CN111841619B - Modified ZSM-5 molecular sieve catalyst, preparation method and application thereof - Google Patents

Modified ZSM-5 molecular sieve catalyst, preparation method and application thereof Download PDF

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CN111841619B
CN111841619B CN202010788496.9A CN202010788496A CN111841619B CN 111841619 B CN111841619 B CN 111841619B CN 202010788496 A CN202010788496 A CN 202010788496A CN 111841619 B CN111841619 B CN 111841619B
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molecular sieve
zsm
catalyst
acid
modified zsm
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CN111841619A (en
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谭伟
侯珂珂
郭振莲
张凤岐
王耀伟
栾波
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Shandong Chambroad Petrochemicals Co Ltd
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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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Abstract

The invention provides a preparation method of a modified ZSM-5 molecular sieve catalyst, which comprises the steps of sequentially carrying out steam treatment, acid washing treatment and roasting on a ZSM-5 molecular sieve, and then carrying out dipping modification in alkaline phosphate aqueous solution to obtain the modified ZSM-5 molecular sieve catalyst; the temperature of the water vapor treatment is 200-800 ℃, the time of the water vapor treatment is 0.5-6 hours, and the space velocity of the water vapor is 0.1-3 h < -1 >; the concentration of the acid solution used in the acid washing treatment is 0.1-2 mol/L, and the solid-liquid ratio in the acid washing treatment is 1g: (6-12) mL, wherein the temperature of the acid washing treatment is 30-120 ℃, and the time of the acid washing treatment is 1-12 hours. The modified ZSM-5 catalyst can reduce the reaction temperature and the reaction pressure, and simultaneously maintain high product yield. The invention also provides a modified ZSM-5 molecular sieve catalyst and application thereof.

Description

Modified ZSM-5 molecular sieve catalyst, preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a modified ZSM-5 molecular sieve catalyst, a preparation method and application thereof.
Background
3-methyl-3-buten-1-ol is an important intermediate in the organic synthesis industry and can be widely used in production and living. 3-methyl-3-buten-1-ol is useful for producing isoprene, which is used as a raw material for synthetic rubber. Can also be isomerized into 3-methyl-2-butene-1-ol, and can be used for synthesizing pyrethroid pesticides, citral and the like. Can also be used as a raw material for producing new generation polycarboxylic acid series high-efficiency water reducing agent, food and medicine additives, etc.
The catalyst for preparing 3-methyl-3-butene-1-ol by condensation reaction of isobutene and formaldehyde mainly comprises an acidic catalyst and a basic catalyst. The earliest British patent 1205397 is SnCl 4 And ZnC1 2 As a catalyst, the 3-methyl-3-buten-1-ol is prepared by the reaction of isobutene and formaldehyde at 15-100 ℃, the formaldehyde conversion rate is low, and the chloride is used, so that the corrosion is serious. CN102659518 SnC1 2 The immobilized silicon-aluminum molecular sieve is used as a catalyst, isobutene and formaldehyde are adopted to prepare 3-methyl-3-buten-1-ol, the yield of the 3-methyl-3-buten-1-ol product is improved, but extremely toxic SnC1 is used 2 So that its application is limited. Patent US4028424 uses phosphate as catalyst, and adopts paraformaldehyde and isobutene at 150-200 ℃ to obtain 3-methyl-3-butene-1-ol with the yield of 65-92% and 3-methyl-2-butene-1-ol with the yield of 1-6%, but the boiling points of the two are very close, and the later separation cost is high. Geng Yanxia of the university of eastern chemical industry and the like (industrial catalysis, 2005, 13, 346-348) reports that isobutene and paraformaldehyde are used as raw materials, sodium dihydrogen phosphate and ZSM-5 molecular sieve modified by the hydrogen phosphate are used as catalysts, and the yield of 3-methyl-3-butene-1-ol reaches 85 percent. However, a great deal of literature and patent experiments prove that the yield of 3-methyl-3-butene-1-ol is difficult to reach 85% by directly using phosphate as a catalyst and directly loading the phosphate on a ZSM-5 molecular sieve as a catalyst. JP55-113732 and JP58-164534 use ZSM series catalyst, and react for 7 hours at 102 ℃ and 0.98MPa, the formaldehyde conversion rate only reaches 58.2%, the total enol selectivity reaches 79.8%, and the formaldehyde conversion rate is lower.
