CN107899609B - Catalyst for producing polyformaldehyde dimethyl ether and preparation method thereof - Google Patents
Catalyst for producing polyformaldehyde dimethyl ether and preparation method thereof Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
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Abstract
The invention discloses a catalyst for producing polyoxymethylene dimethyl ether and a preparation method thereof. The catalyst components comprise a high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve and a binder, wherein the content of the high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve is 60-90 wt% and the balance is the binder on the basis of the weight of the catalyst; the preparation method of the high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve comprises the following steps: the preparation method comprises the steps of uniformly mixing raw materials of a silicon source, an aluminum source, an alkali source, a mixed template agent and water according to a ratio at room temperature, and carrying out pre-crystallization, washing, drying, roasting and modification to obtain the silicon-aluminum-based composite material. Compared with the existing catalyst, the catalyst of the invention has the advantages of easy separation of the catalyst, high conversion rate of reactants and DMM (dimethyl formamide) when being used for preparing polyformaldehyde dimethyl ether from methanol or methylal3‑8The (polyoxymethylene dimethyl ether) has the advantages of high selectivity, environmental friendliness and the like.
Description
Technical Field
The invention relates to a catalyst, in particular to a catalyst for producing polyoxymethylene dimethyl ether and a preparation method thereof.
Background
Polyoxymethylene dimethyl ether (DMM)n) Is a general name of a polyether substance, namely a mixture PODE3-4Can be used as diesel oil additive for improving combustion condition of diesel oil in engine, increasing heat efficiency, and improving diesel oilThe starting performance of the oil engine and the effect of reducing the emission of tail gas black smoke are very obvious; simultaneous PODE2-4The solvent oil can be used as an aromatic-free green environment-friendly solvent, has the dissolving capacity far exceeding that of aromatic hydrocarbon, can be completely mutually dissolved with hydrocarbon solvents, can obviously improve the dissolving performance of solvent oil on rubber and solvent oil, and is an ideal paint solvent and coating solvent; PODE3-4Is also an ideal pesticide solubilizer and can improve the intersolubility of pesticide active components and water. Therefore, the development of the catalyst for producing the polyoxymethylene dimethyl ethers with high efficiency, environmental protection and low cost has important significance.
Patent CN 200580036662 discloses a method for preparing a catalyst by using inorganic acid, sulfonic acid, acidic ion exchange resin and the like as catalysts, reacting trioxane and methylal as raw materials at 100 ℃ and autogenous pressure for 16h, wherein the conversion rate of methylal is 51.3%, and DMM (dimethyl formamide)2-4The selectivity was 41.4%. Although the catalyst is low in cost, the conversion rate of reactants is low, the product selectivity is low, the strong acidity can corrode equipment, the catalyst is not easy to separate products, and the environment is polluted.
Patent CN 201510673672 discloses a catalyst using yellow acid type polystyrene cation exchange resin and permanent magnetic ferrite to react for 4h at 130 ℃ and 0.8MPa autogenous pressure, the methanol conversion rate is 96.5%, DMM2-4The selectivity was 65.7%. However, the sulfonic acid group has poor thermal stability and low degree of freedom, is not easy to exchange with cations of other macromolecules, and has short service life due to the sulfonation reverse reaction of the aromatic sulfonic acid resin.
The patent CN 101182367 discloses a method for preparing a DMM (dimethyl formamide) catalyst, which adopts ionic liquid as a catalyst, adopts methanol or methylal as raw materials, and reacts with trioxymethylene at the reaction temperature of 60-120 ℃, the conversion rate of the trioxymethylene reaches 88.7 percent3-8The selectivity reaches 43.7 to 53.4 percent. The catalyst has the defects of high cost and difficult product separation.
The patent CN 201210325065 discloses a method for loading SO4 by using SBA-15, MCM-41 or MCM-22 molecular sieve as a carrier2-/ZrO2、SO4 2-/Fe2O3、Cl-/TiO2Or Cl-/Fe2O3At least one solid superacid in the reaction system is used as a catalyst, the methanol conversion rate is 91.8 percent, and DMM (dimethyl formamide)2-4The selectivity was 42.8%. However, the irregular pore structure of the solid super acid makes the selectivity of the by-product methylal in the product to be 20-50%, and the large amount of methylal can reduce the flash point of the diesel mixture and thus damage the quality of the diesel mixture.
