CN111068754A - Composite modified molecular sieve catalyst, preparation method and application thereof - Google Patents
Composite modified molecular sieve catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a modified molecular sieve catalyst of 3-methyl-3-butene-1-ol and a preparation method thereof. The 3-methyl-3-butene-1-ol catalyst takes a molecular sieve as a matrix, adopts water vapor and acid washing treatment and alkaline phosphate composite modification, and can be used for the reaction of synthesizing 3-methyl-3-butene-1-ol from isobutene and paraformaldehyde. Compared with the traditional process, the catalyst provided by the invention has the advantages of proper acidity and alkalinity, proper pore channel size and simple preparation method. Meanwhile, the catalyst is subjected to condensation reaction of isobutene and formaldehyde in the pressure reactor, so that the reaction temperature and the reaction pressure are effectively reduced, the catalyst is easy to separate after the reaction, the operation and the energy consumption in the separation aspect are reduced, and the catalyst provides a great application prospect for producing the 3-methyl-3-butene-1-ol by the isobutene condensation method.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a composite modified molecular sieve catalyst, and a preparation method and application thereof.
Background
3-methyl-3-butylene-1-alcohol is a very important chemical intermediate, can be used for producing various fine chemicals such as spices, medicines, pesticides and vitamins, and can also be used as a raw material for producing a new generation of polycarboxylic acid series high-efficiency water reducing agent. In addition, 3-methyl-3-buten-1-ol can be used for synthesizing rubber by generating isoprene through a dehydration reaction, and can also be used for synthesizing pyrethroid pesticides, citral and the like by generating 3-methyl-2-buten-1-ol through an isomerization reaction.
The catalysts used for the condensation reaction of isobutene with formaldehyde to produce 3-methyl-3-buten-1-ol are mainly classified into two types, namely acidic catalysts and basic catalysts. UK patent 1205397 uses SnCl4And ZnC12The catalyst is used for preparing 3-methyl-3-butene-1-ol by reacting isobutene with formaldehyde at 15-100 ℃, the formaldehyde conversion rate is low, and chloride is seriously corroded. CN102659518 adopts SnC12The immobilized silicon-aluminum molecular sieve takes isobutene and formaldehyde as raw materials to synthesize 3-methyl-3-butylene-1-alcohol, the yield of the product 3-methyl-3-butylene-1-alcohol is improved, but the virulent SnC1 is still used2Are catalysts, so that their use is limited. Patent US4028424 uses phosphate as catalyst, and uses paraformaldehyde and isobutylene at 150-200 ℃ to obtain 65% -92% yield of 3-methyl-3-butene-1-ol and 1% -6% yield of 3-methyl-2-butene-1-ol, which have close boiling points and require high cost for later separation. Gunn Yanxia et al (Industrial catalysis, 2005, 13, 346-2PO4And Na2HPO4The catalyst is prepared by loading the catalyst on a ZSM-5 molecular sieve, and the yield of the 3-methyl-3-butene-1-ol reaches 85 percent. However, a large amount of literature and experiments in patent CN 107930686A prove that the yield of 3-methyl-3-butene-1-ol is difficult to reach 85 percent by directly using phosphate as a catalyst and directly loading the phosphate on a ZSM-5 molecular sieve as the catalyst. Japanese patents JP55-113732 and JP58-164534 adopt ZSM series catalysts to react for 7 hours at 102 ℃ and 0.98MPa, the conversion rate of formaldehyde is only 58.2 percent, the total selectivity of enol is 79.8 percent, and the conversion rate of formaldehyde is lower.By adopting a FeMCM-22 catalyst (stud. surf. Sci. Catal.,1999, p507), the selectivity of 3-methyl-3-buten-1-ol reaches 90% under the condition of 60 ℃, but the formaldehyde conversion rate only reaches 45% when the reaction is carried out for 60 hours, and the industrial requirement is far away. CN107930686 adopts an alkaline phosphate modified phosphorus-silicon-aluminum molecular sieve, isobutene and formaldehyde are used as raw materials, the yield of the obtained 3-methyl-3-butylene-1-alcohol relative to formaldehyde is more than 81%, and the selectivity of the obtained 3-methyl-3-butylene-1-alcohol relative to the generated 3-methyl-3-butylene-1-alcohol is more than 95%. However, the molecular sieve has smaller pore channels, and the molecular sieve quickly loses carbon deposition and inactivation under the condition of higher reaction temperature. CN106582788 takes formaldehyde and isobutene as starting materials, takes a modified ZSM-5 molecular sieve as a catalyst, and performs a Prins condensation reaction in a fixed bed reactor to prepare the 3-methyl-3-butene-1-ol, wherein the yield can reach more than 98 percent, but the reaction conditions are harsh, the pressure is more than 20MPa, and the requirement on equipment is high.