The existing preparation method for preparing 3-methyl-3-buten-1-ol by isobutene and formaldehyde, in particular to a Prins condensation reaction preparation method adopting a catalyst, has the problems of low catalyst efficiency, high corrosiveness to reaction equipment and serious environmental pollution. Therefore, providing a more suitable catalyst is one of the problems that one skilled in the art would need to solve.
Disclosure of Invention
The invention aims to provide a modified ZSM-5 molecular sieve catalyst, a preparation method and application thereof, and the modified ZSM-5 molecular sieve catalyst has good catalytic effect, avoids the problems of equipment corrosion and environmental pollution of the traditional acidic catalyst, and simultaneously effectively reduces the reaction temperature and the reaction pressure for preparing 3-methyl-3-butene-1-ol.
The invention provides a preparation method of a modified ZSM-5 molecular sieve catalyst, which comprises the following steps:
sequentially carrying out steam treatment, acid washing treatment and roasting on the ZSM-5 molecular sieve, and then carrying out dipping modification on the ZSM-5 molecular sieve by using alkaline phosphate aqueous solution to obtain a modified ZSM-5 molecular sieve catalyst;
the temperature of the water vapor treatment is 200-800 ℃, the time of the water vapor treatment is 0.5-6 hours, and the space velocity of the water vapor is 0.1-3 h < -1 >;
the concentration of the acid solution used in the acid washing treatment is 0.1-2 mol/L, and the solid-liquid ratio in the acid washing treatment is 1g: (6-12) mL, wherein the temperature of the acid washing treatment is 30-120 ℃, and the time of the acid washing treatment is 1-12 hours.
Preferably, the ZSM-5 molecular sieve has a specific surface area>300m 2 /g, pore volume>0.2cm 3 And/g, the silicon-aluminum ratio is 3-800, and the grain size is 30-3000 nm.
Preferably, the roasting temperature is 300-600 ℃; the roasting time is 2-5 hours.
Preferably, the acid used in the acid washing treatment is one or more of hydrochloric acid, nitric acid, phosphoric acid, acetic acid, citric acid and oxalic acid.
Preferably, the alkaline phosphate is one or more of alkaline metal phosphate, alkaline metal dihydrogen phosphate and alkaline metal hydrogen phosphate;
the alkaline metal is one or more of sodium, potassium, cesium, barium, magnesium and calcium;
the concentration of the alkaline phosphate is 0.1-15 wt%.
Preferably, the temperature of the impregnation is 20-60 ℃, and the time of the impregnation is 2-24 hours.
Preferably, the ZSM-5 molecular sieve after the pickling treatment is dried and roasted in sequence, and then impregnated.
Preferably, the ZSM-5 molecular sieve after impregnation is dried and roasted in sequence to obtain the modified ZSM-5 molecular sieve.
The invention provides a modified ZSM-5 molecular sieve catalyst which is prepared by the preparation method;
the active component in the modified ZSM-5 molecular sieve is P 2 O 5 And a basic metal oxide, said P 2 O 5 The mass fraction of the alkaline metal oxide is 5-30%, and the mass fraction of the alkaline metal oxide is 1-25%;
the alkaline metal oxide is one or more of oxides of sodium, potassium, cesium, barium, magnesium and calcium.
The use of a modified ZSM-5 molecular sieve catalyst as described above as a catalyst in the preparation of 3-methyl-3-buten-1-ol by condensation of isobutylene with formaldehyde.