Patent CN 201210150310 discloses a method for preparing polyoxymethylene dimethyl ethers by using HZSM-5 or HZSM-11 as a catalyst and methanol or dimethyl ether and formaldehyde or trioxymethylene as raw materials. The conversion rate of formaldehyde or trioxymethylene is about 80 percent, and DMM3-8The selectivity is about 30%. Meanwhile, in the catalyst, because the pore channels of the active components ZSM-5 and ZSM-11 are small, carbon deposition is easy to generate to cause catalyst poisoning, and the activity of the catalyst is reduced.
Patent CN 103755535A discloses a catalyst prepared from HMCM-22 molecular sieve, methanol or methylal and toluene trimer as raw materials, and DMM3-8The yield of (A) is 28.23 to 63.00 wt%, and the activity of the catalyst is not described in the patent.
Disclosure of Invention
The invention aims to provide a high-activity high-DMM3-8A selective and environment-friendly MCM-22/ZSM-35 eutectic molecular sieve with high silica-alumina ratio, a preparation method of a catalyst and application thereof in producing polyoxymethylene dimethyl ether from methanol.
The invention provides a catalyst containing an MCM-22/ZSM-35 eutectic molecular sieve, which comprises the MCM-22/ZSM-35 eutectic molecular sieve with high silica alumina ratio and a binder, wherein the content of the MCM-22/ZSM-35 eutectic molecular sieve with high silica alumina ratio is 60-90 wt% and the rest is the content of the binder on the basis of the weight of the catalyst.
The synthesis process of the high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve comprises the following steps: the preparation method comprises the steps of uniformly stirring and mixing raw materials according to the molar ratio of a silicon source to an aluminum source to an alkali source to a template agent to water of 1: 0.001-0.002: 0.005-0.045: 0.1-1: 6-8.5 at room temperature, pre-crystallizing at 75-90 ℃ for 24-72 hours, crystallizing at 180-220 ℃ for 20-96 hours, washing, drying,And (4) roasting to obtain the catalyst. Silicon source, aluminum source and alkali source according to oxide SiO2:Al2O3:Na2And (4) measuring O. The ratio of MWW/FER crystalline phase in the synthesized high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve is 95/5-70/30.
In the catalyst, the content of the MCM-22/ZSM-35 eutectic molecular sieve with high silica-alumina ratio is 60 wt% -90 wt%, and preferably 70 wt% -85 wt%.
The silicon source for synthesizing the high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve is one or more of silica sol, sodium silicate, silica gel or tetraethoxysilane; the aluminum source is one or more of sodium metaaluminate, aluminum sulfate and SB powder; the alkali source is one or more of sodium hydroxide and potassium hydroxide; the mixed template agent is a mixed solution of hexamethylene imine and n-butylamine, wherein the hexamethylene imine accounts for 10-15% (weight ratio), and the n-butylamine accounts for 85-90%.
The crystallization temperature of the MCM-22/ZSM-35 eutectic molecular sieve with high silica-alumina ratio synthesized by the method is preferably 195-215 ℃; the crystallization time is preferably 30-50 h; the roasting conditions are as follows: roasting at 550 ℃ for 2-3 h, and roasting at 580 ℃ for 3-6 h. The ratio of MWW/FER crystal phase in the synthesized eutectic molecular sieve is 95/5-70/30, preferably 85/15-70/30.
The catalyst is a modified molecular sieve with high silica-alumina ratio MCM-22/ZSM-35, and the modification conditions are that the concentration of ammonium acetate and/or acetic acid solution is 0.01-0.5 mol/L, the liquid-solid volume ratio of the ammonium acetate and/or acetic acid solution to the molecular sieve is 6-8: 1, the temperature is 60-70 ℃, and the treatment time is 1-4 hours.
The adhesive is alumina and/or silicon dioxide.
The preparation method of the catalyst comprises the following steps: uniformly mixing a high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve, a binder, sesbania powder and dilute nitric acid, kneading, molding, drying and roasting to obtain a catalyst; the addition amounts of the sesbania powder and the dilute nitric acid are respectively 0.5 wt% -5.0 wt% and 1.0 wt% -10.0 wt% of the total weight of the eutectic molecular sieve and the binder component dry basis.
