is 450 ℃, and the lower olefin (C) is higher 2 ＝ +C 3 ＝ ) The selectivity can reach over 84 percent, and the conversion life before the conversion rate is reduced to 50 percent is over 13 hours. CN109110782A discloses a preparation method of SSZ-13 molecular sieve, wherein ethanol is used as a solvent to replace part of water, and the preparation method can be used in chemical processes such as MTO.
CN109534354A discloses a synthesis method of SSZ-13 molecular sieve, which can effectively shorten the reaction time by 10% and improve the yield by 5% when used in MTO reaction, and has better economic benefit. CN109701619A discloses an SSZ-13/SSZ-39 composite structure molecular sieve and a synthesis method thereof, methanol is used as a raw material, the molecular sieve is used for MTO reaction, and the mass space velocity is 0.1h at 400 DEG C -1 And under the condition that the pressure is 10MPa, the yield of the ethylene, the propylene and the isobutene reaches 82.3 percent, a better technical effect is obtained, but the space velocity is lower. CN110156046 discloses a preparation method of SSZ-13 molecular sieve and application of SSZ-13 molecular sieve, the nano SSZ-13 molecular sieve is prepared by adopting a one-step method, polyacrylamide is introduced, and the space velocity is 1.2h when the nano SSZ-13 molecular sieve is applied to MTO reaction -1 The reaction temperature is 400 ℃, the service life of the catalyst can reach 420min, the total selectivity of ethylene and propylene is more than 85%, but the prepared nano molecular sieve has separation problem in the aspect of industrialization.
The synthesis methods all adopt a large amount of expensive N, N, N-trimethyl-1-amantadine, but the synthesis cost of the SSZ-13 molecular sieve is higher due to the expensive price of the template agent, so that the popularization and the application of the SSZ-13 molecular sieve are greatly limited.
There is a document (chem. Commu,2011,47,9783) reporting a method for preparing Cu-SSZ-13 molecular sieves by in situ synthesis. The method uses a complex (Cu-TEPA) formed by tetravinyl penta-ammonium (TEPA) and Cu species as an SSZ-13 molecular sieve structure directing agent, avoids the use of expensive N, N, N-trimethyl-1-adamantane ammonium, and has remarkable advantages in synthesis cost, but the synthesized Cu-SSZ-13 molecular sieve has narrow silicon-aluminum ratio adjustable range and higher Cu content, is directly used for MTO reaction, and has lower catalytic performance.
CN11010465 reports a method for directly synthesizing an alkali-free Cu-SSZ-13 molecular sieve and a catalyst thereof,the method comprises the steps of mixing a copper source, deionized water and organic amine, stirring to form a uniform aqueous solution, adding quaternary ammonium base, a template agent, aluminum hydroxide and a silicon source, stirring and mixing to form a uniform mixed solution, and crystallizing the mixed solution under the hydrothermal conditions of autogenous pressure and a certain crystallization temperature to obtain the Cu-SSZ-13 molecular sieve free of alkali metal. Since the Cu content is higher, it is mainly used in NH 3 -SCR reaction. CN109999897 discloses a method for synthesizing Cu-SSZ-13 in a sodium-free system in one step, wherein an aluminum source, a silicon source, a copper-ammonia complex and a copper ion load regulator are used for preparing initial gel; and crystallizing the initial gel, filtering, washing, drying and roasting to obtain the Cu-SSZ-13 molecular sieve, wherein the application direction of the molecular sieve is not mentioned.