At present, the preparation method of condensing isobutene and formaldehyde Prins to generate 3-methyl-3-butene-1-ol under the condition of a catalyst generally has the problems of low catalyst efficiency, high corrosivity to reaction equipment and serious environmental pollution. Therefore, the development of a more suitable catalyst has become one of the problems that the skilled person needs to solve.
Disclosure of Invention
In view of the above, the present invention aims to provide a composite modified molecular sieve catalyst, a preparation method and an application thereof, wherein the catalyst prepared by the method has high catalytic activity.
The invention provides a preparation method of a composite modified molecular sieve catalyst, which comprises the following steps:
the molecular sieve is put at 400-700 ℃ for 0.2-2 h-1And then, after water vapor treatment for 0.5-5 h, soaking in 0.35-0.45 mol/L inorganic acid aqueous solution or organic acid aqueous solution at the solid-to-liquid ratio (g/ml) of 1: 9.5-10.5 at the temperature of 40-120 ℃ for 2-12 h, filtering, drying and roasting, then soaking in alkaline phosphate aqueous solution, drying again and roasting again to obtain the composite modified molecular sieve catalyst.
Preferably, the basic phosphate is selected from one or more of sodium phosphate, potassium phosphate, dihydrogen phosphate and hydrogen phosphate;
the inorganic acid in the inorganic acid aqueous solution is selected from one or more of hydrochloric acid, nitric acid and phosphoric acid;
the organic acid in the organic acid aqueous solution is selected from one or more of acetic acid, citric acid and oxalic acid.
Preferably, the molecular sieve is selected from one or more of HZSM-5, HZSM-11, H β, HY, HZSM-12, HZSM-22 and HM.
Preferably, the molecular sieve has a specific surface area>300m2G, pore volume>0.2cm3The silicon-aluminum ratio is 3-300.
Preferably, the dipping temperature is 20-40 ℃, and the dipping time is 6-20 h.
Preferably, the drying temperature is 80-120 ℃, and the drying time is 4-10 h; the roasting temperature is 400-550 ℃, and the roasting time is 2-5 h.
Preferably, the temperature of the secondary drying is 60-120 ℃, and the time of the secondary drying is 5-12 h; the temperature of the secondary roasting is 300-600 ℃, and the time of the secondary roasting is 4-6 h.
Preferably, the active component P of the modifier in the composite modified molecular sieve catalyst2O5And an alkali metal oxide, P being calculated on the weight of the whole solid catalyst after modification2O5The content of the alkali metal oxide is 5-35% by mass, and the content of the alkali metal oxide is 5-30% by mass.
The invention provides a composite modified molecular sieve catalyst prepared by the preparation method of the technical scheme.
The invention provides a preparation method of 3-methyl-3-butene-1-ol, which comprises the following steps:
reacting isobutene and paraformaldehyde in a molar ratio of 5-15: 1 at the temperature of 180-230 ℃ under the pressure of 5-15 MPa in the presence of a catalyst to obtain 3-methyl-3-buten-1-ol;
the catalyst is the composite modified molecular sieve catalyst prepared by the preparation method of the technical scheme or the composite modified molecular sieve catalyst of the technical scheme.
