CN1301598A - MeAPSO-56 molecular sieve and its synthesizing method - Google Patents

Abstract

The anhydrous state composition of a metallosilicoaluminophosphate molecular _sieve MeAPSO-56 can be expressed as _: mR·nMe·( _SixAlyPz )O ₂ , where R is the template agent present in the micropores of the molecular sieve, and m represents the mole ( _Six Al _y P _z )O ₂ corresponds to the number of moles of the template agent, m=0.05～0.3; Me is the metal atom entering the molecular sieve framework, n is the mole of Me per mole of ( _Six Al _y P _z )O ₂ Number, n=0.001～0.20. x, y, and z represent the mole fractions of Si, Al, and P respectively, and the ranges are x=0.01-0.98, y=0.01-0.60, z=0.01-0.52, and x+y+z=1. The molecular sieve has ion exchange performance and adsorption performance. Can be applied to a variety of hydrocarbon reactions.

Description

MeAPSO-56 molecular sieve and its synthesis method

The invention provides a novel microporous metal silicoaluminophosphate molecular sieve MeAPSO-56 and a synthesis method thereof.

In 1984, USP 4,440,871 disclosed the synthesis of a variety of silicoaluminophosphate molecular sieves with different structures, these molecular sieves are SAPO-5, SAPO-11, SAPO-16, SAPO-17, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-37, SAPO-40, SAPO-41, SAPO-42 and SAPO-44. Some molecular sieves with small pore structure, such as SAPO-34, have been successfully used in MTG, MTO and other processes, and have shown good catalytic performance. Since then, some silicoaluminophosphate molecular sieves with different structures have been synthesized one after another. SAPO-56 is a silicoaluminophosphate molecular sieve with a new structure synthesized by Stephen T.Wilson et al. in 1994 (USP5,370,851).

Metal molecular sieves introduce metals into the framework of molecular sieves, so that they have some characteristics different from the original molecular sieves. US Patent No. 4,554,143, No. 4,752,651, No. 4,853,179 have successively reported the synthesis methods of several metal aluminophosphates, but no report on the study of MeAPSO-56 molecular sieve has been seen.

The metallosilicoaluminophosphate molecular sieve MeAPSO-56 synthesized by the present invention is characterized in that the anhydrous chemical composition of the synthesized molecular sieve can be expressed as: mR·nMe·(SixAlyPz)O ₂ , wherein R is the template agent present in the micropores of the molecular sieve , m represents the number of moles of template agent per mole of (SixAlyPz)O ₂ , m=0.05～0.3; Me is the metal atom entering the molecular sieve framework, n is the number of moles of Me corresponding to each mole of (SixAlyPz)O ₂ , n=0.001 ~0.20. x, y, and z represent the mole fractions of Si, Al, and P respectively, and their ranges are x=0.01～0.98, y=0.01～0.60, z=0.01～0.52, and x+y+z=1;

In the metal silicoaluminophosphate molecular sieve MeAPSO-56, the metal atom Me is one or any of vanadium, copper, molybdenum, zirconium, titanium, cobalt, manganese, magnesium, iron, nickel and zinc, and at least part of MeO ₂ tetrahedra form a molecular sieve framework and exist in molecular sieves.

The metal silicoaluminophosphate molecular sieve synthesized by the present invention can be used as ion exchanger and adsorbent, and the catalyst made by it can be applied in various hydrocarbon reactions, such as catalytic cracking, reforming, polymerization, alkylation, desorption Alkylation, transalkylation, isomerization, hydrocyclization, dehydrogenation and hydrogenation reactions, etc.

The synthetic MeAPSO-56 molecular sieve of the present invention is characterized in that the preparation process is as follows:

(1) Mixing silicon source material, aluminum source material, phosphorus source material, metal salt, templating agent and water in proportion under stirring to obtain an initial gel mixture;

(2) Transfer the initial gel mixture material into a stainless steel synthesis kettle and seal it, and crystallize at 100-250°C for not less than 1 hour, preferably 2-100 hours;

(3) Separating the solid crystalline product from the mother liquor, washing with deionized water until neutral, and drying in the air at 80-130°C to obtain the original powder of metal silicoaluminophosphate molecular sieve;

(4) Calcining the raw molecular sieve powder in air at 300-700°C for not less than 3 hours to obtain the active metal silicoaluminophosphate molecular sieve catalyst.