There are documents (Su Yu, 2013.42 (10): 1075-1079.) that when Cu-SSZ-13 is applied in MTO reaction, although the conversion of methanol is high and the selectivity of ethylene and propylene is high, the reaction temperature is high, the single-pass lifetime is short, only 60min, which is lower than that of the SSZ-13 molecular sieve synthesized by other methods in MTO. The reason is that a large amount of organic copper amine complex is introduced in the synthesis process, so that the content of active component copper in the catalyst is too high, side reaction is aggravated, and pore channels are blocked. Therefore, it is necessary to adopt a reasonable method to remove Cu in the Cu-SSZ-13 molecular sieve, but the Cu removing process also has to influence the relative crystallinity of the SSZ-13 molecular sieve, so that the relative crystallinity of the SSZ-13 molecular sieve has to be improved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of an SSZ-13 molecular sieve for MTO catalytic reaction, which solves the technical problems that the content of copper in a Cu-SSZ-13 molecular sieve in the prior art is difficult to prepare and the copper is easy to block in the MTO reaction, and has the advantages of controllable copper content, adjustable silicon-aluminum molar ratio, high catalytic activity and the like.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of SSZ-13 molecular sieve for MTO catalytic reaction comprises the following steps:
(1) Preparation of Cu-SSZ-13 molecular sieve: mixing an aluminum source, a silicon source, a sodium source, water and a copper-amine complex compound according to the proportion of 1.0Al 2 O 3 :10～35SiO 2 :3.0～5.0Na 2 O:200～300H 2 Mixing O with the molar ratio of 2.0-4.0 Cu-TEPA at room temperature, then controlling the temperature to be 130-175 ℃ for reaction for 96-144 h, washing the product with deionized water, and drying at 100 ℃ for 12h to obtain the Cu-SSZ-13 molecular sieve;
(2) Removing Cu by using strong acid and weak alkali salt: adding the Cu-SSZ-13 molecular sieve into a strong acid weak base salt solution, carrying out ion exchange for 4-12 h at the temperature of 80-120 ℃, drying at the constant temperature of 100 ℃ after washing, and repeating for multiple times to obtain the SSZ-13 molecular sieve without Cu;
(3) Secondary crystallization of the molecular sieve: taking the SSZ-13 molecular sieve without Cu as a seed crystal, adding a silicon source, an aluminum source, a sodium source, water and an N, N, N-trimethyl adamantane ammonium hydroxide template agent according to Al 2 O 3 ∶SiO 2 ∶Na 2 O∶H 2 The mol ratio of O to TMADAOH is 1: 20-60: 1-16: 600-1800: mixing the components in a ratio of 0-1 to obtain gel, and performing secondary crystallization to obtain the SSZ-13 molecular sieve for the MTO catalytic reaction.
The silicon source in the step (1) and the step (3) is water glass, silica sol, silica gel or amorphous SiO 2 Powder, si (OCH) 3 ) 4 And Si (OC) 2 H 5 ) 4 The aluminum source is one or a mixture of several of sodium metaaluminate, pseudo-boehmite, amorphous aluminum hydroxide powder and aluminum isopropoxide, and the sodium source is one or two of sodium hydroxide or sodium oxide. .
The copper source in the copper-amine complex is one or more of copper sulfate, copper nitrate or copper acetate.
The organic amine in the copper-amine complex is tetraethylenepentamine.
The strong acid weak base salt comprises one or more of ammonium chloride, ammonium nitrate or ammonium sulfate.
The concentration of the strong acid weak base salt solution is 0.1-2 mol/L, and the solid-to-liquid ratio after the Cu-SSZ-13 molecular sieve is added is 0.01-0.1 g/mL.
The mass ratio of the seed crystal to the gel in the secondary crystallization process is 0.05-1.
The secondary crystallization condition is crystallization for 48 to 72 hours at 130 to 175 ℃. The secondary crystallization is utilized to adjust the silicon-aluminum ratio of the SSZ-13 molecular sieve and the acidity of the SSZ-13 molecular sieve, so as to achieve the purposes of reducing the MTO reaction temperature, further improving the methanol conversion rate and the diene selectivity.
