CN116037128A - Catalyst and preparation method thereof, and method for preparing 4-methyl-1-pentene by dehydrating methyl isobutyl carbinol - Google Patents

Catalyst and preparation method thereof, and method for preparing 4-methyl-1-pentene by dehydrating methyl isobutyl carbinol Download PDF

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CN116037128A
CN116037128A CN202111262302.2A CN202111262302A CN116037128A CN 116037128 A CN116037128 A CN 116037128A CN 202111262302 A CN202111262302 A CN 202111262302A CN 116037128 A CN116037128 A CN 116037128A
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catalyst
oxide
group
source
weight
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向良玉
张筱榕
田保亮
彭晖
唐国旗
宋超
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/615—100-500 m2/g
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
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Abstract

The invention relates to the technical field of alcohol dehydration, in particular to a method for preparing 4-methyl-1-pentene by dehydrating methyl isobutyl carbinol, which comprises the following steps of: 80 to 99.85wt% of a main active component, 0.04 to 9wt% of a group IIA oxide, 0.06 to 8wt% of a group IB oxide, and 0.05 to 7.5wt% of a group IIB oxide; the main active component is selected from at least one of IVB group oxide, IIIA group oxide and IVA group oxide; the catalyst provided by the invention has higher catalytic activity and higher selectivity for generating 4-methyl-1-pentene (alpha-olefin) when being used for methyl isobutyl carbinol dehydration reaction.

Description

Catalyst and preparation method thereof, and method for preparing 4-methyl-1-pentene by dehydrating methyl isobutyl carbinol
Technical Field
The invention relates to the technical field of alcohol dehydration, in particular to a method for preparing 4-methyl-1-pentene by dehydrating methyl isobutyl carbinol.
Background
4-methyl-1-pentene (abbreviated as 4MP 1) is an important branched alpha-olefin, has great application prospect as an important organic chemical raw material, and is superior to LLDPE prepared by using 1-butene or 1-hexene as a comonomer in the aspects of impact resistance, tear resistance, optical properties and the like on the one hand when being copolymerized with ethylene to prepare high-quality linear low-density polyethylene (LLDPE); on the other hand, the polymer can also be used as a monomer for manufacturing poly-4-methyl-1-pentene (TPX), and the TPX can be used in the artificial leather industry for manufacturing high-performance leather release paper; in addition, certain higher alpha-olefins may be copolymerized into impact resistant polymers; in addition, it can be used for producing chemical products such as methyl isobutyl ketone, 2-isobutyl-6-methyl heptene-1, isoprene, etc. At present, the main methods for preparing 4-methyl-1-pentene (4 MP 1) are a propylene dimerization method and a methyl isobutyl carbinol dehydration method, wherein the propylene dimerization method is applied to practical industrial production.
A catalyst for propylene dimerization and a method for preparing the same are disclosed in PCT/IB 2019/055898. The catalyst in the invention is a mixed metal oxide loaded with alkali metal or alkali metal complex, and the mixed metal oxide carrier comprises at least one of metal in 1 st row and metal in 3 rd row, metal in 4 th row or lanthanide. Wherein the alkali metal is sodium (Na), potassium (K), cesium (Cs) or a complex or mixture thereof. The catalyst may have less than 50wt% metal carbonate by using sodium zirconate loaded with potassium metal or a NaK alloy as catalyst, the branched aliphatic olefin having a selectivity of 60% after 6 hours; the ratio of 4-methyl-1-pentene to methylpentene was 93% with potassium zirconate loaded with a NaK alloy as catalyst. However, metallic potassium has strong reducibility and can react with various carriers, thus limiting its further application.
CN111574317a discloses a process for synthesizing 4-methyl-1-pentene, which comprises using alkali salt loaded with alkali metal as catalyst, wherein the alkali metal comprises Na, K and NaK alloy; the propylene is subjected to dimerization reaction on the basis of dehydration and deoxidation, then a separation tower is adopted to separate the mixture, the purity of the 4-methyl-1-pentene obtained through the separation process can reach 99.5%, the yield reaches 85%, and meanwhile, the byproduct of 1-hexene and other alpha-olefins meets the industrial requirements on the 4-methyl-1-pentene polymerization reaction. However, alkali metal catalysts on carbonates have a considerable initiation time and can structurally deteriorate during use.
The production chain distance of 4-methyl-1-pentene has a certain distance to realize industrialization so far, so that a new method and key technology for producing 4-methyl-1-pentene are urgently needed to be explored.
Disclosure of Invention
The invention aims to solve the problems of long initiation time, easily degraded structure, strong reducibility, easy reaction with a carrier and the like of a catalyst for preparing 4-methyl-1-pentene in the prior art, and provides the catalyst and a preparation method thereof as well as a method for preparing 4-methyl-1-pentene by dehydrating methyl isobutyl carbinol.
In order to achieve the above object, the present invention provides in a first aspect a catalyst comprising, based on the total amount of the catalyst: 80 to 99.85wt% of a main active component, 0.04 to 9wt% of a group IIA oxide, 0.06 to 8wt% of a group IB oxide, and 0.05 to 7.5wt% of a group IIB oxide; the main active component is selected from at least one of IVB group oxide, IIIA group oxide and IVA group oxide.
In a second aspect, the present invention provides a method of preparing a catalyst, wherein the method comprises: the main active component source, the IIA source, the IB source and the IIB source are mixed according to the weight ratio of 1:0.0001-0.2:0.0001-0.2: mixing 0.0005-0.2 in solvent to obtain mixed solution; then, the mixed solution is contacted with a precipitator for coprecipitation reaction, and the obtained reaction product is aged; then roasting the aged product; wherein the primary active ingredient source is selected from at least one of a group IVB source, a group IIIA source and a group IVA source.