The invention provides a preparation method of a modified ZSM-5 molecular sieve catalyst, which comprises the following steps: sequentially carrying out steam treatment, acid washing treatment and roasting on the ZSM-5 molecular sieve, and then carrying out dipping modification in alkaline phosphate aqueous solution to obtain a modified ZSM-5 molecular sieve catalyst; the temperature of the water vapor treatment is 200-800 ℃, the time of the water vapor treatment is 0.5-6 hours, and the space velocity of the water vapor is 0.1-3 h < -1 >; the concentration of the acid solution used in the acid washing treatment is 0.1-2 mol/L, and the solid-liquid ratio in the acid washing treatment is 1g: (6-12) mL, wherein the temperature of the acid washing treatment is 30-120 ℃, and the time of the acid washing treatment is 1-12 hours. The water vapor, acid washing treatment and alkaline phosphate modification treatment in the invention can adjust the pore structure distribution and acidity (strength and acid quantity) of the ZSM-5 molecular sieve to obtain the catalyst with proper acidity and alkalinity and proper pore channel size. Compared with the prior art, the modified ZSM-5 catalyst has higher catalytic activity and better product diffusivity, can reduce the reaction temperature and the reaction pressure, and simultaneously keeps high product yield. Experimental results show that the modified ZSM-5 molecular sieve catalyst is applied to the reaction of preparing 3-methyl-3-buten-1-ol by condensation reaction of isobutene and paraformaldehyde, the molar ratio of isobutene to formaldehyde is 5-15:1 under the conditions that the reaction temperature is 180-230 ℃ and the reaction pressure is 8-15 MPa, the yield of the product 3-methyl-3-buten-1-ol is up to 95% and the conversion rate of formaldehyde is up to 100%, and the preparation efficiency is effectively improved. And the catalyst is easy to separate after the reaction, so that the operation and energy consumption in the separation aspect are reduced, and the problems of equipment corrosion and environmental pollution caused by the liquid acid catalyst in the traditional production process are solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 shows the yield of 3-methyl-3-buten-1-ol as a function of the number n of catalyst uses in the examples of the present invention.
Detailed Description
The invention provides a preparation method of a modified ZSM-5 molecular sieve catalyst, which comprises the following steps:
sequentially carrying out steam treatment, acid washing treatment and roasting on the ZSM-5 molecular sieve, and then carrying out dipping modification in alkaline phosphate aqueous solution to obtain a modified ZSM-5 molecular sieve catalyst;
the temperature of the water vapor treatment is 200-800 ℃, the time of the water vapor treatment is 0.5-6 hours, and the space velocity of the water vapor is 0.1-3 h < -1 >;
the concentration of the acid solution used in the acid washing treatment is 0.1-2 mol/L, and the solid-liquid ratio in the acid washing treatment is 1g: (6-12) mL, wherein the temperature of the acid washing treatment is 30-120 ℃, and the time of the acid washing treatment is 1-12 hours.
The ZSM-5 molecular sieve catalyst is subjected to steam treatment, acid washing treatment, roasting and alkaline phosphate modification in sequence to obtain the catalyst with proper acidity and alkalinity and proper pore size, and has higher catalytic activity.
Specifically, the ZSM-5 molecular sieve catalyst is preferably subjected to steam treatment and acid washing in sequence, filtering, drying and roasting in sequence after acid washing, finally, soaking in alkaline phosphate aqueous solution, and drying and roasting again to obtain the modified ZSM-5 molecular sieve catalyst.
In the present invention, the ZSM-5 molecular sieve has a specific surface area>300m 2 /g, pore volume>0.2cm 3 And/g, the silicon-aluminum ratio is 3-800, and the grain size is 30-3000 nm. In one embodiment of the invention, the silicon to aluminum ratio is 60. In the present invention, the physicochemical properties of the ZSM-5 molecular sieves of different grain sizes used in the specific examples are shown in Table 1.