The prepared SSZ-13 molecular sieve has excellent methanol conversion rate and diene selectivity. Also has better low-temperature reaction performance. The reaction of methanol on molecular sieve catalyst is acid catalyzed, and the acidity reduction effect is the cause of deactivation. The main factor causing the acidity to decrease is that carbon deposits cover the acid sites of the catalyst. On the other hand, the removal effect of a large amount of water vapor in the reaction product on the framework aluminum of the molecular sieve at a high temperature also causes the acidity of the molecular sieve to be reduced. When the reaction temperature is lower (400 ℃), the dealumination effect of the steam on the SSZ-13 molecular sieve is not obvious, and carbon deposition is the main reason for deactivation. The reaction is carried out at 500 ℃, the influence of water vapor on the SAPO-34 molecular sieve cannot be ignored, and the reduction of acidity is the comprehensive result of two factors [17] . In the actual reaction process, the carbon deposit on the catalyst can be regenerated by a method of introducing air and burning off, and the dealumination of the water vapor changes the composition and the pore size of the molecular sieve, so that the process is an irreversible process. The effect of steam dealumination is therefore the main factor in determining the actual service life of the catalyst in a high temperature process. Under the low-temperature condition of MTO reaction, the SSZ-13 molecular sieve is favorable for reducing high-carbon byproducts and is favorable for separating product gas in process. The service life of the catalyst can be prolonged, the size of the regenerator for the deactivated catalyst can be designed to be smaller, and more investment can be saved.
The application can greatly reduce the usage amount of the N, N, N-trimethyl adamantane ammonium hydroxide template agent. The Cu-TEPA is prepared from a copper sulfate solution and a tetraethylenepentamine solution, and the copper sulfate and the tetraethylenepentamine have lower cost; the traditional template agent N, N, N-trimethyl-1-adamantane ammonium hydroxide is expensive. The former has small dosage in preparing sol, and can reduce the cost by 50 to 200 times. As can be seen, the Cu-TEPA used as a template agent greatly reduces the synthesis cost of SSZ-13.
The Cu removal process may influence the relative crystallinity of the SSZ-13 molecular sieve, and in order to repair the damaged framework of the molecular sieve during Cu removal, a secondary crystallization method is adopted to improve the crystallinity. The molecular sieve after Cu demetalization can be used as a crystal seed in a secondary crystallization process, a crystal growth interface is provided for molecular sieve crystallization, a structure-oriented effect is generated, the using amount of a template agent N, N, N-trimethyl adamantane ammonium hydroxide is reduced, and the silicon-aluminum ratio can be further adjusted.
The prepared SSZ-13 molecular sieve is used for catalyzing MTO reaction, and the category of MTO reaction catalysts is expanded. Compared with the traditional MTO catalyst, the technical scheme disclosed by the invention has the following advantages:
(1) The SSZ-13 molecular sieve reduces the reaction temperature, reduces the energy consumption, prolongs the service life and reduces the operation cost in the process under the condition of keeping higher reaction activity and diene selectivity.
(2) Greatly reduces the usage amount of expensive template agent N, N, N-trimethyl adamantane ammonium hydroxide and reduces the preparation cost.
(3) By removing Cu from the Cu-SSZ-13 molecular sieve and performing secondary crystallization treatment, the silicon-aluminum ratio can be adjusted, the surface acidity can be adjusted, the relative crystallinity can be improved, and the MTO reaction performance can be improved.