In a third aspect the present invention provides a catalyst prepared according to the method of the second aspect.
In a fourth aspect, the present invention provides a process for preparing 4-methyl-1-pentene by dehydration of methyl isobutyl carbinol, said process comprising: the methyl isobutyl carbinol is contacted with the catalyst according to the first aspect or the third aspect in the presence or absence of a carrier gas in a reactor to carry out dehydration reaction.
Through the technical scheme, the catalyst provided by the invention has higher catalytic activity and higher selectivity for generating 4-methyl-1-pentene (alpha-olefin) when being used for methyl isobutyl carbinol dehydration reaction; through long-period service life examination, the catalyst provided by the invention has stable catalytic performance, and is capable of accelerating the reaction rate, reducing carbon deposition and slowing down the blocking of pore channels.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As previously mentioned, the first aspect of the present invention provides a catalyst comprising, based on the total amount of the catalyst: 80 to 99.85wt% of a main active component, 0.04 to 9wt% of a group IIA oxide, 0.06 to 8wt% of a group IB oxide, and 0.05 to 7.5wt% of a group IIB oxide; the main active component is selected from at least one of IVB group oxide, IIIA group oxide and IVA group oxide.
The inventors of the present invention found that by introducing a specific content of a secondary active component (group IIA oxide, group ib oxide, and group iib oxide) into a main component, the amount of acidic and medium-strong acidic centers of the catalyst can be controlled within a certain range, and the carbon deposition phenomenon of the catalyst in the dehydration reaction of methyl isobutyl methanol can be suppressed, the catalytic performance of the catalyst can be improved, the selectivity of 4-methyl-1-pentene can be increased, and the occurrence of side reactions (cyclization, dehydrogenation, or hydrogenation) can be suppressed, thereby promoting the efficient progress of the dehydration reaction of methyl isobutyl methanol.
According to the invention, the catalyst preferably comprises, based on the total amount of the catalyst: 90 to 99.65wt% of a primary active ingredient, 0.08 to 4.5wt% of a group IIA oxide, 0.15 to 3wt% of a group IB oxide, and 0.12 to 2.8wt% of a group IIB oxide; under the above preferred conditions, the content of acidic and medium-strong acidic centers in the catalyst can be further optimized, and the selectivity of the catalyst to the product 4-methyl-1-pentene (alpha-olefin) can be improved.
According to the invention, in order to further increase the selectivity of 4-methyl-1-pentene, the weight ratio of the primary active component to the secondary active component is preferably between 10 and 100:1, preferably 15-75:1, a step of; further preferably, in the secondary active component, the weight ratio of the group IIA oxide, the group ib oxide and the group iib oxide is 0.1 to 20:0.1-25:1, preferably 0.25-18:0.3-8:1, more preferably 0.5-9:0.8-4:1.
In some preferred embodiments of the present invention, the content of the main active component is 80 parts by weight or more, preferably 90 to 99.65 parts by weight, for example, 90 parts by weight, 90.5 parts by weight, 91 parts by weight, 91.5 parts by weight, 92 parts by weight, 92.5 parts by weight, 93 parts by weight, 93.5 parts by weight, 94 parts by weight, 94.5 parts by weight, 95 parts by weight, 95.5 parts by weight, 96 parts by weight, 96.5 parts by weight, 97 parts by weight, 97.5 parts by weight, 98 parts by weight, 98.5 parts by weight, 99 parts by weight, 99.65 parts by weight, or any value in the range consisting of any two of the above, per 100 parts by weight of the catalyst.
In some preferred embodiments of the present invention, the group IIA oxide is contained in an amount of 0.04 to 9 parts by weight, preferably 0.08 to 4.5 parts by weight, for example, may be 0.08 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, or any value in the range of any two of the above values, per 100 parts by weight of the catalyst.
In some preferred embodiments of the present invention, the group IB oxide may be contained in an amount of 0.06 to 8 parts by weight, preferably 0.15 to 3 parts by weight, for example, 0.12 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 0.75 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, or any value in the range of any two values mentioned above, per 100 parts by weight of the catalyst, based on the total amount of the catalyst.
In some preferred embodiments of the present invention, the group IIB oxide may be present in an amount of 0.05 to 7.5 parts by weight, preferably 0.12 to 2.8 parts by weight, for example, 0.12 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 0.75 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 2.8 parts by weight, or any value in the range of any two values set forth above, per 100 parts by weight of the catalyst, based on the total amount of the catalyst.
In the present invention, preferably, the main active component is at least one selected from the group consisting of zirconium dioxide, aluminum oxide, titanium dioxide and silicon dioxide; more preferably zirconium dioxide.
According to the invention, the secondary active component is introduced to improve the pore channel diffusivity and the pore structure stability of the catalyst, reduce unnecessary side reactions and better exert the performance of the catalyst; preferably, the group IIA oxide is selected from at least one of magnesium oxide, calcium oxide, strontium oxide and barium oxide; more preferably calcium oxide and/or magnesium oxide.
In the present invention, preferably, the group ib oxide is selected from copper oxide and/or silver oxide; more preferably copper oxide or silver oxide.
In the present invention, preferably, the group IIB oxide is selected from zinc oxide or chromium oxide, most preferably zinc oxide.