In the preparation process of the above-mentioned MeAPSO-56 molecular sieve of the present invention, the silicon source used is one or more mixtures in silica sol, silica gel, water glass, active silica or orthosilicate; Aluminum source is One or a mixture of aluminum salts, aluminates, activated alumina, aluminum alkoxides, pseudoboehmite or pseudoboehmite; phosphorus source is orthophosphoric acid, phosphate, organic phosphides or phosphorus One or a mixture of two oxides; the metal is one of the oxides, inorganic salts or organic salts of vanadium, copper, molybdenum, zirconium, titanium, cobalt, manganese, magnesium, iron, nickel and zinc, etc. one or a mixture of any several; the templating agent is one or a mixture of N', N', N, N-tetramethyl-1,6-hexanediamine, tripropylamine or n-propylamine.

The ratio between the raw materials (according to the molecular ratio of oxides) is:

Me/Al ₂ O ₃ =0.01～0.7;

SiO ₂ /Al ₂ O ₃ =0.1～10;

P ₂ O ₅ /Al ₂ O ₃ =0.5～15;

H ₂ O/Al ₂ O ₃ =10～100;

R/Al ₂ O ₃ =0.7～6; R is a mixture of one or several templating agents;

In addition, in the above preparation method, the synthetic crystallization pressure is autogenous pressure or filled with nitrogen, air or inert gas of 0.01-1 Mpa.

The present invention is described in detail below by way of examples.

Example 1 SAPO-56

Dissolve 12.75g of activated alumina (containing Al ₂ O ₃ 73.0wt%) in 75ml of deionized water, and add 10.40g of silica sol (containing SiO ₂ 40wt%) and 26.28g of orthophosphoric acid (containing H ₃ PO ₄ 85wt%) in sequence under stirring %). Finally, 40 g of N',N',N,N-tetramethyl-1,6-hexanediamine was added, stirred and mixed evenly, and then the mixture was transferred into a stainless steel synthesis kettle and sealed. Crystallize at 200°C and autogenous pressure for 24 hours, wash the solid product with deionized water until neutral, dry in air at 100°C, and roast in air at 550°C for 5 hours to obtain SAPO-56 molecular sieve. The XRD analysis is shown in Table 1 shown.

Table 1 No. 2θ d() 100×I/I ₀ 123456789101112131415161718 7.3808.61011.53012.84015.49017.31017.72020.18021.61021.96023.44025.87027.78029.90030.32031.31033.43034.470 11.968910.26167.66866.88905.71585.11885.00124.39684.10894.04423.79213.44123.20882.98592.94552.85462.67822.5998 1858563536446578100243636672438332719

Example 2 TiAPSO-56

Dissolve 12.10g of activated alumina (containing Al ₂ O ₃ 73.0wt%) in 70ml of deionized water, and add 10.40g of silica sol (containing SiO ₂ 40wt%) and 26.28g of orthophosphoric acid (containing H ₃ PO ₄ 85wt%) in sequence under stirring %) to prepare solution A. Mix 2.85g of titanium sulfate (96%) and 5ml of deionized water uniformly to obtain solution B. Add solution B to A with vigorous stirring and stir for not less than 30 minutes. Finally, 40 g of N',N',N,N-tetramethyl-1,6-hexanediamine was added, stirred and mixed evenly, and then the mixture was transferred into a stainless steel synthesis kettle and sealed. Crystallize at 200°C and autogenous pressure for 24 hours, wash the solid product with deionized water until neutral, dry in air at 100°C, and roast in air at 550°C for 5 hours to obtain TiAPSO-56 molecular sieve. The XRD analysis is shown in Table 2 shown. Comparing Table 2 and Table 1, it can be seen that the relative intensity of each diffraction peak in Table 2 changes, indicating that titanium atoms enter the molecular sieve framework to change the pore size and interplanar spacing.