Drawings
FIG. 1 is an XRD pattern of an SSZ-13 molecular sieve prepared by using a copper amine complex as a template;
FIG. 2 is an XRD pattern of an SSZ-13 molecular sieve prepared by using a copper amine complex as a template after Cu removal;
FIG. 3 is an XRD pattern of SSZ-13 molecular sieve prepared by using copper amine complex as a template agent after Cu removal and secondary crystallization;
FIG. 4 is a microscopic morphology photograph of SSZ-13 molecular sieve prepared by using copper amine complex as template agent after Cu removal and secondary crystallization;
FIG. 5 is an XRD pattern of an SSZ-13 molecular sieve prepared with N, N, N-trimethyladamantane ammonium hydroxide as a template;
FIG. 6 is a microscopic morphology photograph of an SSZ-13 molecular sieve prepared by using N, N, N-trimethyladamantane ammonium hydroxide as a template agent.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
A preparation method of SSZ-13 molecular sieve for MTO catalytic reaction comprises the following steps:
(1) Preparation of Cu-SSZ-13 molecular sieve: mixing an aluminum source, a silicon source, a sodium source, water and a copper-amine complex compound according to the proportion of 1.0Al 2 O 3 :10～35SiO 2 :3.0～5.0Na 2 O:200～300H 2 O is 2.0 to 4.0 mol percent, cu-TEPA is mixed at room temperature, stirring is carried out for 30min by a stirring paddle, the mixture is put into a steel reaction kettle with a polytetrafluoroethylene lining, the mixture reacts for 96h to 144h at the temperature of 130 ℃ to 175 ℃, after the reaction is finished, a product is washed by deionized water and dried for 12h at the temperature of 100 ℃ to obtain the Cu-SSZ-13 molecular sieve (S1), and the silicon source used in the step is water glass, silica sol, silica gel and amorphous SiO 2 Powder, si (OCH) 3 ) 4 And Si (OC) 2 H 5 ) 4 One or a plurality of mixtures, the aluminum source is one or a plurality of mixtures of sodium metaaluminate, pseudo-boehmite, amorphous aluminum hydroxide powder and aluminum isopropoxide, the sodium source is one or two of sodium hydroxide or sodium oxide, the copper source in the copper-amine complex is one or a plurality of copper sulfate, copper nitrate or copper acetate, the organic amine is one or a plurality of tetraethylenepentamine or other primary amines which can form a complex with the ionic radius of about 0.73 with copper;
(2) And (2) removing most Cu in the S1 molecular sieve by adopting strong acid and weak base salt with the concentration of 0.1-2 mol/L, including ammonium chloride, ammonium nitrate or ammonium sulfate: and (2) adding the S1 sample into a strong acid and weak base salt solution with the solid-to-liquid ratio of 0.01-0.1 g/mL, carrying out ion exchange for 4-12 h under the water bath condition of 80-120 ℃, washing, and drying for 2h at constant temperature of 100 ℃. And repeating the steps for multiple times to obtain a molecular sieve sample S2. Wherein the mass fraction of Cu is at most 0.01-1%
(3) S2, secondary crystallization of the molecular sieve: taking the molecular sieve sample S2 prepared in the step (2) as a seed crystal, and adding a silicon source, an aluminum source, a sodium source, an N, N, N-trimethyl adamantane ammonium hydroxide template agent and water according to 1.0Al 2 O 3 ∶20～60SiO 2 ∶1～16Na 2 O∶600～1800H 2 Mixing the mixture of O and 0-1 TMAdaOH in a molar ratio to obtain gel, performing secondary crystallization on the gel at the temperature of 130-175 ℃ for 48-72 h to obtain the SSZ-13 molecular sieve, wherein the mass ratio of the seed crystal to the gel is 0.05-1.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Comparative example 1
Preparation of Cu-SSZ-13 molecular sieve: sodium aluminate, water glass, sodium hydroxide, deionized water and copper amine complex compound are mixed according to the formula of n (Al) 2 O 3 ):n(SiO 2 ):n(Na 2 O):n(H 2 N (Cu-TEPA) in a molar ratio of 1. Putting into a steel reaction kettle with a polytetrafluoroethylene lining, and reacting for 96 hours at 130 ℃. After the reaction is finished, washing the product with deionized water, and drying at 100 ℃ for 12h to obtain the Cu-SSZ-13 molecular sieve (S1), wherein FIG. 1 is an XRD (X-ray diffraction) spectrum of the SSZ-13 molecular sieve prepared by using a copper amine complex as a template agent. Relative crystallinity was set to 100% by XRD detection.