TABLE 1 physicochemical Properties of ZSM-5 molecular sieves of different grain sizes
Grain size S BET a (m 2 ·g -1 ) V T b (cm 3 ·g -1 )
80nm 383 0.41
200nm 378 0.24
800nm 354 0.22
3μm 294 0.18
a:BET surface area；b:Total pore volume at P/Po＝0.99。
Preferably, the ZSM-5 molecular sieve is placed in a fixed bed tubular reactor for steam treatment; the temperature of the water vapor treatment is 200-800 ℃, preferably 300-700 ℃, more preferably 300-500 ℃; specifically, in embodiments of the present invention, it may be 300 ℃,500 ℃, or 700 ℃; the water vapor treatment time is 0.5 to 6 hours, preferably 1 to 3 hours. The space velocity of the water vapor treatment is 0.1 to 3 hours -1 Preferably 1 to 1.5h -1 . In one embodiment of the invention, the space velocity of the water vapor treatment is 1h -1 The time was 1h. And discharging the molecular sieve from the tubular reactor after the water vapor treatment is finished.
Soaking the ZSM-5 molecular sieve subjected to the water vapor treatment in an acid solution for pickling treatment, wherein the acid solution is preferably an aqueous solution of inorganic acid or an aqueous solution of organic acid, and the inorganic acid is preferably one or more of hydrochloric acid, nitric acid and phosphoric acid; the organic acid is preferably one or more of acetic acid, citric acid and oxalic acid; the concentration of the acid solution is preferably 0.1 to 2mol/L, more preferably 0.2 to 0.8mol/L, and in particular, may be 0.2mol/L, 0.5mol/L, or 0.8mol/L in the embodiment of the present invention. The solid-to-liquid ratio of the ZSM-5 molecular sieve after the water vapor treatment to the aqueous solution of the inorganic acid is preferably 1g: (6-12) mL, more preferably 1g: (8-10) mL; specifically, in the embodiment of the present invention, 1g may be: 10mL; the solid-to-liquid ratio of the ZSM-5 molecular sieve after the water vapor treatment to the organic acid aqueous solution is preferably 1g: (6-12) mL, more preferably 1g: (8-10) mL; specifically, in the embodiment of the present invention, 1g may be: 10mL. The soaking in the acid solution is preferably performed in a mode of multiple soaking; the number of soaking times is preferably 1 to 3; the time of each soaking is preferably 2-4 hours.
And (3) filtering the ZSM-5 molecular sieve soaked in the acid solution, and sequentially drying and roasting. The drying temperature is preferably 80-120 ℃, more preferably 90-110 ℃ and most preferably 100 ℃; specifically, in one embodiment of the present invention, the drying temperature may be 120 ℃; the drying time is preferably 4 to 24 hours, more preferably 6 to 20 hours, and most preferably 8 to 15 hours; specifically, in one embodiment of the present invention, the drying time may be 12 hours.
The firing temperature is preferably 400 to 600 ℃, more preferably 500 ℃, and in particular, in one embodiment of the present invention, the firing temperature is 500 ℃; the firing time is preferably 2 to 6 hours, more preferably 3 to 5 hours, and in particular, may be 5 hours in one embodiment of the present invention.
The ZSM-5 molecular sieve after roasting is immersed in alkaline phosphate aqueous solution, taken out and dried and roasted again, and the modified ZSM-5 molecular sieve catalyst is obtained.
In the invention, the alkaline phosphate is preferably one or more of alkaline metal phosphate, alkaline metal dihydrogen phosphate and alkaline metal hydrogen phosphate, and the alkaline metal is alkali metal and/or alkaline earth metal, and the alkali metal preferably comprises one or more of sodium, potassium and cesium; the alkaline earth metal preferably comprises one or more of barium, magnesium and calcium. Specifically, the alkaline phosphate may be one or more of sodium phosphate, potassium phosphate, calcium phosphate, barium phosphate, magnesium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, sodium hydrogen phosphate and magnesium hydrogen phosphate, and in particular, in one embodiment of the present invention, sodium hydrogen phosphate may be used. The concentration of the alkaline phosphate is preferably 0.1 to 6wt%.