Table 2 No. 2θ d() 100×I/I ₀ 1234567891011121314151617 7.3408.55911.48012.79015.44017.26017.68019.65020.14021.57023.41025.84027.76030.28031.27033.41034.440 12.034110.32157.70186.91585.73425.13355.01254.51414.40544.11653.79693.44513.21102.94932.85812.67982.6020 20646135354247187910032366036302615

Comparative example 1

The amount of N,N,N',N'-tetramethyl-1,6-hexanediamine in Example 2 was changed to 10 g. At this time, the ratio of template agent to Al ₂ O ₃ in the reaction mixture material was 0.62. The dosage, addition order and crystallization conditions of the remaining components were kept unchanged, and the product was TiAPSO-11 molecular sieve, and its XRD analysis is shown in Table 3.

table 3 No. 2θ d() 100×I/I ₀ 123456789101112 8.0709.45013.20015.70020.51021.05022.76023.24024.78026.70028.74033.020 10.94709.35136.70195.63994.32684.21703.90393.82433.59003.33603.10372.7105 2056244777939110029303325

Example 3 FAPSO-56

Dissolve 15.90g of activated alumina (containing Al ₂ O ₃ 73.0wt%) in 70ml of deionized water, and add 12.80g of silica sol (containing SiO ₂ 40wt%) and 19.50g of orthophosphoric acid (containing H ₃ PO ₄ 85wt%) in sequence under stirring %) to prepare solution A. At the same time, 3.27g of iron sulfate (96%) and 5ml of deionized water were uniformly mixed to obtain solution B. Add solution B to A with vigorous stirring and stir for not less than 30 minutes. Finally, 40 g of N',N',N,N-tetramethyl-1,6-hexanediamine was added, stirred and mixed evenly, and then the mixture was transferred into a stainless steel synthesis kettle and sealed. Crystallize at 200°C and autogenous pressure for 24 hours, wash the solid product with deionized water until neutral, dry in air at 100°C, and roast in air at 550°C for 5 hours to obtain FAPSO-56 molecular sieve. The XRD analysis is shown in Table 4 shown. Comparing Table 4 and Table 1, it can be seen that the relative intensity of each diffraction peak in Table 4 changes, indicating that iron atoms enter the molecular sieve framework to change the pore size and interplanar spacing.

Table 4 No. 2θ d() 100×I/I ₀ 123456789101112131415161718 7.3608.55911.48012.81015.45017.27017.70019.66020.15021.58023.42025.84027.77029.87030.28031.28033.42034.460 12.004110.32157.70186.90505.73065.13055.00684.51194.40324.11463.79533.44513.20992.98882.94932.85722.67902.6005 1449602828401001565764535982131262717

Embodiment 4 (ZrAPSO-56)

Solution B in Example 2 was changed to 3.71g zirconium oxychloride (ZrOCl ₂ 8H ₂ O 99%) mixed with 5ml deionized water, and 36g tripropylamine was used as template agent instead of N',N',N,N- Tetramethyl-1,6-hexamethylenediamine, the dosage, addition sequence and crystallization conditions of the other components were unchanged, and the product was ZrAPSO-56 molecular sieve, and its XRD analysis is shown in Table 5. Comparing Table 5 and Table 1, it can be seen that the relative intensity of each diffraction peak in Table 5 changes, indicating that zirconium atoms enter the molecular sieve framework to change the pore size and interplanar spacing.

table 5 No. 2θ d() 100×I/I ₀ 1234567891011121314151617 7.3608.58011.51012.82015.48017.28017.70020.18021.61023.43025.89027.75030.33031.34033.42034.50050.650 11.985110.28557.68556.89975.72695.12465.01254.39684.10893.79373.43863.21222.94452.85192.67902.59761.8008 21616340354667771003944783736292218

Example 5 MnAPSO-56

Solution B in Example 2 is changed to 2.82g manganese acetate (MnAc2 4H2O 99%) is mixed with 5ml deionized water, template agent adopts 10gN ', N ', N, N-tetramethyl-1,6-hexyl The mixing of amine and 25g n-propylamine, the amount of all other components, the order of addition and the crystallization conditions are unchanged, the product is MnAPSO-56 molecular sieve, and its XRD analysis is shown in Table 6. Comparing Table 6 and Table 1, it can be seen that the relative intensity of each diffraction peak in Table 6 changes, indicating that manganese atoms enter the molecular sieve framework to change the pore size and interplanar spacing.