Comparative example 2
Preparation of Cu-SSZ-13 molecular sieve: sodium aluminate, water glass, sodium hydroxide, deionized water and copper amine complex according to n (Al) 2 O 3 ):n(SiO 2 ):n(Na 2 O):n(H 2 N (Cu-TEPA) at a molar ratio of 1. Putting the mixture into a steel reaction kettle with a polytetrafluoroethylene lining, and reacting for 96 hours at 130 ℃. After the reaction was completed, the product was washed with deionized water and dried at 100 ℃ for 12 hours to obtain a Cu-SSZ-13 molecular sieve (S1).
And (3) removing Cu: adding 2g of the synthesized sample into 50mL of ammonium nitrate solution with the concentration of 1mol/L, carrying out ion exchange for 4h under the condition of 80 ℃ water bath, washing, drying for 2h at constant temperature of 100 ℃, and repeating for 3 times. Obtaining a molecular sieve sample (S2), wherein FIG. 2 is an XRD (X-ray diffraction) spectrum of the SSZ-13 molecular sieve prepared by using the copper-amine complex as the template agent after Cu removal. Relative crystallinity was 80% by XRD.
Example 1.
Preparation of SSZ-13 molecular sieve by using copper amine complex as template agent
Preparation of Cu-SSZ-13 molecular sieve: sodium metaaluminate, water glass, sodium hydroxide, deionized water and copper ammonium complex compound according to n (Al) 2 O 3 ):n(SiO 2 ):n(Na 2 O):n(H 2 N (Cu-TEPA) at a molar ratio of 1. Putting into a steel reaction kettle with a polytetrafluoroethylene lining, and reacting for 96 hours at 130 ℃. After the reaction was completed, the product was washed with deionized water and dried at 100 ℃ for 12 hours to obtain a Cu-SSZ-13 molecular sieve (S1).
And (3) removing Cu: adding 2g of synthesized S1 sample into 50mL of ammonium nitrate solution with the concentration of 1mol/L, carrying out ion exchange for 4h under the condition of 80 ℃ water bath, washing, drying for 2h at constant temperature of 100 ℃, and repeating for 3 times. A sample of molecular sieve (S2) was obtained.
Secondary crystallization: taking the obtained S2 molecular sieve as a seed crystal, wherein the mass ratio of the seed crystal to gel is 1, taking silica sol (30%) as a silicon source, aluminum isopropoxide as an aluminum source, sodium hydroxide as a sodium source, and N, N, N-trimethyl adamantane ammonium hydroxide as a template agent according to the formula of N (Al) 2 O 3 )∶n(SiO 2 )∶n(Na 2 O)∶n(H 2 O):n (TMADAOH) = 1:20: 1: 600:0, crystallizing at 175 ℃ for 96 hours to prepare the SSZ-13 molecular sieve, and recording the molecular sieve as Z1. Fig. 3 is an XRD spectrum of the SSZ-13 molecular sieve prepared with the copper amine complex as the template after Cu removal and secondary crystallization, and fig. 4 is a microscopic morphology photograph of the SSZ-13 molecular sieve prepared with the copper amine complex as the template after Cu removal and secondary crystallization, and the relative crystallinity is 110% by XRD detection. The resulting product was analyzed by X-ray fluorescence spectroscopy and the results are shown in Table 2.
Example 2.
Preparation of SSZ-13 molecular sieve by using copper amine complex as template agent
Preparation of Cu-SSZ-13 molecular sieve: mixing pseudoboehmite (CP) and Si (OCH) 3 ) 4 (AR), sodium oxide (AR), deionized water and cuprammonium complex as per n (Al) 2 O 3 ):n(SiO 2 ):n(Na 2 O):n(H 2 N (Cu-TEPA) at a molar ratio of 1. Putting into a steel reaction kettle with a polytetrafluoroethylene lining, and reacting for 108h at 140 ℃. After the reaction was completed, the product was washed with deionized water and dried at 100 ℃ for 12 hours to obtain a Cu-SSZ-13 molecular sieve (S1).