Drying conditions for the catalyst preparation of the invention: the drying temperature is 100-120 ℃, and the drying time is 2-12 h; roasting conditions are as follows: the roasting temperature is 500-600 ℃, and the roasting time is 4-10 h.
The catalyst of the invention is suitable for the reaction of preparing polyoxymethylene dimethyl ether by converting methanol or methylal. The catalyst can be applied to a stainless steel high-pressure reaction kettle. The conditions for preparing the polyoxymethylene dimethyl ethers by converting the methanol or the methylal are as follows: the mass ratio of the methanol or methylal to the trioxymethylene is 1.0-6.0, the reaction temperature is 100-200 ℃, the reaction time is 5-40 h, and the catalyst consumption is 0.2-6.0 wt% of the total reactants.
Compared with the prior art, the MCM-22/ZSM-35 eutectic molecular sieve is synthesized by using the mixed template agent and adopting a synthesis mode of pre-crystallization and high-temperature crystallization, so that the crystallization time can be effectively reduced, the eutectic molecular sieve with a proper crystal phase ratio can be obtained, and the synthesis cost can be obviously reduced. The synthesized MCM-22/ZSM-35 eutectic molecular sieve with high silica-alumina ratio has the pore canal properties of the two molecular sieves and also has proper acid strength and acid content, so when the molecular sieve is used for producing the catalyst of the polyformaldehyde dimethyl ether after being modified, the catalyst and the product are easy to separate, the catalyst activity is high (the highest conversion rate of methanol or methylal is 99.8 percent), and the DMM has high activity3-8High selectivity (up to 70.89%), environment friendliness, etc.
Drawings
FIG. 1 is an XRD pattern of the MCM-22 molecular sieve synthesized in comparative example 1
FIG. 2 is an XRD pattern of MCM-22/ZSM-35 synthesized in example 1
FIG. 3 is an XRD pattern of MCM-22/ZSM-35 synthesized in example 2
FIG. 4 is an XRD pattern of MCM-22/ZSM-35 synthesized in example 3
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
210g of silica gel, 1.2g of sodium metaaluminate, 14.6g of sodium hydroxide, 26.3g of template agent (10 wt% of which is hexamethyleneimine and 90 wt% of which is n-butylamine) and 442g of deionized water are sequentially mixed and stirred uniformly, added into a 1L high-pressure reaction kettle, pre-crystallized for 48h at 75 ℃, crystallized for 60h at 180 ℃ and autogenous pressure, washed, dried at 120 ℃ for 10h, calcined at 500 ℃ for 3h, calcined at 583 ℃ for 5h to obtain MCM-22/ZSM-35 eutectic molecular sieve raw powder with high silica-alumina ratio, mixed with ammonium acetate solution with concentration of 0.5 mol/L and ammonium solid-liquid ratio of 1:6, treated in 70 ℃ water bath for 3h, washed, dried and calcined at 550 ℃ for 3 h.
60g of the modified MCM-22/ZSM-35 eutectic molecular sieve is mixed with 30g of alumina, 4g of sesbania powder and 6g of dilute nitric acid, extruded into strips, dried for 3 hours at 80 ℃ and roasted for 4 hours at 550 ℃ to obtain the catalyst A.
Example 2
179g of silica gel, 0.8g of sodium metaaluminate, 8.7g of sodium hydroxide, 130g of template agent (12 wt% of hexamethyleneimine and 88 wt% of n-butylamine) and 430g of deionized water are sequentially mixed and stirred uniformly, added into a 1L high-pressure reaction kettle, pre-crystallized for 72h at 85 ℃, crystallized for 72h at 200 ℃ and autogenous pressure, washed, dried for 3h at 120 ℃, roasted for 3h at 500 ℃, roasted for 5h at 583 ℃ to obtain MCM-22/ZSM-35 eutectic molecular sieve raw powder with high silica-alumina ratio, the raw powder is mixed with ammonium acetate solution with concentration of 0.1 mol/L in a solid-liquid ratio of 1:7, treated in 80 ℃ water bath for 2h, washed, dried and roasted for 3h at 550 ℃.
Taking 70g of the modified MCM-22/ZSM-35 eutectic molecular sieve, mixing with 28g of alumina, 2g of sesbania powder and 3g of dilute nitric acid, extruding into strips, drying at 80 ℃ for 3h, and roasting at 550 ℃ for 4h to obtain the catalyst B.