In the present invention, the catalyst should also have a specific surface area and pore volume in order to increase the selectivity of the catalyst to α -olefins. Preferably, the specific surface area of the catalyst is 75-165m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the Further preferably, the pore volume of the catalyst is 0.05-0.6mL.g -1 The method comprises the steps of carrying out a first treatment on the surface of the More preferably, the catalyst has a pore volume content of 70-90% in the range of 1.7-2.6nm, for example 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90% or any value in the range of any two values mentioned above, based on the total pore volume of the catalyst.
In the present invention, the specific surface area, pore volume and pore ratio of the pores of different pore radii of the catalyst are measured by a nitrogen adsorption-desorption method, see in particular GB/T6609.35-2009.
According to the invention, the ammonia adsorption capacity of the catalyst is preferably 0.18-0.38 mmol.g -1 Preferably 0.18 to 0.21mmol g -1 . Further preferably, the content of the medium strong acid center is less than 45% based on the total amount of the medium strong acid center and the weak acid center of the catalyst; the amount of the strong acid center in the catalyst means that the catalyst adopts NH 3 TPD test method, NH at 250-450 DEG C 3 Amount of desorption。
The present invention is not particularly limited in the manner of compounding the main component and the group IIA oxide, the group IB oxide, and the group IIB oxide, which may be supported on the main component or dispersed in the main component; preferably dispersed in the main component in the present invention. In the present invention, the dispersion or loading of the group IIA oxide, the group IB oxide, and the group IIB oxide has little influence on the microstructure of the catalyst, and therefore, the obtained catalyst has a similar pore structure to the main component structure.
In the invention, the catalyst can be prepared by adopting the existing method.
In a preferred embodiment of the present invention, the second aspect of the present invention provides a method of preparing a catalyst, wherein the method comprises: the main active component source, the IIA source, the IB source and the IIB source are mixed according to the weight ratio of 1:0.0001-0.2:0.0001-0.2: mixing 0.0005-0.2 in solvent to obtain mixed solution; then, the mixed solution is contacted with a precipitator for coprecipitation reaction, and the obtained reaction product is aged; then roasting the aged product; wherein the primary active ingredient source is selected from at least one of a group IVB source, a group IIIA source and a group IVA source.
In the above catalyst preparation method, those skilled in the art will understand that: if the primary active ingredient source is provided already with the desired amounts of group IIA source, group IB source and group IIB source, then only such a feedstock (primary active ingredient source) need be used for shaping, and if the primary active ingredient source is provided with a low (insufficient) level of group IIA source, group IB source and group IIB source or element, then the desired element may be additionally introduced.
In the present invention, since the group IIA source, the group IB source and the group IIB source are introduced during the preparation of the main active component, the group IIA oxide, the group IB oxide and the group IIB oxide are mainly present in the bulk phase of the main active component, i.e., dispersed in the main active component.
According to the invention, preferably, the group IVB source is a compound containing a group IVB element, preferably selected from a zirconium source and/or a titanium source; preferably, the zirconium source is selected from at least one of zirconium oxychloride, zirconium nitrate, zirconyl nitrate and zirconyl sulfate, more preferably zirconium oxychloride; the titanium source is preferably selected from titanium dioxide; preferably, the group IVA source is a compound containing a group IVA element, preferably selected from a silicon source; preferably the silicon source is selected from aqueous sodium silicate solutions; the group IIIA source is a compound containing a group IIIA element, preferably selected from aluminium sources; preferably the aluminium source is selected from pseudo-boehmite.
According to the invention, preferably, the precipitant is selected from at least one of ammonia, urea, sodium hydroxide and sodium carbonate, preferably ammonia.
In the present invention, the group IIA source is present in the form of a solution of a group IIA salt (referred to as solution A) selected from at least one of a group IIA nitrate, a group IIA formate, a group IIA oxalate and a group IIA lactate; preferably group IIA nitrate; further preferably, the group IIA nitrate is selected from at least one of magnesium nitrate, calcium nitrate, strontium nitrate, and barium nitrate; the solvent in the solution is selected from water and/or ethanol, preferably water.
In the invention, the group IB source exists in the form of a solution (called solution B) of a group IB salt, wherein the group IB salt is selected from at least one of group IB nitrate, group IB formate, group IB oxalate and group IB lactate; preferably a group IB nitrate; further preferably, the group IB nitrate is selected from copper nitrate and/or silver nitrate; the solvent in the solution is selected from water and/or ethanol, preferably water.
In the present invention, the group IIB source is present as a solution of a group IIB salt (referred to as solution C), preferably an aqueous solution of a zinc salt; the zinc salt is at least one of zinc nitrate, zinc formate, zinc oxalate and zinc lactate; preferably zinc nitrate; the solvent in the solution is selected from water and/or ethanol, preferably water.
The invention can mix the solution A, the solution B and the solution C and then add the mixture into a system containing a main active component source, or add the mixture into the system containing the main active component source separately; when separately added to the system containing the main active ingredient source, the order of addition of the solution a, the solution B, and the solution C is not particularly limited.
According to the invention, preferably, the aging conditions include: the temperature is 65 to 95℃and may be, for example, 65℃and 70℃and 75℃and 80℃and 85℃and 90℃and 95℃or any value in the range of any two values; preferably, the aging time is 0.5 to 9 hours, and may be, for example, 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours, or any value in the range of any two values mentioned above.
According to the present invention, preferably, the method further comprises: centrifuging, washing and drying the aged product; the drying time can be reasonably selected according to the drying temperature, the amount of materials and the type of drying equipment, and the condition that the water content of the dried materials does not influence the subsequent roasting is taken into account. Preferably, the drying temperature is 70 to 140 ℃, for example, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, or any value in the range of any two values; the drying time is 4-19h; for example, the value may be 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 14h, 14.5h, 15h, 15.5h, 16h, 16.5h, 17h, 17.5h, 18h, 18.5h, 19h, or any value in the range of any two values.