And (3) removing Cu: adding 2g of the synthesized S1 sample into 50mL of ammonium chloride solution with the concentration of 1.2mol/L, carrying out ion exchange for 6h under the condition of 80 ℃ water bath, washing, drying for 2h at constant temperature of 100 ℃, and repeating for 3 times. A sample of molecular sieve (S2) was obtained.
Secondary crystallization: the obtained S2 molecular sieve is used as a seed crystal, the mass ratio of the seed crystal to the gel is 0.05, and the amorphous SiO is 2 The powder is a silicon source, aluminum isopropoxide is an aluminum source, N, N, N-trimethyl adamantane ammonium hydroxide is a template agent, sodium hydroxide is a sodium source, and the formula is shown in the specification 2 O 3 )∶n(SiO 2 )∶n(Na 2 O)∶n(H 2 O): n (TMADAOH) = 1: 30: 4: 800: hydrothermal crystallization is carried out according to the molar ratio of 0.2, and the SSZ-13 molecular sieve is prepared and is marked as Z2. Relative crystallinity was 150% by XRD detection. The resulting product was analyzed by X-ray fluorescence spectroscopy and the results are shown in Table 2.
Example 3.
The synthesis of SSZ-13 molecular sieve using copper amine complex as template agent as described in example 1, except that the differences are shown in Table 1:
TABLE 1
The resulting product was analyzed by X-ray fluorescence spectroscopy, and the results are shown in Table 2.
TABLE 2
| Sample numbering | Actual SiO 2 /Al 2 O 3 | Mass fraction/% of Cu |
| Z1 | 6.2 | 0.93 |
| Z2 | 15.8 | 0.82 |
| Z3 | 19.5 | 0.68 |
| Z4 | 24.9 | 0.59 |
| Z5 | 26.8 | 0.57 |
| Z6 | 32.4 | 0.49 |
Comparative example 3
Preparation of SSZ-13 molecular sieve by using N, N, N-trimethyl adamantane ammonium hydroxide as template agent
Silica sol (30%) is used as a silicon source, sodium metaaluminate is used as an aluminum source, N, N, N-trimethyl adamantane ammonium hydroxide is used as a template agent according to the formula of N (Al) 2 O 3 )∶n(SiO 2 )∶n(Na 2 O)∶n(H 2 O):n (TMADAOH) = 1:20: 1: 600:10, filling the synthetic solution into a polytetrafluoroethylene-lined steel reaction kettle, and crystallizing at 175 ℃ for 96 hours to obtain the SSZ-13 molecular sieve, wherein the figure 5 shows an XRD (X-ray diffraction) pattern of the SSZ-13 molecular sieve prepared by using N, N, N-trimethyl adamantane ammonium hydroxide as a template agent, and the figure 6 shows a microscopic morphology picture of the SSZ-13 molecular sieve prepared by using N, N, N-trimethyl adamantane ammonium hydroxide as a template agent. The actual SiO is obtained by analysis of X-ray fluorescence spectrum analysis 2 /Al 2 O 3 Was 11.6.
Example 4.
The SSZ-13 molecular sieve is used for catalyzing the reaction of preparing olefin from methane:
catalyzing the reaction of preparing olefin from methane: and (3) roasting the obtained catalyst raw powder in a muffle furnace at 600 ℃ for 6h, then tabletting, and crushing to 20-40 meshes. 1g of the sample was weighed and loaded into a fixed bed reactor for MTO evaluation. Activating for 1.5 hours at 500 ℃ by introducing nitrogen, and then cooling to 450 ℃. The methanol is carried by nitrogen, the flow rate of the nitrogen is 15ml/min, the partial pressure of the methanol is 9.3KPa, and the mass space velocity is 0.5-2h -1 And the ratio of alcohol to water is 40:60. the product obtained was analyzed by on-line gas chromatography (Agilent 7890) and the results are given in Table 3. It can be seen therein that 6 samples all had very high catalytic lifetimes, with the overall yield of ethylene and propylene exceeding 83.0%.