Example 3:
167g of silica gel, 0.67g of sodium metaaluminate, 6.1g of sodium hydroxide, 131g of template agent (15 wt% of hexamethyleneimine and 85 wt% of n-butylamine) and 441g of deionized water are sequentially mixed and stirred uniformly, added into a 1L high-pressure reaction kettle, pre-crystallized for 72h at 85 ℃, crystallized for 24h at 210 ℃ and autogenous pressure, washed, dried at 120 ℃ for 3h, roasted at 500 ℃ for 3h, roasted at 583 ℃ for 5h to obtain MCM-22/ZSM-35 eutectic molecular sieve raw powder with high silica-alumina ratio, the raw powder is mixed with 0.3 mol/L solution of ammonium acetate solution with solid-liquid ratio of 1:5, treated in 80 ℃ water bath for 2h, washed, dried and roasted at 550 ℃ for 4 h.
And mixing 80g of the modified MCM-22/ZSM-35 eutectic molecular sieve with 18g of alumina, 3g of sesbania powder and 3g of dilute nitric acid, extruding into strips, drying at 80 ℃ for 3h, and roasting at 550 ℃ for 4h to obtain the catalyst C.
Example 4:
adding a catalyst A into a reaction kettle, wherein the mass fraction of the catalyst A is 3%, adding methanol and trioxymethylene with the molar ratio of 1:1, stirring, reacting at the temperature of 150 ℃ for 10 hours, and centrifuging the reactant to obtain a liquid product, and analyzing the liquid product by using a gas chromatography. The results show that the conversion of methanol is 99.3%, DMM in the product3-8The yield of (D) was 38.43 wt%.
Example 5:
adding 5 mass percent of catalyst B into a reaction kettle, adding methanol and trioxymethylene with the molar ratio of 2:1, stirring, reacting at 180 ℃ for 20 hours, and centrifuging the reactant to analyze a liquid product by using a gas chromatography. The results show that the conversion of methanol is 99.5%, DMM3-8The yield of (B) was 43.76% by weight.
Example 6:
adding a C catalyst into a reaction kettle, wherein the mass fraction of the C catalyst is 5%, adding methanol and trioxymethylene with the molar ratio of 3:1, stirring, heating to 200 ℃, reacting for 20 hours, and centrifuging the reactant to obtain a liquid product, and analyzing the liquid product by using a gas chromatography. The results showed that the conversion of methanol was 99.7%, DMM3-8The yield of (B) was 47.63 wt%.
Example 7:
adding 6 mass percent of catalyst B into a reaction kettle, adding methylal and trioxymethylene with the molar ratio of 6:1, stirring, reacting at 200 ℃ for 15 hours, centrifuging the reactants, and analyzing the liquid product by using a gas chromatography. The results show that the conversion of methanol is 99.8%, for DMM3-8The yield of (D) was 69.02 wt%
Example 8:
adding a C catalyst into a reaction kettle, wherein the mass fraction of the C catalyst is 6%, adding methylal and trioxymethylene with the molar ratio of 8:1, stirring, reacting at the temperature of 200 ℃ for 15 hours, and centrifuging the reactants to obtain a liquid product, and analyzing the liquid product by using a gas chromatography. The results show that the conversion of methanol is 99.8%, for DMM3-8The yield of (D) was 70.89 wt%.
Comparative example 1:
adding 103g of silica gel, 2.1g of sodium metaaluminate, 5.7g of sodium hydroxide, 51.2g of template hexamethyleneimine and 535g of deionized water into a 1L high-pressure reaction kettle in sequence, crystallizing at 150 ℃ and autogenous pressure for 160h, washing, drying, roasting at 550 ℃ for 3h, and roasting at 580 ℃ for 5h to obtain MCM-22 molecular sieve raw powder, mixing the raw powder with an acetic acid solution ammonium solid-liquid ratio of 0.3 mol/L of 1:5, treating in 80 ℃ water bath for 2h, washing, drying, and roasting at 550 ℃ for 4 h.
60g of the modified MCM-22 molecular sieve is mixed with 30g of alumina, 5g of sesbania powder and 5g of dilute nitric acid, extruded into strips, dried for 3 hours at 80 ℃, and roasted for 3 hours at 550 ℃ to obtain a catalyst D.