According to the present invention, the calcination is capable of removing crystal water in the salt and decomposing the salt to form an oxide, and preferably, the conditions of the calcination include: the temperature is 500-1000 ℃ and the time is 2-18h; illustratively, the firing temperature may be 500 ℃, 525 ℃, 550 ℃, 600 ℃, 625 ℃, 650 ℃, 675 ℃, 700 ℃, 725 ℃, 750 ℃, 800 ℃, 825 ℃, 850 ℃, 900 ℃, 925 ℃, 950 ℃, 1000 ℃, or any value in the range of any two values stated above; the firing time may be 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, 15h, 15.5h, 16h, 16.5h, 17h, 17.5h, 18h, or any value in the range of any two values recited above.
In a third aspect the present invention provides a catalyst prepared according to the method of the second aspect.
Preferably, the catalyst comprises, based on the total amount of the catalyst: 80 to 99.85wt% of a main active component, 0.04 to 9wt% of a group IIA oxide, 0.06 to 8wt% of a group IB oxide, and 0.05 to 7.5wt% of a group IIB oxide; preferably, the group IIA oxide, group IB oxide and group IIB oxide are present in a weight ratio of 0.1 to 20:0.1-25:1, a step of; the main active component is selected from at least one of IVB group oxide, IIIA group oxide and IVA group oxide;
preferably, the specific surface area of the catalyst is 75-165m 2 ·g -1 The method comprises the steps of carrying out a first treatment on the surface of the The pore volume of the catalyst is 0.05-0.60 mL.g -1 The method comprises the steps of carrying out a first treatment on the surface of the Further preferably, the catalyst has a pore volume content in the range of from 70 to 90% of the total pore volume of the catalyst, the pore volume being in the range of from 1.7 to 2.6 nm.
Preferably, the catalyst has an ammonia adsorption amount of 0.18 to 0.38 mmol.g -1 The method comprises the steps of carrying out a first treatment on the surface of the The content of the medium strong acid center is less than 45 percent based on the total amount of the medium strong acid center and the weak acid center of the catalyst; in the present invention, the total amount of the strong acid center and the weak acid center in the catalyst is the ammonia adsorption amount of the catalyst.
In a fourth aspect, the present invention provides a method for preparing 4-methyl-1-pentene by dehydrating methyl isobutyl carbinol, wherein the method comprises: contacting methyl isobutyl carbinol with the catalyst according to the first aspect or the third aspect in a reactor in the presence or absence of a carrier gas to carry out dehydration reaction;
preferably, the conditions of the dehydration reaction include: the temperature is 240-360 ℃, preferably 260-340 ℃; the pressure is 0.08-0.24MPa; the volume space velocity of the liquid phase is 0.15 to 0.75h -1 Preferably 0.2-0.5h -1 ；
Preferably, when the carrier gas is present, the flow rate of the carrier gas is 15-45mL min -1 Preferably 15-40mL min -1 。
In the invention, the type of the reactor can be selected according to actual requirements, and can be a fixed bed reactor, a high-pressure stirred tank reactor or a tubular reactor; preferably a fixed bed reactor.
In the following examples, the elemental composition of the catalyst was analyzed by plasma emission spectrometry (ICP-MS); test instrument: VISTA Pro CCD spectrometer (Varian);
the specific surface area, pore volume and the ratio of pore volume of different pore diameters of the catalyst are measured by a nitrogen adsorption-desorption method (BET), see GB/T6609.35-2009; instrument name: a fully automatic physico-chemical adsorption analyzer (Automatic Micropore & Chemisorption Analyzer); instrument model: ASAP2420, MICromeritcs, U.S. A.;
the ammonia adsorption amount of the catalyst adopts NH 3 -TPD test, desorption temperature 120-600 ℃, test conditions: accurately weighing about 0.1g of sample, placing into a sample tube, and purging with He gas at 10deg.C for min -1 Heating to 600 deg.C, standing for 1 hr, cooling to 120 deg.C, and changing gas into 10% NH 3 The mixture of He and the catalyst is adsorbed for 60min, then the mixture is changed into He and purged for 1h, counting is started after the baseline is stabilized, and the temperature is 10 ℃ for min -1 And (5) heating to 600 ℃, keeping for 30min, stopping recording, and completing the experiment. Integrating and calculating the peak area to obtain NH 3 Desorption amount (basic site of catalyst); test instrument: a full-automatic chemical adsorption instrument (Automated Catalyst Characterization System); instrument model: autochem 2920, MICROMERITICS, inc. of America;
the amount of the strong acid center in the catalyst is the same as that of the ammonia adsorption amount test method of the catalyst, except that: the desorption temperature is 250-450 ℃;
the carbon deposition amount of the catalyst adopts O 2 -TPO test, test conditions are: accurately weighing 0.2g of sample, taking argon with the flow rate of 40mL/min as carrier gas, pretreating the sample at 150 ℃ for 60min, cooling to 100 ℃, performing temperature programming oxidation process by programming at the speed of 10 ℃/min to 900 ℃ under the condition that the mixed gas of oxygen with the flow rate of 40mL/min and argon (the oxygen volume fraction is 20%) is taken as analysis gas, and detecting CO in the temperature programming process 2 Signals of gases such as CO. Test instrument: a full-automatic programmed temperature chemical adsorption instrument; instrument model: autochem II 2920, micromeritics Inc. of America.