The results of the measurement were as follows:
TABLE 3
Comparative example 4.
SAPO-34 molecular sieve for MTO catalytic reaction
Taking raw powder of the SAPO-34 molecular sieve catalyst to perform tabletting and crushing the raw powder to 20 to 40 meshes. 1g of the sample was weighed and loaded into a fixed bed reactor for MTO evaluation. Activating for 1.5 hours at 500 ℃ by introducing nitrogen, and then cooling to 450 ℃. The methanol is carried by nitrogen, the flow rate of the nitrogen is 15ml/min, the partial pressure of the methanol is 9.3KPa, and the mass space velocity is 0.5-2h -1 And the ratio of alcohol to water is 40:60. the product obtained was analyzed by on-line gas chromatography (Agilent 7890) and the results are given in Table 4.
The results of the measurement were as follows:
TABLE 4
Example 5.
Preparation of SSZ-13 molecular sieve by using copper amine complex as template agent
Preparation of Cu-SSZ-13 molecular sieve: sodium metaaluminate, si (OC) 2 H 5 ) 4 Sodium hydroxide, deionized water and copper ammonium complex as per n (Al) 2 O 3 ):n(SiO 2 ):n(Na 2 O):n(H 2 N (Cu) at a molar ratio of 1. Putting into a steel reaction kettle with a polytetrafluoroethylene lining, and reacting at 130 ℃ for 144h, wherein the copper source in the copper-ammonium complex is copper sulfate, and the organic amine is tetraethylenepentamine. After the reaction was completed, the product was washed with deionized water and dried at 100 ℃ for 12 hours to obtain a Cu-SSZ-13 molecular sieve (S1).
And (3) removing Cu: adding the synthesized S1 sample into an ammonium nitrate solution with the concentration of 0.1mol/L, controlling the solid-liquid ratio at 0.01g/mL, carrying out ion exchange at 80 ℃ for 12h, washing, drying at 100 ℃ for 2h, and repeating for 5 times. A sample of molecular sieve (S2) was obtained.
Secondary crystallization: the obtained S2 molecular sieve is used as a seed crystal, the mass ratio of the seed crystal to the gel is 0.1, and the water glassIs silicon source, amorphous aluminum hydroxide powder is aluminum source, sodium oxide is sodium source, and n (Al) is used 2 O 3 )∶n(SiO 2 )∶n(Na 2 O)∶n(H 2 O) = 1:20: 1: 600, and carrying out hydrothermal crystallization to prepare the SSZ-13 molecular sieve.
Example 6.
Preparation of SSZ-13 molecular sieve by using copper amine complex as template agent
Preparation of Cu-SSZ-13 molecular sieve: mixing aluminum isopropoxide, silica gel, sodium hydroxide, deionized water and copper ammonium complex according to n (Al) 2 O 3 ):n(SiO 2 ):n(Na 2 O):n(H 2 N (Cu) in a molar ratio of 1. Putting the mixture into a steel reaction kettle with a polytetrafluoroethylene lining, and reacting for 96 hours at 175 ℃, wherein the copper source in the copper-ammonium complex is copper acetate, and the organic amine is tetraethylenepentamine. After the reaction was completed, the product was washed with deionized water and dried at 100 ℃ for 12 hours to obtain a Cu-SSZ-13 molecular sieve (S1).
And (3) removing Cu: adding the synthesized S1 sample into an ammonium sulfate solution with the concentration of 2mol/L, controlling the solid-to-liquid ratio to be 0.1g/mL, carrying out ion exchange at 120 ℃ for 4h, washing, drying at 100 ℃ for 2h, and repeating for 2 times. A sample of molecular sieve (S2) was obtained.