In the present invention, the impregnation temperature is preferably 20 to 60 ℃, more preferably 30 to 50 ℃, most preferably 20 to 30 ℃, and in particular, in the embodiment of the present invention, the impregnation may be at normal temperature, that is, at 20 to 25 ℃; the impregnation time is preferably 2 to 24 hours, more preferably 5 to 24 hours, and most preferably 8 to 20 hours. The impregnation is preferably carried out in a multiple impregnation mode; the time of each soaking is preferably 2-6 hours; the number of times of impregnation is preferably 3 to 5.
The re-drying temperature is preferably 80-120 ℃, more preferably 90-110 ℃ and most preferably 100 ℃; specifically, in one embodiment of the present invention, the drying temperature may be 120 ℃; the drying time is preferably 4 to 24 hours, more preferably 6 to 20 hours, and most preferably 8 to 15 hours; specifically, in one embodiment of the present invention, the drying time may be 12 hours.
The re-firing temperature is preferably 400 to 600 ℃, more preferably 500 ℃, and in particular, in one embodiment of the present invention, the firing temperature is 500 ℃; the firing time is preferably 2 to 6 hours, more preferably 3 to 5 hours, and in particular, may be 5 hours in one embodiment of the present invention.
According to the modification method, firstly, the ZSM-5 molecular sieve is subjected to steam treatment, the silicon-aluminum ratio of the molecular sieve can be adjusted to a certain extent, secondary holes with a certain proportion are generated due to removal of framework aluminum of the molecular sieve in the steam treatment, but the removed framework aluminum can block pore channels and generate L acid with a certain proportion, so that an acidic aqueous solution with a certain concentration is required to be used for treatment, and non-framework aluminum generated due to the steam treatment or non-framework aluminum contained in the molecular sieve before treatment is removed, so that the blocked pore channels of the molecular sieve are exposed, and the diffusion performance of reactants and products and the capacity of containing carbon deposition are increased; simultaneously, the acid amount of the molecular sieve and the ratio of the B acid to the L acid are adjusted. And finally, loading the active component alkaline phosphate so that the molecular sieve has proper acid quantity, acid strength and proper pore channel structure, and has better reaction performance and stability. The water vapor treatment temperature, time and airspeed in the water vapor treatment process in the modification method of the invention; selection of acid type, concentration of acid aqueous solution, acid treatment temperature, acid treatment time and solid-to-liquid ratio in the acid washing process; the loading and type of active components can have a major impact on the final catalyst performance.
The invention also provides a modified ZSM-5 molecular sieve catalyst which is prepared according to the preparation method.
Active component P of modifier in modified ZSM-5 molecular sieve catalyst in the invention 2 O 5 And alkali/alkaline earth metal oxides; p is calculated according to the weight of the whole modified solid catalyst 2 O 5 The mass percentage of the catalyst is 5-30%, and the mass percentage of the alkali metal/alkaline earth metal oxide is 1-25%. Specifically, in the embodiment of the invention, the active component of the modifier in the modified ZSM-5 molecular sieve catalyst comprises 25 percent of P 2 O 5 And 20% Na 2 O。
The invention also provides an application of the modified ZSM-5 molecular sieve catalyst as a catalyst in preparing 3-methyl-3-buten-1-ol by condensing isobutene and formaldehyde, namely, the invention also provides a preparation method of 3-methyl-3-buten-1-ol, which comprises the following steps:
reacting isobutene with paraformaldehyde in the presence of a catalyst to obtain 3-methyl-3-buten-1-ol; preferably, paraformaldehyde, toluene and isobutene are mixed and reacted in the presence of a catalyst to obtain 3-methyl-3-buten-1-ol;
the catalyst is the modified ZSM-5 molecular sieve catalyst.