Table 6 No. 2θ d() 100×I/I ₀ 1234567891011121314151617181920 7.3808.60011.52012.83014.81015.49017.29017.71019.66020.17021.60021.94023.45025.86027.79029.90030.28031.30033.44034.470 11.968910.27357.67526.89435.97675.71585.12465.00404.51194.39894.11084.04793.79053.44253.20762.98592.94932.85542.67742.5998 19565838123744681981100223737712539332920

Example 6 CoAPSO-56

Solution B among the embodiment 2 becomes 2.05g cobalt acetate (CoAc 4H O 99.5%) mixes with 5ml deionized water. The dosage, addition order and crystallization conditions of the other components remain unchanged, and the product is CoAPSO-56 molecular sieve.

Example 7 NiAPSO-56

Solution B among the embodiment 2 becomes 2.45g nickel nitrate (Ni(NO3) 6H2O 98%) mixes with 5ml deionized water. The dosage, addition order and crystallization conditions of the other components remain unchanged, and the product is NiAPSO-56 molecular sieve.

Comparative example 2

2.45g of nickel nitrate (Ni(NO3) 2.6H2O 98%) in Example 7 was changed to 19.6g and mixed with 15ml of deionized water. At this time, the molar ratio of metal to Al ₂ O ₃ was 0.75. The dosage, addition sequence and crystallization conditions of the remaining components were unchanged, and the product was an unknown crystal, and its XRD analysis is shown in Table 7.

Table 7 No. 2θ d() 100×I/I ₀ 123456789101112 13.84019.67022.00024.16027.99031.39034.45040.02042.58047.36051.74055.980 6.39344.50964.03703.68073.18562.84752.60122.25112.12151.91751.76541.6413 43436100151418786114

Example 8 CuAPSO-56

Solution B among the embodiment 2 becomes 3.05g copper sulfate (Cu(SO4) 6H2O 98%) mixes with 5ml deionized water. The dosage, addition order and crystallization conditions of the other components remain unchanged, and the product is CuAPSO-56 molecular sieve.

Example 9

The sample obtained in Example 2 was calcined in air at 550°C for 4 hours. Weigh 2 g of the calcined sample and add it into 100 ml of 1M copper chloride solution. Exchange at 50°C for 12 hours, and repeat the exchange 4 times. The obtained sample was filtered, washed with deionized water and dried at 100°C to obtain the sample Cu-TiAPSO-56 after copper ion exchange.

Example 10

A part of the sample obtained in Example 2 was taken out and put into a small crucible, and was baked at 550° C. for 4 hours by feeding air. After accurately weighing the mass of the sample, place it in a desiccator filled with saturated saline. Leave at room temperature for 12 hours. The water absorption value of the sample is obtained by weighing the change in mass before and after the sample. Experiments show that TiAPSO-56 molecular sieve has adsorption property, and its adsorption value for water at room temperature is 29.6%.

Example 11

The sample obtained in Example 1 was calcined at 550° C. for 4 hours in air. Then press into tablets and crush to 20-40 mesh. A 1.28g sample was weighed and loaded into a fixed-bed reactor to evaluate the methanol conversion to light olefins (MTO) reaction. Methanol is carried by nitrogen, its weight space velocity WHSV is 2.0h ^-1 , the reaction temperature is 450°C, and the reaction products are analyzed by online gas chromatography. The results show that the conversion rate of methanol is 100%, the selectivity to C ₂ ⁼ and C ₃ ⁼ is over 70%, and the initial selectivity to C ₂ ⁼ and C ₃ ⁼ is over 60%. It shows that TiAPSO-56 molecular sieve has high activity for MTO reaction.

From the results of the above examples, it can be seen that the present invention uses N', N', N, N-tetramethyl-1,6-hexanediamine, tripropylamine or n-propylamine as the template and controls the amount of the template , MeAPSO-56 molecular sieves can be synthesized by using different metal salts. The synthesis process is simple, the reaction conditions are easy to control, and the method is suitable for industrial application. In addition, the MeAPSO-56 molecular sieve synthesized by the present invention can be used as an ion exchange agent and adsorbent after roasting, and can be used as a catalyst for various hydrocarbon reactions, especially for the reaction of methanol conversion to light olefins, which has a high The high catalytic activity and selectivity to products create conditions for the industrialization of this reaction process.