The invention provides a preparation method of a composite modified molecular sieve catalyst, which comprises the following steps: the molecular sieve is put at 400-700 ℃ for 0.2-2 h-1And then, after water vapor treatment for 0.5-5 h, soaking in 0.35-0.45 mol/L inorganic acid aqueous solution or organic acid aqueous solution at a solid-to-liquid ratio (g/ml) of 1: 9.5-10.5 at 40-120 ℃ for 2-12 h, filtering, drying and roasting, then soaking in alkaline phosphate aqueous solution, drying again and roasting again to obtain the composite modified molecular sieve catalyst. The molecular sieve is subjected to water vapor treatment, acid washing and alkaline phosphate composite modification, so that the obtained composite modified molecular sieve catalyst has high catalytic activity. The composite modified molecular sieve catalyst can catalyze the condensation of isobutene and paraformaldehyde to generate 3-methyl-3-butene-1-ol; the catalyst can effectively reduce the reaction temperature and the reaction pressure, so that the selectivity of the 3-methyl-3-butene-1-ol is higher, the highest yield of the catalyst relative to formaldehyde is 90%, the conversion rate of the formaldehyde is up to 100%, and the preparation efficiency is effectively improved.
Drawings
FIG. 1 is an SEM image of a catalyst prepared in example 1 of the present invention;
FIG. 2 is NH of the catalyst prepared in example 1 of the present invention3-a TPD map;
FIG. 3 is CO of the catalyst prepared in example 1 of the present invention2-TPD map.
Detailed Description
The invention provides a preparation method of a composite modified molecular sieve catalyst, which comprises the following steps:
the molecular sieve is put at 400-700 ℃ for 0.2-2 h-1And then, after water vapor treatment for 0.5-5 h, soaking in 0.35-0.45 mol/L inorganic acid aqueous solution or organic acid aqueous solution at 40-120 ℃ for 2-12 h, filtering, drying, roasting, soaking in alkaline phosphate aqueous solution, drying again and roasting again to obtain the composite modified molecular sieve catalyst.
The molecular sieve is subjected to water vapor treatment, acid washing and alkaline phosphate composite modification, so that the obtained composite modified molecular sieve catalyst has high catalytic activity. The composite modified molecular sieve catalyst can catalyze the condensation of isobutene and paraformaldehyde to generate 3-methyl-3-butene-1-ol; the catalyst can effectively reduce the reaction temperature and the reaction pressure, so that the selectivity of the 3-methyl-3-butene-1-ol is higher, the highest yield of the catalyst relative to formaldehyde is 90%, the conversion rate of the formaldehyde is up to 100%, and the preparation efficiency is effectively improved.
In the invention, the molecular sieve catalyst has larger specific surface area, can provide larger catalytic reaction sites, also has selective catalytic capability, strong catalytic specificity and simple separation and recycling, and is preferably selected from one or more of HZSM-5, HZSM-11, H β, HY, HZSM-12, HZSM-22 and HM>300m2G, pore volume>0.2cm3The silicon-aluminum ratio is 3-300. The specific surface area of the molecular sieve is preferably 330-600 m2·g-1The pore volume is 0.28-0.46 cm3The silicon-aluminum ratio is 5-80.
The physicochemical properties of the molecular sieves employed in the specific examples of the present invention are shown in Table 1:
TABLE 1 physicochemical Properties of different molecular sieves
a:BET surface area；b:Total pore volume at P/Po＝0.99.
The invention preferably places the molecular sieve in a fixed bed tubular reactor for water vapor treatment; the temperature of the water vapor treatment is 400-700 ℃, and preferably 500-600 ℃; the time of the water vapor treatment is 0.5-5 h, preferably 1-3 h. The airspeed of water vapor treatment is 0.2-2 h-1Preferably 0.8 to 1.5 hours-1More preferably 1 to 1.5 hours-1. In the specific embodiment, the temperature of the water vapor treatment is 500 ℃ and 1h-1The time is 1 h.