In the present invention, the molar ratio of isobutylene to formaldehyde is preferably (5 to 15): 1, more preferably (8 to 12): 1, in particular, in an embodiment of the present invention, may be 15:1, a step of; the temperature of the reaction is preferably 180 to 230 ℃, more preferably 190 to 220 ℃, most preferably 200 to 210 ℃, and in particular, in the embodiment of the invention, the temperature can be 180 ℃,200 ℃ or 230 ℃; the pressure of the reaction is preferably 5 to 15MPa, more preferably 8 to 12MPa, and in particular, in the embodiment of the present invention, may be 5MPa,8MPa or 15MPa; the reaction time is preferably 1 to 5 hours, more preferably 2 to 4 hours, most preferably 2 to 3 hours, and in particular, may be 2 hours in the embodiment of the present invention.
The invention provides a preparation method of a modified ZSM-5 molecular sieve catalyst, which comprises the following steps: sequentially carrying out steam treatment, acid washing treatment and roasting on the ZSM-5 molecular sieve, and then carrying out dipping modification in alkaline phosphate aqueous solution to obtain a modified ZSM-5 molecular sieve catalyst; the temperature of the water vapor treatment is 200-800 ℃, the time of the water vapor treatment is 0.5-6 hours, and the space velocity of the water vapor is 0.1-3 h < -1 >; the concentration of the acid solution used in the acid washing treatment is 0.1-2 mol/L, and the solid-liquid ratio in the acid washing treatment is 1g: (6-12) mL, wherein the temperature of the acid washing treatment is 30-120 ℃, and the time of the acid washing treatment is 1-12 hours. The water vapor, acid washing treatment and alkaline phosphate modification treatment in the invention can adjust the pore structure distribution and acidity (strength and acid quantity) of the ZSM-5 molecular sieve to obtain the catalyst with proper acidity and alkalinity and proper pore channel size. Compared with the prior art, the modified ZSM-5 catalyst has higher catalytic activity and better product diffusivity, can reduce the reaction temperature and the reaction pressure, and simultaneously keeps high product yield. Experimental results show that the modified ZSM-5 molecular sieve catalyst is applied to the reaction of preparing 3-methyl-3-buten-1-ol by condensation reaction of isobutene and paraformaldehyde, the molar ratio of isobutene to formaldehyde is 5-15:1 under the conditions that the reaction temperature is 180-230 ℃ and the reaction pressure is 8-15 MPa, the yield of the product 3-methyl-3-buten-1-ol is up to 95% and the conversion rate of formaldehyde is up to 100%, and the preparation efficiency is effectively improved. And the catalyst is easy to separate after the reaction, so that the operation and energy consumption in the separation aspect are reduced, and the problems of equipment corrosion and environmental pollution caused by the liquid acid catalyst in the traditional production process are solved.
In order to further illustrate the present invention, the following examples are provided to illustrate a modified ZSM-5 molecular sieve catalyst, its preparation method and application, but should not be construed as limiting the scope of the invention.
Example 1
Molecular sieve ZSM-5 (silicon-aluminum ratio 60, grain size 80 nm) was used at 300℃for 1h -1 Treating with water vapor for 1 hr, pickling with 0.2mol/L dilute nitric acid for 1 hr, filtering, stoving at 120 deg.c, roasting at 500 deg.c for 5 hr, and final treatment in sodium hydrogen phosphateSoaking in water solution for 3-5 times at normal temperature for 2-6 hr, stoving at 120 deg.c for 12 hr and roasting at 500 deg.c for 5 hr to obtain modified ZSM-5 molecular sieve catalyst, named Z-1.