Example 1
369g of zirconyl nitrate, 9.13g of calcium nitrate tetrahydrate, 1.97g of copper nitrate trihydrate and 4.32g of zinc nitrate hexahydrate are dissolved in 3L of deionized water to prepare the zirconium element with the concentration of 0.53mol L -1 、Ca 2+ The concentration is 0.013mol L -1 、Cu 2+ At a concentration of 0.003mol L -1 、Zn 2+ The concentration is 0.005mol L -1 Is a mixed solution of (a) and (b); dropwise adding an ammonia water solution (25 wt%) into the mixture under the conditions of water bath at 85 ℃ and vigorous stirring, and adjusting the pH to 9.9 to obtain a precipitate system; standing the precipitate system in a beaker for 2.5h; then, centrifugal separation is carried out, and the obtained precipitate is washed with deionized water to a pH=6.5, and then dried at 70 ℃ for 2 hours and at 130 ℃ for 2 hours; finally, roasting the dried product in a muffle furnace at 500 ℃ for 2 hours to obtain a sample ZrO 2 CaO/CuO/ZnO, designated as catalyst A-1, and the test results are shown in tables 1 and 2.
Example 2
220.74g of pseudo-boehmite, 27.48g of calcium nitrate tetrahydrate, 3.71g of silver nitrate and 1.19g of zinc nitrate hexahydrate were dissolved in 3L of deionized water; dropwise adding an ammonia water solution (25 wt%) into the mixture under the conditions of water bath at 65 ℃ and vigorous stirring, and adjusting the pH to 10 to obtain a precipitate system; standing the sediment system in a beaker for 2.4 hours; then, centrifugal separation is carried out, and the obtained precipitate is washed with deionized water to a pH=6.5, and then dried at 80 ℃ for 2 hours and at 120 ℃ for 2 hours; finally, roasting the dried product in a muffle furnace at 900 ℃ for 2 hours to obtain a sample Al 2 O 3 /CaO/Ag 2 O/ZnO, designated as catalyst A-2, and the test results are shown in tables 1 and 2.
Example 3
127.79g of titanium dioxide, 0.54g of calcium nitrate tetrahydrate, 4.50g of silver nitrate and 6.54g of zinc nitrate hexahydrate are dissolved in 3L of deionized water; dropwise adding an ammonia water solution (25 wt%) into the mixture under the conditions of water bath at 95 ℃ and vigorous stirring, and adjusting the pH to 9.9 to obtain a precipitate system; standing the sediment system in a beaker for 2.4 hours; then, centrifugal separation is carried out, and the obtained precipitate is washed with deionized water to have the pH value of=6.5, and then dried for 2 hours at 750 ℃ and then dried for 2 hours at 135 ℃; finally, roasting the dried product in a muffle furnace at 900 ℃ for 2 hours to obtain a sample TiO 2 /CaO/Ag 2 O/ZnO, designated as catalyst A-3, and the test results are shown in tables 1 and 2.
Example 4
195.2g of sodium silicate, 9.37g of tetrahydrateCalcium nitrate, 1.45g copper nitrate trihydrate, 0.93g zinc nitrate hexahydrate were dissolved in 3L deionized water; dropwise adding an ammonia water solution (25 wt%) into the mixture under the conditions of 70 ℃ water bath and vigorous stirring, and adjusting the pH to 10 to obtain a precipitate system; standing the precipitate system in a beaker for 2.5h; then, centrifugal separation is carried out, and the obtained precipitate is washed with deionized water to a pH=6.5, and then dried at 85 ℃ for 2 hours and 140 ℃ for 2 hours; finally, roasting the dried product in a muffle furnace at 550 ℃ for 2 hours to obtain a sample SiO 2 CaO/CuO/ZnO, designated as catalyst A-4, and the test results are shown in tables 1 and 2.
Example 5
369g of zirconyl nitrate, 0.66g of calcium nitrate tetrahydrate, 8.67g of silver nitrate and 2.38g of zinc nitrate hexahydrate are dissolved in 3L of deionized water to prepare the zirconium element with the concentration of 0.53mol L -1 、Ca 2+ The concentration is 0.001mol L -1 、Ag + The concentration is 0.017mol L -1 、Zn 2+ At a concentration of 0.003mol L -1 Is a mixed solution of (a) and (b); dropwise adding an ammonia water solution (25 wt%) into the mixture under the conditions of water bath at 65 ℃ and vigorous stirring, and adjusting the pH to 10.1 to obtain a precipitate system; standing the precipitate system in a beaker for 2.5h; then, centrifugal separation is carried out, and the obtained precipitate is washed with deionized water to a pH=6.5, and then dried at 85 ℃ for 2 hours and at 135 ℃ for 2 hours; finally, roasting the dried product in a muffle furnace at 700 ℃ for 2 hours to obtain a sample ZrO 2 /CaO/Ag 2 O/ZnO, designated as catalyst A-5, and the test results are shown in tables 1 and 2.
Example 6
369g of zirconyl nitrate, 37.4g of calcium nitrate tetrahydrate, 0.43g of silver nitrate and 6.05g of cadmium nitrate tetrahydrate are dissolved in 3L of deionized water to prepare the zirconium element with the concentration of 0.54mol L -1 、Ca 2+ At a concentration of 0.053mol L -1 、Ag + The concentration is 0.00088mol L -1 、Cd 2+ The concentration is 0.006mol L -1 Is a mixed solution of (a) and (b); dropwise adding an ammonia water solution (25 wt%) into the mixture under the conditions of water bath at 60 ℃ and vigorous stirring, and adjusting the pH to 9.8 to obtain a precipitate system; standing the sediment system in a beaker for 2.4 hours; then enterCentrifugal separation is carried out, and the obtained precipitate is washed by deionized water until the pH value is=6.5, then dried for 2 hours at 90 ℃ and dried for 2 hours at 125 ℃; finally, roasting the dried product in a muffle furnace at 650 ℃ for 2 hours to obtain a sample ZrO 2 /CaO/Ag 2 The O/CdO, designated catalyst A-6, was tested and the results are shown in tables 1 and 2.