And discharging the water vapor from the tubular reactor after the water vapor treatment is finished. Soaking the molecular sieve subjected to water vapor treatment in 0.35-0.45 mol/L inorganic acid aqueous solution or organic acid aqueous solution at 40-120 ℃ for 2-12 h. The inorganic acid in the inorganic acid aqueous solution is selected from one or more of hydrochloric acid, nitric acid and phosphoric acid; the organic acid in the organic acid aqueous solution is selected from one or more of acetic acid, citric acid and oxalic acid. The solid-to-liquid ratio (g/mL) of the molecular sieve subjected to water vapor treatment and the inorganic acid aqueous solution is preferably 1: 9.5-10.5; the solid-to-liquid ratio (g/mL) of the molecular sieve subjected to water vapor treatment and the organic acid aqueous solution is preferably 1: 9.5-10.5. In a specific embodiment, the solid-to-liquid ratio is 1: 10. The concentration of the inorganic acid aqueous solution or the organic acid aqueous solution is 0.35 to 0.45mol/L, preferably 0.38 to 0.42 mol/L; in a specific example, the concentration of the aqueous solution of the inorganic acid or the aqueous solution of the organic acid is 0.4 mol/L. Soaking preferably for multiple times; the soaking frequency is preferably 1-3 times; the time of each soaking is preferably 2-4 h.
Soaking in acid solution, filtering, drying and roasting; the drying temperature is preferably 80-120 ℃, and the drying time is preferably 4-10 h; the roasting temperature is preferably 400-550 ℃, and the roasting time is preferably 2-5 h. In the specific embodiment, the drying temperature is 100 ℃; the roasting temperature is 550 ℃, and the roasting time is 5 hours.
And soaking the roasted molecular sieve in an alkaline phosphate aqueous solution, drying and roasting again to obtain the composite modified molecular sieve catalyst. In the present invention, the basic phosphate is selected from one or more of sodium phosphate, potassium phosphate, dihydrogen phosphate and hydrogen phosphate, preferably from one or more of sodium hydrogen phosphate, potassium dihydrogen phosphate and sodium dihydrogen phosphate. In the invention, the dipping temperature is preferably 20-40 ℃, and the dipping time is 6-20 h. The impregnation is preferably carried out in a multiple impregnation mode; the time of each impregnation is preferably 2-4 h; the number of dipping times is preferably 3 to 5.
In the invention, the temperature for secondary drying is preferably 60-120 ℃, and the time for secondary drying is preferably 5-12 h; the temperature of the secondary roasting is preferably 300-600 ℃, and the time of the secondary roasting is preferably 4-6 h. In a specific embodiment, the temperature for drying again is 100 ℃; the drying time is 10 h; the temperature of the secondary roasting is 550 ℃, and the time of the secondary roasting is 4 hours or 5 hours.
The inventionThe active component P of the modifier in the composite modified molecular sieve catalyst prepared by the method2O5And an alkali metal oxide including Na2O、K2O; calculated as the weight of the entire solid catalyst after modification, P2O5The content of (a) is 5-35% by mass, preferably 10-30% by mass, and the content of the alkali metal oxide is 5-30% by mass, preferably 10-30% by mass. In a specific embodiment, the active component of the modifier in the composite modified molecular sieve catalyst comprises 17% of P2O5And 15% of Na2O; or 21% of P2O5And 18% of Na2O; 21% of P2O5And 19% of Na2O; 19% of P2O5And 15% of Na2O; or 20% of P2O5And 17% of K2O; or 18% of P2O5And 16% of K2O; or 19% of P2O5And 18% of Na2O; or 18% of P2O5And 17% of Na2O; or P2O5And 16% of Na2O; or 16% of P2O5And 14% of K2O。
The invention provides a composite modified molecular sieve catalyst prepared by the preparation method of the technical scheme.
In the present invention, the catalyst has suitable acidity and alkalinity and suitable pore size.
The invention also provides a preparation method of the 3-methyl-3-butene-1-ol, which comprises the following steps:
reacting isobutene and paraformaldehyde in a molar ratio of 5-15: 1 at the temperature of 180-230 ℃ under the pressure of 5-15 MPa in the presence of a catalyst to obtain 3-methyl-3-buten-1-ol;
the catalyst is the composite modified molecular sieve catalyst in the technical scheme.
Compared with the catalyst in the prior art, the catalyst can reduce the reaction temperature and the reaction pressure, so that the selectivity of the 3-methyl-3-butene-1-ol is higher. The catalyst is easy to separate after reaction, reduces the operation and energy consumption in the separation aspect, and solves the problems that the liquid acid catalyst corrodes equipment and pollutes the environment in the traditional production process.