Example 2
Molecular sieve ZSM-5 (silicon-aluminum ratio 60, grain size 80 nm) was followed by a reaction at 500℃for 1h -1 Treating water vapor for 1h, then washing with 0.2mol/L dilute nitric acid for 1h, filtering, drying at 120 ℃ and roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution for 3-5 times at normal temperature, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h and roasting at 500 ℃ for 5h, thus obtaining the modified ZSM-5 molecular sieve catalyst which is denoted as Z-2.
Example 3
Molecular sieve ZSM-5 (silicon-aluminum ratio 60, grain size 80 nm) was used at 700℃for 1h -1 Treating water vapor for 1h, then washing with 0.2mol/L dilute nitric acid for 1h, filtering, drying at 120 ℃ and roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution for 3-5 times at normal temperature, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h and roasting at 500 ℃ for 5h, thus obtaining the modified ZSM-5 molecular sieve catalyst which is denoted as Z-3.
Example 4
Molecular sieve ZSM-5 (silicon-aluminum ratio 60, grain size 80 nm) was followed by a reaction at 500℃for 1h -1 Treating water vapor for 1h, then carrying out acid washing for 3h by 0.2mol/L dilute nitric acid, filtering, drying at 120 ℃ and roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution for 3-5 times at normal temperature, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h and roasting at 500 ℃ for 5h, thus obtaining the modified ZSM-5 molecular sieve catalyst which is denoted as Z-4.
Example 5
Molecular sieve ZSM-5 (silicon-aluminum ratio 60, grain size 80 nm) was followed by a reaction at 500℃for 1h -1 Treating water vapor for 1h, then carrying out acid washing for 1h by 0.5mol/L dilute nitric acid, filtering, drying at 120 ℃ and roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution for 3-5 times at normal temperature, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h and roasting at 500 ℃ for 5h, thus obtaining the modified ZSM-5 molecular sieve catalyst which is denoted as Z-5.
Example 6
Molecular sieve ZSM-5 (silicon-aluminum ratio 60, grain size 80 nm) was followed by a reaction at 500℃for 1h -1 Treating water vapor for 1h, then carrying out acid washing for 1h by 0.8mol/L dilute nitric acid, filtering, drying at 120 ℃ and roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution for 3-5 times at normal temperature, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h and roasting at 500 ℃ for 5h, thus obtaining the modified ZSM-5 molecular sieve catalyst which is denoted as Z-6.
Example 7
Molecular sieve ZSM-5 (silicon-aluminum ratio 60, grain size 200 nm) was followed by a reaction at 500℃for 1h -1 Treating water vapor for 1h, washing with 0.2mol/L dilute nitric acid for 1h, filtering, drying at 120 ℃ and roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution for 3-5 times at normal temperature, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h and roasting at 500 ℃ for 5h, thus obtaining the modified ZSM-5 molecular sieve catalyst which is denoted as Z-7.
Example 8
Molecular sieve ZSM-5 (silicon-aluminum ratio 60, grain size 800 nm) was used at 500℃for 1h -1 Treating water vapor for 1h, washing with 0.2mol/L dilute nitric acid for 1h, filtering, drying at 120 ℃ and roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution for 3-5 times at normal temperature, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h and roasting at 500 ℃ for 5h, thus obtaining the modified ZSM-5 molecular sieve catalyst which is denoted as Z-8.
Example 9
Molecular sieve ZSM-5 (silicon-aluminum ratio 60, grain size 3 μm) was used at 500℃for 1h -1 Treating water vapor for 1h, washing with 0.2mol/L dilute nitric acid for 1h, filtering, drying at 120 ℃ and roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution for 3-5 times at normal temperature, wherein the soaking time is 2-6 h each time, drying at 120 ℃ for 12h and roasting at 500 ℃ for 5h, thus obtaining the modified ZSM-5 molecular sieve catalyst which is denoted as Z-9.