Example 7
369g of zirconyl nitrate, 18.81g of magnesium nitrate hexahydrate, 12.46g of copper nitrate trihydrate and 0.86g of zinc nitrate hexahydrate are dissolved in 3L of deionized water to prepare the zirconium element with the concentration of 0.54mol L -1 、Mg 2+ The concentration is 0.024mol L -1 、Cu 2+ The concentration is 0.022mol L -1 、Zn 2+ The concentration is 0.001mol L -1 Is a mixed solution of (a) and (b); dropwise adding an ammonia water solution (25 wt%) into the mixture under the conditions of 75 ℃ water bath and intense stirring, and regulating the pH to be 10.1 to obtain a precipitate system; standing the precipitate system in a beaker for 2.7h; then, centrifugal separation is carried out, and the obtained precipitate is washed with deionized water to a pH=6.5, and then dried at 70 ℃ for 2 hours and at 135 ℃ for 2 hours; finally, roasting the dried product in a muffle furnace at 800 ℃ for 2 hours to obtain a sample ZrO 2 MgO/CuO/ZnO, designated as catalyst A-7, and the test results are shown in tables 1 and 2.
Example 8
369g of zirconyl nitrate, 0.13g of barium nitrate, 51.82g of copper nitrate trihydrate and 0.36g of zinc nitrate hexahydrate are dissolved in 3L of deionized water to prepare the zirconium element with the concentration of 0.54mol L -1 、Ba 2+ The concentration is 0.00017mol L -1 、Cu 2+ The concentration is 0.066mol L -1 、Zn 2+ At a concentration of 0.0004mol L -1 Is a mixed solution of (a) and (b); dropwise adding an ammonia water solution (25 wt%) into the mixture under the conditions of water bath at 85 ℃ and vigorous stirring, and regulating the pH to 10 to obtain a precipitate system; standing the precipitate system in a beaker for 2.8 hours; then, centrifugal separation is carried out, and the obtained precipitate is washed with deionized water to a pH=6.5, and then dried at 85 ℃ for 2 hours and 125 ℃ for 2 hours; finally, roasting the dried product in a muffle furnace at 850 ℃ for 2 hours to obtain a sample ZrO 2 BaO/CuO/ZnO, noted as catalystThe test results of the chemical agent A-8 are shown in tables 1 and 2.
Example 9
369g of zirconyl nitrate, 36.24g of strontium nitrate, 0.17g of silver nitrate and 54.05g of zinc nitrate hexahydrate are dissolved in 3L of deionized water to prepare the zirconium element with the concentration of 0.54mol L -1 、Sr 2+ At a concentration of 0.057mol L -1 、Ag + The concentration is 0.00034mol L -1 、Zn 2+ The concentration is 0.0606mol L -1 Is a mixed solution of (a) and (b); dropwise adding an ammonia water solution (25 wt%) into the mixture under the conditions of water bath at 90 ℃ and vigorous stirring, and adjusting the pH to 10.1 to obtain a precipitate system; standing the sediment system in a beaker for 2.3 hours; then, centrifugal separation is carried out, and the obtained precipitate is washed with deionized water to a pH=6.5, and then dried at 90 ℃ for 2 hours and at 130 ℃ for 2 hours; finally, roasting the dried product in a muffle furnace at 650 ℃ for 2 hours to obtain a sample ZrO 2 /SrO/Ag 2 O/ZnO, designated as catalyst A-9, and the test results are shown in tables 1 and 2.
Comparative example 1
A catalyst was prepared in the same manner as in example 1 except that zirconia powder was used as a main active component source and that the catalyst was prepared at a calcination temperature of 500℃to give a sample ZrO 2 (powder)/CaO/CuO/ZnO was designated as catalyst D-1, and the test results are shown in tables 1 and 2.
Comparative example 2
A catalyst was prepared in the same manner as in example 1 except that zirconia powder was used as a main active component source and the catalyst was prepared at a calcination temperature of 1200℃and cooled to give a sample ZrO 2 (powder)/CaO/CuO/ZnO, designated as catalyst D-2, and the test results are shown in tables 1 and 2.
Comparative example 3
369g of zirconyl nitrate, 9.13g of calcium nitrate tetrahydrate and 1.97g of copper nitrate trihydrate are dissolved in 3L of deionized water to prepare the zirconium element with the concentration of 0.53mol L -1 、Ca 2+ The concentration is 0.013mol L -1 、Cu 2+ At a concentration of 0.003mol L -1 Is a mixed solution of (a) and (b); dropwise adding ammonia water in water bath at 85 ℃ under vigorous stirringThe solution (25 wt%) was adjusted to a pH of 9.9 to give a precipitate system; standing the precipitate system in a beaker for 2.5h; then, centrifugal separation is carried out, and the obtained precipitate is washed with deionized water to a pH=6.5, and then dried at 70 ℃ for 2 hours and at 130 ℃ for 2 hours; finally, roasting the dried product in a muffle furnace at 500 ℃ for 2 hours to obtain a sample ZrO 2 CaO/CuO, designated as catalyst D-3, and the test results are shown in tables 1 and 2.