In order to further illustrate the present invention, the following examples are provided to describe in detail a composite modified molecular sieve catalyst, its preparation method and its application, but they should not be construed as limiting the scope of the present invention.
Example 1
HZSM-5 is firstly heated at 500 ℃ for 1h-1Treating with water vapor for 1h, then pickling with 0.4mol/L dilute nitric acid for 2h, drying at 100 ℃, roasting at 550 ℃ for 5h, then soaking in a sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-4 hours each time, drying again at 100 ℃ for 10h, and roasting again at 550 ℃ for 5h to obtain the water vapor treatment-pickling-sodium hydrogen phosphate composite modified molecular sieve catalyst, which is marked as C-1.
Through detection, the composite modified molecular sieve catalyst contains 17 percent of P in the weight of the whole catalyst2O5And 15% of Na2O。
FIG. 1 is an SEM image of a C-1 catalyst prepared in example 1 of the present invention.
FIG. 2 is NH of C-1 catalyst prepared in example 1 of the present invention3-a TPD map;
FIG. 3 is CO of the C-1 catalyst prepared in example 1 of the present invention2-TPD map.
TABLE 2 physicochemical Properties of the C-1 catalyst prepared in example 1
a:BET surface area；b:Totalpore volume at P/Po＝0.99.
Example 2
HZSM-5 is firstly heated at 500 ℃ for 1h-1Treating with water vapor for 1h, then pickling with 0.4mol/L diluted hydrochloric acid for 2h, drying at 100 ℃, roasting at 550 ℃ for 5h, then soaking in sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-4 h each time, drying again at 100 ℃ for 10h, and roasting again at 550 ℃ for 5h to obtain a water vapor partThe physical-pickling-sodium hydrogen phosphate composite modified molecular sieve catalyst is marked as C-2. Through detection, the composite modified molecular sieve catalyst contains P accounting for 21 percent of the weight of the whole catalyst2O5And 18% of Na2O。
Example 3
HZSM-5 is firstly heated at 500 ℃ for 1h-1Treating with water vapor for 1h, then pickling with 0.4mol/L oxalic acid for 2h, drying at 100 ℃, roasting at 550 ℃ for 5h, then soaking in a sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-4 hours each time, drying again at 100 ℃ for 10h, and roasting again at 550 ℃ for 5h to obtain the water vapor treatment-pickling-sodium hydrogen phosphate composite modified molecular sieve catalyst, which is recorded as C-3. Through detection, the composite modified molecular sieve catalyst contains P accounting for 21 percent of the weight of the whole catalyst2O5And 19% of Na2O。
Example 4
HZSM-5 is firstly heated at 500 ℃ for 1h-1Treating with water vapor for 1h, then pickling with 0.4mol/L citric acid for 2h, drying at 100 ℃, roasting at 550 ℃ for 5h, then soaking in a sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-4 h each time, drying again at 100 ℃ for 10h, and roasting again at 550 ℃ for 4h to obtain the water vapor treatment-pickling-sodium hydrogen phosphate composite modified molecular sieve catalyst, which is recorded as C-4. Through detection, the composite modified molecular sieve catalyst contains P accounting for 19 percent of the weight of the whole catalyst2O5And 15% of Na2O。
Example 5
HZSM-11 is first carried out at 500 ℃ for 1h-1Treating with water vapor for 1h, then pickling with 0.4mol/L dilute nitric acid for 2h, drying at 120 ℃, roasting at 550 ℃ for 5h, then soaking in a potassium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-4 h each time, drying again at 100 ℃ for 10h, and roasting again at 550 ℃ for 4h to obtain the water vapor treatment-pickling-potassium hydrogen phosphate composite modified molecular sieve catalyst, which is marked as C-5. Through detection, the composite modified molecular sieve catalyst contains P accounting for 20 percent of the weight of the whole catalyst2O5And 17% of K2O。
Example 6