Secondary crystallization: the obtained S2 molecular sieve is used as a seed crystal, and the mass ratio of the seed crystal to the gel is 1,Si (OCH) 3 ) 4 The silicon source is pseudo-boehmite as an aluminum source, the sodium hydroxide is a sodium source, the N, N, N-trimethyl adamantane ammonium hydroxide is a template agent according to the formula of N (Al) 2 O 3 )∶n(SiO 2 )∶n(Na 2 O)∶n(H 2 O): n (TMADAOH) = 1: 60: 16: 1800:1, and performing hydrothermal crystallization to prepare the SSZ-13 molecular sieve.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiments described above are intended to facilitate a person of ordinary skill in the art in understanding and using the invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (7)
1. A method for preparing SSZ-13 molecular sieve for MTO catalytic reaction is characterized by comprising the following steps:
(1) Preparation of Cu-SSZ-13 molecular sieve: mixing an aluminum source, a silicon source, a sodium source, water and a copper-amine complex compound according to 1.0Al 2 O 3 :10~35SiO 2 :3.0~5.0Na 2 O:200~300H 2 Mixing O with the molar ratio of 2.0-4.0 Cu-TEPA at room temperature, then controlling the temperature to be 130-175 ℃ for reaction for 96h-144h, and washing and drying a product to obtain the Cu-SSZ-13 molecular sieve;
(2) Removing Cu by using strong acid and weak alkali salt: adding a Cu-SSZ-13 molecular sieve into a strong acid and weak base salt solution, carrying out ion exchange for 4-12h at the temperature of 80-120 ℃, drying at the constant temperature of 100 ℃ after washing, and repeating for multiple times to obtain the SSZ-13 molecular sieve without Cu, wherein the strong acid and weak base salt comprises one or more of ammonium chloride, ammonium nitrate or ammonium sulfate;
(3) Secondary crystallization of the molecular sieve: taking the SSZ-13 molecular sieve without Cu as a seed crystal, adding a silicon source, an aluminum source, a sodium source, water and an N, N, N-trimethyl adamantane ammonium hydroxide template agent according to Al 2 O 3 ∶SiO 2 ∶Na 2 O∶H 2 The molar ratio of O to TMADAOH is 1:20 to 60: 1 to 16: 600 to 1800:0~1, obtaining gel after mixing, and preparing the SSZ-13 molecular sieve for the MTO catalytic reaction after secondary crystallization.
2. The method of claim 1, wherein the silicon source used in step (1) and step (3) is selected from the group consisting of water glass, silica sol, silica gel, and amorphous SiO 2 Powder, si (OCH) 3 ) 4 And Si (OC) 2 H 5 ) 4 The aluminum source is one or a mixture of several of sodium metaaluminate, pseudo-boehmite, amorphous aluminum hydroxide powder and aluminum isopropoxide, and the sodium source is one or two of sodium hydroxide or sodium oxide.
3. The method as claimed in claim 1, wherein the copper source of the copper amine complex is one or more of copper sulfate, copper nitrate and copper acetate.
4. The method of claim 1, wherein the organic amine of the copper-amine complex is tetraethylenepentamine.
5. The method for preparing the SSZ-13 molecular sieve for the MTO catalytic reaction as claimed in claim 1, wherein the concentration of the strong acid and weak base salt solution is 0.1 to 2mol/L, and the solid-to-liquid ratio after the Cu-SSZ-13 molecular sieve is added is 0.01 to 0.1g/mL.
6. The method as claimed in claim 1, wherein the mass ratio of the seed crystal to the gel in the secondary crystallization process is 0.05 to 1.
7. The preparation method of the SSZ-13 molecular sieve for the catalytic reaction of MTO according to claim 1, wherein the secondary crystallization condition is crystallization at 130-175 ℃ for 48h-72h.
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