Comparative example 4
A catalyst was prepared in the same manner as in example 1 except that 72g of zinc nitrate hexahydrate was dissolved in 3L of deionized water to obtain a sample ZrO 2 CaO/CuO/ZnO, designated as catalyst D-4, and the test results are shown in tables 1 and 2.
Comparative example 5
369g of zirconyl nitrate, 9.13g of calcium nitrate tetrahydrate and 4.32g of zinc nitrate hexahydrate are dissolved in 3L of deionized water to prepare the zirconium element with the concentration of 0.53mol L -1 、Ca 2+ The concentration is 0.013mol L -1 、Zn 2+ The concentration is 0.005mol L -1 Is a mixed solution of (a) and (b); dropwise adding an ammonia water solution (25 wt%) into the mixture under the conditions of water bath at 85 ℃ and vigorous stirring, and adjusting the pH to 9.9 to obtain a precipitate system; standing the precipitate system in a beaker for 2.5h; then, centrifugal separation is carried out, and the obtained precipitate is washed with deionized water to a pH=6.5, and then dried at 70 ℃ for 2 hours and at 130 ℃ for 2 hours; finally, roasting the dried product in a muffle furnace at 500 ℃ for 2 hours to obtain a sample ZrO 2 CaO/ZnO, designated as catalyst D-5, and the test results are shown in tables 1 and 2.
Comparative example 6
A catalyst was prepared in the same manner as in example 1 except that 72g of copper nitrate trihydrate was weighed and dissolved in 3L of deionized water to obtain a sample ZrO 2 CaO/CuO/ZnO, designated as catalyst D-6, and the test results are shown in tables 1 and 2.
Comparative example 7
369g of zirconyl nitrate, 1.97g of copper nitrate trihydrate and 4.32g of zinc nitrate hexahydrate are dissolved in 3L of deionized water to prepare the zirconium element with the concentration of 0.53mol L -1 、Cu 2+ At a concentration of 0.003mol L -1 、Zn 2+ The concentration is 0.005mol L -1 Is a mixed solution of (a) and (b); dropwise adding an ammonia water solution (25 wt%) into the mixture under the conditions of water bath at 85 ℃ and vigorous stirring, and adjusting the pH to 9.9 to obtain a precipitate system; standing the precipitate system in a beaker for 2.5h; then, centrifugal separation is carried out, and the obtained precipitate is washed with deionized water to a pH=6.5, and then dried at 70 ℃ for 2 hours and at 130 ℃ for 2 hours; finally, roasting the dried product in a muffle furnace at 500 ℃ for 2 hours to obtain a sample ZrO 2 The catalyst was designated as catalyst D-7, and the test results are shown in tables 1 and 2.
Comparative example 8
A catalyst was prepared in the same manner as in example 1, except that 124g of calcium nitrate tetrahydrate was weighed and dissolved in 3L of deionized water to obtain a sample ZrO 2 CaO/CuO/ZnO, designated as catalyst D-8, and the test results are shown in tables 1 and 2.
Comparative example 9
A catalyst was prepared in the same manner as in example 1 except that the catalyst was prepared at a calcination temperature of 250℃to give a sample ZrO 2 CaO/CuO/ZnO (250 ℃ C.) was designated as catalyst D-9, and the test results are shown in tables 1 and 2.
Comparative example 10
A catalyst was prepared in the same manner as in example 1 except that the catalyst was prepared at a calcination temperature of 1000℃to give a sample ZrO 2 CaO/CuO/ZnO (1000 ℃ C.) was designated as catalyst D-10, and the test results are shown in tables 1 and 2.
TABLE 1
Figure BDA0003326221450000161
Figure BDA0003326221450000171
Note that: * the amount refers to the weight of group IIA oxide relative to 100g of catalyst;
** the content refers to the weight of group IB oxide relative to 100g of catalyst;
*** the content refers to the weight of group IIB oxide relative to 100g of catalyst.
TABLE 2
Figure BDA0003326221450000172
Note that: * the medium strong acid refers to the percentage content of the amount of the medium strong acid center of the catalyst based on the total amount of the weak acid center and the amount of the medium strong acid center of the catalyst;
* 1.7-2.6nm means that the pore volume with the pore diameter in the range of 1.7-2.6nm accounts for the percentage of the total pore volume of the catalyst.
Test example 1
This test example is used to illustrate the process for the preparation of 4-methyl-1-pentene by dehydration of methyl isobutyl carbinol (MIBC).
50mL of the catalyst was weighed and charged into a fixed bed reactor, and preheated at 300℃for 1 hour with nitrogen, methyl isobutyl carbinol was fed into the reaction system by means of a metering pump, and the liquid phase volume space velocity of methyl isobutyl carbinol was 0.3 hour -1 The dehydration reaction was carried out in a reactor at 310℃and at 0.1MPa, and after the reaction was stabilized (i.e., after 500 hours of reaction), the reaction solution was sampled and analyzed, and the analysis results are shown in Table 2.
The sampling analysis method is gas chromatography analysis, and calibration is carried out by preparing a correction factor of a standard sample;
conversion and selectivity were calculated based on the molar content of each component in the reaction liquid (methyl isobutyl carbinol is abbreviated as MIBC, 4-methyl-1-pentene is 4MP1, 4-methyl-2-pentene is 4MP2, and methyl isobutyl ketone is MIBK).