H β is firstly carried out at 500 ℃ for 1H-1Treating with water vapor for 1h, then pickling with 0.4mol/L dilute nitric acid for 2h, drying at 120 ℃, roasting at 550 ℃ for 5h, then soaking in monopotassium phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-4 h each time, drying again at 100 ℃ for 10h, and roasting again at 550 ℃ for 4h to obtain the water vapor treatment-pickling-monopotassium phosphate composite modified molecular sieve catalyst, which is marked as C-6. Through detection, the composite modified molecular sieve catalyst contains 18 percent of P in the weight of the whole catalyst2O5And 16% of K2O。
Example 7
The HY is firstly at 500 ℃ for 1 hour-1Treating with water vapor for 1h, then pickling with 0.4mol/L dilute nitric acid for 2h, drying at 120 ℃, roasting at 550 ℃ for 5h, then soaking in sodium dihydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-4 h each time, drying again at 100 ℃ for 10h, and roasting again at 550 ℃ for 4h to obtain the water vapor treatment-pickling-sodium dihydrogen phosphate composite modified molecular sieve catalyst, which is marked as C-7. Through detection, the composite modified molecular sieve catalyst contains P accounting for 19 percent of the weight of the whole catalyst2O5And 18% of Na2O。
Example 8
HZSM-12 is first carried out at 500 ℃ for 1h-1Treating with water vapor for 1h, then pickling with 0.4mol/L dilute nitric acid for 2h, drying at 120 ℃, roasting at 550 ℃ for 5h, then soaking in a sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-4 h each time, drying again at 100 ℃ for 10h, and roasting again at 550 ℃ for 4h to obtain the water vapor treatment-pickling-sodium hydrogen phosphate composite modified molecular sieve catalyst, which is marked as C-8. Through detection, the composite modified molecular sieve catalyst contains 18 percent of P in the weight of the whole catalyst2O5And 17% of Na2O。
Example 9
HZSM-22 is firstly processed at 500 ℃ for 1h-1Treating with water vapor for 1h, then pickling with 0.4mol/L dilute nitric acid for 2h, drying at 120 ℃, roasting at 550 ℃ for 5h, then soaking in a sodium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-4 h each time, drying again at 100 ℃ for 10h, and roasting again at 550 ℃ for 4h to obtain the water vapor treatment-pickling-sodium hydrogen phosphate composite modified molecular sieve catalyst, which is marked as C-9. ThroughDetecting that the composite modified molecular sieve catalyst contains 19 percent of P in the weight of the whole catalyst2O5And 16% of Na2O。
Example 10
The HM is firstly 500 ℃ and is 1h-1Treating with water vapor for 1h, then pickling with 0.4mol/L dilute nitric acid for 2h, drying at 120 ℃, roasting at 550 ℃ for 5h, then soaking in a potassium hydrogen phosphate aqueous solution at normal temperature for 3-5 times, wherein the soaking time is 2-4 h each time, drying again at 100 ℃ for 10h, and roasting again at 550 ℃ for 4h to obtain the water vapor treatment-pickling-potassium hydrogen phosphate composite modified molecular sieve catalyst, which is marked as C-10. Through detection, the composite modified molecular sieve catalyst contains P accounting for 16 percent of the weight of the whole catalyst2O5And 14% of K2O。
The activity of the catalysts prepared in examples 1 to 10 was evaluated. The evaluation conditions were: a500 mL high-pressure reaction kettle is adopted, 1.0g of catalyst, 6g of paraformaldehyde and 60-100 g of toluene are filled in the high-pressure reaction kettle, the high-pressure reaction kettle is sealed, and nitrogen is introduced to remove air in the kettle. Starting an isobutene metering pump, and controlling the feeding amount of isobutene to be 100-160 g. Controlling the reaction temperature to be 180-250 ℃, controlling the reaction pressure to be 8-15 MPa, reacting for 2-5 h, and removing the residual isobutene and the catalyst. After the reaction, the formaldehyde conversion rate of the sample is obtained by liquid chromatography and potentiometric titration quantitative analysis, and the 3-methyl-3-butene-1-ol yield is obtained by gas chromatography quantitative analysis. The results data are the average results under these conditions. The results are shown in Table 3:
TABLE 3 results of the reactions under different experimental conditions