Claims (12)

1. A metal silicoaluminophosphate molecular sieve MeAPSO-56 is characterized in that the chemical composition in anhydrous state is expressed as mR nMe (SixAlyPz)O ₂ ; wherein R is the template agent present in the micropores of the molecular sieve, and m represents per mole (SixAlyPz)O 2 ; )O ₂ in the number of moles of template agent, m=0.05～0.3; Me is the metal atom entering the molecular sieve framework, n is the mole number of Me in each mole of (SixAlyPz)O ₂ , n=0.001～0.20. x, y, and z represent mole fractions of Si, Al, and P respectively, and the ranges are x=0.01-0.98, y=0.01-0.60, z=0.01-0.52, and x+y+z=1. 2. The metallosilicoaluminophosphate molecular sieve MeAPSO-56 according to claim 1 is characterized in that the metal atom Me is one or any of vanadium, copper, molybdenum, zirconium, titanium, cobalt, manganese, magnesium, iron, nickel and zinc Several kinds, and at least part of them exist in molecular sieves with MeO ₂ tetrahedrons forming the molecular sieve framework. 3. A method for synthesizing metal silicoaluminophosphate molecular sieve MeAPSO-56 is characterized in that it is carried out according to the following steps: (1) Mixing silicon source material, aluminum source material, phosphorus source material, metal salt, templating agent and water in proportion under stirring to obtain an initial gel mixture; (2) Transfer the initial gel mixture material into a stainless steel synthesis kettle, seal it, and crystallize it at 100-250°C for no less than 1 hour; (3) Separating the solid crystalline product from the mother liquor, washing with deionized water until neutral, and drying in the air at 80-130°C to obtain the original powder of metal silicoaluminophosphate molecular sieve; (4) Calcining the raw molecular sieve powder in air at 300-700°C for not less than 3 hours to obtain the active metal silicoaluminophosphate molecular sieve catalyst. 4. According to the synthetic metal silicoaluminophosphate molecular sieve MeAPSO-56 described in claim 3, it is characterized in that each raw material proportioning (by oxide molecular ratio) used is: Me/Al ₂ O ₃ =0.01～0.7; SiO ₂ /Al ₂ O ₃ =0.1～10; P ₂ O ₅ /Al ₂ O ₃ =0.5～15; H ₂ O/Al ₂ O ₃ =10～100; R/Al ₂ O ₃ =0.7～6; R is a mixture of one or several templating agents; 5. According to the method for the metallosilicoaluminophosphate molecular sieve MeAPSO-56 of synthesis described in claim 3, it is characterized in that used silicon source is a kind of in silica sol, silica gel, water glass, activated silica or orthosilicate or a mixture of several. 6. According to the method for the metallosilicoaluminophosphate molecular sieve MeAPSO-56 of synthesis described in claim 3, it is characterized in that the aluminum source used is aluminum salt, aluminate, activated alumina, alkoxy aluminum, pseudoboehmite or pseudothin One or more mixtures of diaspores. 7. According to the method for the metallosilicoaluminophosphate molecular sieve MeAPSO-56 synthesized according to claim 3, it is characterized in that the phosphorus source used is one or more mixtures of orthophosphoric acid, phosphate, organic phosphides or phosphorus oxides. 8. According to the method for the metal silicoaluminophosphate molecular sieve MeAPSO-56 synthesized according to claim 3, it is characterized in that the template used is N', N', N,N-tetramethyl-1,6-hexanediamine, tris One or more mixtures of propylamine or n-propylamine. 9. According to the method for synthesizing metallosilicoaluminophosphate molecular sieve MeAPSO-56 according to claim 3, it is characterized in that the source of metal used is vanadium, copper, molybdenum, zirconium, titanium, cobalt, manganese, magnesium, iron, nickel and zinc etc. One or any mixture of oxides, inorganic salts or organic salts. 10. According to the method for synthesizing metallosilicoaluminophosphate molecular sieve MeAPSO-56 according to claim 3, it is characterized in that the crystallization pressure of synthesis is autogenous pressure or filled with nitrogen, air or inert gas of 0.01～1Mpa. 11. A metal silicoaluminophosphate molecular sieve MeAPSO-56 according to claim 1, used as ion exchanger and adsorbent. 12. The metal silicoaluminophosphate molecular sieve MeAPSO-56 according to claim 1 is used as an adsorbent.