Comparative example 2:
adding a catalyst D into a reaction kettle, wherein the mass fraction of the catalyst D is 6%, adding methanol and trioxymethylene with the molar ratio of 4:1, stirring, reacting at the temperature of 200 ℃ for 20 hours, and centrifuging the reactant to obtain a liquid product, and analyzing the liquid product by using a gas chromatography. The results show that the conversion of methanol is 90.5%, for DMM3-8The yield of (D) was 34.72 wt%.
Comparative example 3:
adding a catalyst D into a reaction kettle, wherein the mass fraction of the catalyst D is 6%, the molar ratio of methylal to trioxymethylene is 6:1, stirring, reacting at 200 ℃ for 30 hours, and centrifuging the reactant to obtain a liquid product, and analyzing the liquid product by using a gas chromatography. The results show that the conversion of methanol is 91.6%, for DMM3-8The yield of (D) was 54.72 wt%.
Claims (11)
1. A catalyst for producing polyoxymethylene dimethyl ether comprises high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve and binder, wherein the content of the high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve is 60 wt% -90 wt%, and the balance is the binder;
the high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve is prepared by the following steps: stirring the raw materials at room temperature according to the molar ratio of 1: 0.001-0.002: 0.005-0.045: 0.1-1: 6-8.5 of silicon source, aluminum source, alkali source, mixed template agent and waterUniformly mixing, pre-crystallizing at 75-90 ℃ for 24-72 h, crystallizing at 180-220 ℃ for 20-96 h, washing, drying, roasting and modifying to obtain the product; the silicon source, the aluminum source and the alkali source are oxide SiO2、Al2O3、Na2Measuring O; the mixed template agent comprises, by mass, 10-15 wt% of hexamethyleneimine and 85-90 wt% of n-butylamine.
2. The catalyst of claim 1, wherein the high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve has a content of 60 wt% to 85 wt%.
3. The catalyst according to claim 1, characterized in that the silicon source for synthesizing the high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve is one or more of silica sol, sodium silicate, silica gel and ethyl orthosilicate; the aluminum source is one or more of sodium metaaluminate, aluminum sulfate and SB powder; the alkali source is one or two of sodium hydroxide and potassium hydroxide.
4. The catalyst according to claim 1, wherein the temperature for synthesizing the high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve is 195-215 ℃.
5. The catalyst according to claim 1, wherein the crystallization time for synthesizing the high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve is 30-50 h.
6. The catalyst of claim 1, wherein the calcination conditions for synthesizing the high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve are as follows: roasting at 550 ℃ for 2-3 h, and then roasting at 580 ℃ for 3-6 h.
7. The catalyst of claim 1, wherein the modification conditions comprise that the ammonium acetate and/or acetic acid solution is treated for 1-4 hours at a concentration of 0.01-0.5 mol/L, a liquid-solid volume ratio of the ammonium acetate and/or acetic acid solution to the high silica-alumina ratio MCM-22/ZSM-35 eutectic molecular sieve of 6-8: 1 and a temperature of 60-70 ℃, and the catalyst is washed, dried and roasted for 2-6 hours at 550 ℃.
8. The catalyst according to claim 1, characterized in that the binder is alumina and/or silica.
9. A process for preparing a catalyst as claimed in any one of claims 1 to 8, comprising the steps of: uniformly mixing a high silica alumina ratio MCM-22/ZSM-35 eutectic molecular sieve, a binder, sesbania powder and dilute nitric acid, kneading, molding, drying and roasting to obtain a catalyst; the addition amounts of the sesbania powder and the dilute nitric acid are respectively 0.5 wt% -5.0 wt% and 1.0 wt% -10.0 wt% of the total weight of the eutectic molecular sieve and the binder component dry basis.
10. The method for preparing a catalyst according to claim 9, characterized in that the drying conditions are: the drying temperature is 100-120 ℃, and the drying time is 2-12 h; the roasting condition is as follows: the roasting temperature is 500-600 ℃, and the roasting time is 4-10 h.
11. The catalyst of any one of claims 1 to 8, which is used in a reaction for preparing polyoxymethylene dimethyl ether by conversion of methanol or methylal.
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