From the above examples, the present invention provides a preparation method of a composite modified molecular sieve catalyst, comprising the following steps: the molecular sieve is put at 400-700 ℃ for 0.2-2 h-1Treating with water vapor for 0.5-5 h, soaking in 0.35-0.45 mol/L inorganic acid aqueous solution or organic acid aqueous solution at 40-120 deg.C for 2-12 h, filtering, oven drying, roasting, soaking in alkaline phosphate aqueous solution, oven drying again, and soaking in alkaline phosphate aqueous solution againAnd (5) roasting to obtain the composite modified molecular sieve catalyst. The molecular sieve is subjected to water vapor treatment, acid washing and alkaline phosphate composite modification, so that the obtained composite modified molecular sieve catalyst has high catalytic activity. The composite modified molecular sieve catalyst can catalyze the condensation of isobutene and paraformaldehyde to generate 3-methyl-3-butene-1-ol; the catalyst can effectively reduce the reaction temperature and the reaction pressure, so that the selectivity of the 3-methyl-3-butene-1-ol is higher, the highest yield of the catalyst relative to formaldehyde is 90%, the conversion rate of the formaldehyde is up to 100%, and the preparation efficiency is effectively improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a composite modified molecular sieve catalyst comprises the following steps:
the molecular sieve is put at 400-700 ℃ for 0.2-2 h-1And (2) after water vapor treatment for 0.5-5 h, soaking in 0.35-0.45 mol/L inorganic acid aqueous solution or organic acid aqueous solution at a solid-to-liquid ratio (g/ml) of 1: 9.5-10.5 at 40-120 ℃ for 2-12 h, filtering, drying, roasting, soaking in alkaline phosphate aqueous solution, drying again and roasting again to obtain the composite modified molecular sieve catalyst.
2. The method according to claim 1, wherein the basic phosphate is selected from one or more of sodium phosphate, potassium phosphate, dihydrogen phosphate and hydrogen phosphate;
the inorganic acid in the inorganic acid aqueous solution is selected from one or more of hydrochloric acid, nitric acid and phosphoric acid;
the organic acid in the organic acid aqueous solution is selected from one or more of acetic acid, citric acid and oxalic acid.
3. The method of claim 1, wherein the molecular sieve is selected from one or more of HZSM-5, HZSM-11, H β, HY, HZSM-12, HZSM-22 and HM.
4. The composite modified molecular sieve catalyst of claim 3, wherein the molecular sieve has a specific surface area>300m2G, pore volume>0.2cm3The silicon-aluminum ratio is 3-300.
5. The composite modified molecular sieve catalyst of claim 1, wherein the impregnation temperature is 20-40 ℃ and the impregnation time is 6-20 h.
6. The preparation method according to claim 1, wherein the drying temperature is 80-120 ℃, and the drying time is 4-10 h; the roasting temperature is 400-550 ℃, and the roasting time is 2-5 h.
7. The preparation method of claim 1, wherein the temperature of the re-drying is 60-120 ℃, and the time of the re-drying is 5-12 h; the temperature of the secondary roasting is 300-600 ℃, and the time of the secondary roasting is 4-6 h.
8. The method of claim 1, wherein the active component of the composite modified molecular sieve catalyst is P2O5And an alkali metal oxide; wherein, P is calculated according to the weight of the whole solid catalyst after modification2O5The content of the alkali metal oxide is 5-35% by mass, and the content of the alkali metal oxide is 5-30% by mass.
9. A composite modified molecular sieve catalyst prepared by the preparation method of any one of claims 1 to 8.
10. A preparation method of 3-methyl-3-buten-1-ol comprises the following steps:
reacting isobutene and paraformaldehyde in a molar ratio of 5-15: 1 at the temperature of 180-230 ℃ under the pressure of 5-15 MPa in the presence of a catalyst to obtain 3-methyl-3-buten-1-ol;
the catalyst is a composite modified molecular sieve catalyst prepared by the preparation method of any one of claims 1 to 8 or a composite modified molecular sieve catalyst of claim 9.
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