The activity of the catalysts prepared in examples 1 to 9 was evaluated. The evaluation conditions were: a500 mL autoclave was used, and 1.0g of the catalyst, 6g of paraformaldehyde and 60g of toluene were placed in the autoclave, sealed, and nitrogen was introduced to remove air from the autoclave. The isobutene metering pump was started and the isobutene feed was controlled at 160g. The molar ratio of isobutene to formaldehyde was 15. The reaction temperature is controlled to be 230 ℃, the reaction pressure is controlled to be 15MPa, the reaction is carried out for 2 hours, and the rest isobutene and the catalyst are removed. And (3) quantitatively analyzing the reacted sample by liquid chromatography and potentiometric titration to obtain formaldehyde conversion rate and quantitatively analyzing by gas chromatography to obtain the yield of the 3-methyl-3-butene-1-ol. The result data are all average results under this condition. The specific reaction results are shown in Table 2.
TABLE 2 reactivity of different catalysts
Figure BDA0002622921430000101
The catalysts obtained by carrying out steam, acid washing treatment, roasting and alkaline phosphate modification on ZSM-5 molecular sieves with different grain sizes (80 nm,200nm,800nm and 3 μm) are respectively corresponding to Z2, Z7, Z8 and Z9, and are used for preparing 3-methyl-3-buten-1-ol from isobutene and paraformaldehyde, and under the optimized reaction conditions, the variation of the yield of the 3-methyl-3-buten-1-ol along with the using times n of the catalyst is shown in figure 1. From the graph, the yield of 3-methyl-3-buten-1-ol is not obviously reduced after the catalyst Z2 is repeatedly used for 10 times, the yield of 3-methyl-3-buten-1-ol is obviously reduced after the catalyst Z7 is repeatedly used for 10 times, the yield of 3-methyl-3-buten-1-ol is obviously reduced after the catalyst Z8 is repeatedly used for 5 times, and the yield of 3-methyl-3-buten-1-ol is obviously reduced after the catalyst Z9 is repeatedly used for 3 times.
According to the data obtained in experimental examples 1-9, the modified ZSM-5 molecular sieve catalyst provided by the invention is used for synthesizing 3-methyl-3-buten-1-ol from isobutene and paraformaldehyde, the yield of 3-methyl-3-buten-1-ol relative to formaldehyde can be up to 95% under the optimized reaction condition, the formaldehyde conversion rate is up to 100%, and the preparation efficiency is effectively improved. Compared with the existing catalyst which is used for synthesizing 3-methyl-3-buten-1-ol by taking isobutene and paraformaldehyde as raw materials, the catalyst can effectively reduce the reaction temperature and the reaction pressure, effectively reduce the cost and has better commercial value.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (1)

1. The application of the modified ZSM-5 molecular sieve catalyst in improving the repeated use performance of the catalyst in the preparation of 3-methyl-3-buten-1-ol by condensing isobutene and formaldehyde;
the modified ZSM-5 molecular sieve catalyst is prepared according to the following preparation method:
the molecular sieve ZSM-5 with the silicon-aluminum ratio of 60 and the grain size of 80nm is firstly carried out at 500 ℃ for 1h -1 Treating water vapor for 1h, then carrying out acid washing for 1h by 0.2mol/L dilute nitric acid, filtering, drying at 120 ℃ and roasting at 500 ℃ for 5h, finally soaking in sodium hydrogen phosphate aqueous solution for 2-6 h at normal temperature for 3-5 times, drying at 120 ℃ for 12h and roasting at 500 ℃ for 5h to obtain a modified ZSM-5 molecular sieve catalyst;
the active component in the modified ZSM-5 molecular sieve is P 2 O 5 And a basic metal oxide, said P 2 O 5 The mass fraction of the alkaline metal oxide is 5-30%, and the mass fraction of the alkaline metal oxide is 1-25%;
the alkaline metal oxide is sodium oxide;
specific surface area of the ZSM-5 molecular sieve>300m 2 /g, pore volume>0.2cm 3 And/g, silicon-aluminum ratio 60, and grain size 80nm.
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