MIBC conversion = 100% -n 1 /[(n 1 +n 2 +n 3 +n 4 )+2×n 5 ]×100％
4MP1 selectivity = n 2 /[(n 2 +n 3 +n 4 )+2×n 5 ]×100％
4MP2 selectorSelectivity = n 3 /[(n 2 +n 3 +n 4 )+2×n 5 ]×100％
Wherein n is 1 The molar content of MIBC in the reaction solution; n is n 2 The molar content of 4MP1 in the reaction liquid; n is n 3 The molar content of 4MP2 in the reaction liquid; n is n 4 The molar content of MIBK in the reaction liquid; n is n 5 The molar content of the oligomer in the reaction solution.
4MP1 duty cycle = 4MP 1/(4MP2+4MP1). Times.100%
The 4MP1 ratio is the ratio of 4MP1 selectivity to the sum of 4MP1 and 4MP2 selectivity, i.e. the ratio of alpha-olefin to the sum of alpha-olefin and beta-olefin, indicating that the reaction produces more alpha-olefin, i.e. the selectivity of alpha-olefin is high.
TABLE 3 Table 3
Figure BDA0003326221450000181
Figure BDA0003326221450000191
As can be seen from Table 3, the conversion and selectivity of the composite catalysts A-1 to A-9 were not significantly changed after the catalytic reaction for 1800 hours compared with 500 hours, the conversion reduction of MIBC was not higher than 1.5%, the reduction of 4MP1 was not higher than 1%, the conversion and selectivity of the comparative catalysts D-1 to D-10 were significantly reduced after the catalytic reaction for 1800 hours compared with 500 hours, the conversion was reduced by 20-40%, and the 4MP1 was reduced by 22% -44%. In addition, after 1800 hours of catalytic reaction, the carbon deposition amount of the catalyst prepared by the embodiment of the invention is lower than 2wt%; the carbon deposition of the catalyst prepared by the comparative example reaches 3.5 to 7.6 weight percent, which shows that the catalyst prepared by the embodiment of the invention has longer service life.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (12)

1. A catalyst characterized in that the catalyst comprises, based on the total amount of the catalyst: 80 to 99.85wt% of a main active component, 0.04 to 9wt% of a group IIA oxide, 0.06 to 8wt% of a group IB oxide, and 0.05 to 7.5wt% of a group IIB oxide;
the main active component is selected from at least one of IVB group oxide, IIIA group oxide and IVA group oxide.
2. The catalyst of claim 1, wherein the catalyst comprises, based on the total amount of the catalyst: 90 to 99.65wt% of a main active component, 0.08 to 4.5wt% of a group IIA oxide, 0.15 to 3wt% of a group IB oxide, and 0.12 to 2.8wt% of a group IIB oxide.
3. The catalyst of claim 1 or 2, wherein the weight ratio of the group IIA oxide, the group ib oxide, and the group iib oxide is from 0.1 to 20:0.1-25:1, preferably 0.5-9:0.8-4:1.
4. A catalyst according to any one of claims 1 to 3, wherein the primary active component is selected from at least one of zirconium dioxide, aluminium oxide, titanium dioxide and silicon dioxide;
preferably, the group IIA oxide is selected from at least one of magnesium oxide, calcium oxide, strontium oxide, and barium oxide;
preferably, the group ib oxide is selected from copper oxide and/or silver oxide;
preferably, the group IIB oxide is selected from zinc oxide.
5. The catalyst according to any one of claims 1 to 4, wherein the specific surface area of the catalyst is 75 to 165m 2 ·g -1 ；
Preferably, the pore volume of the catalyst is 0.05-0.6mL.g -1 ；
Preferably, the catalyst has a pore volume content in the range of from 70 to 90% of the total pore volume of the catalyst, the pore size being in the range of from 1.7 to 2.6 nm.
6. The catalyst according to any one of claims 1 to 5, wherein the ammonia adsorption amount of the catalyst is 0.18 to 0.38 mmol.g -1 ；
Preferably, the content of the medium strong acid center is less than 45% based on the total of the medium strong acid center and the weak acid center of the catalyst.
7. A method of preparing a catalyst, the method comprising: the main active component source, the IIA source, the IB source and the IIB source are mixed according to the weight ratio of 1:0.0001-0.2:0.0001-0.2: mixing 0.0005-0.2 in solvent to obtain mixed solution; then, the mixed solution is contacted with a precipitator for coprecipitation reaction, and the obtained reaction product is aged; then roasting the aged product;
wherein the primary active ingredient source is selected from at least one of a group IVB source, a group IIIA source and a group IVA source.
8. The method according to claim 7, wherein the group IVB source is a compound containing a group IVB element, preferably selected from a zirconium source and/or a titanium source; preferably, the zirconium source is selected from at least one of zirconium oxychloride, zirconium nitrate, zirconyl nitrate and zirconyl sulfate;
preferably, the titanium source is selected from titanium dioxide;
preferably, the group IVA source is a compound containing a group IVA element, preferably selected from a silicon source; preferably the silicon source is selected from aqueous sodium silicate solutions;
preferably, the group IIIA source is a group IIIA element-containing compound, preferably selected from aluminum sources; preferably the aluminium source is selected from pseudo-boehmite;
preferably, the precipitant is selected from at least one of ammonia, urea, sodium hydroxide and sodium carbonate, preferably ammonia.
9. The method of claim 7 or 8, wherein the aging conditions comprise: the temperature is 65-95 ℃ and the time is 0.5-9h;
preferably, the roasting conditions include: the temperature is 500-1000 ℃ and the time is 2-18h.
10. A catalyst prepared by the process of any one of claims 7-9.
11. A method for preparing 4-methyl-1-pentene by dehydrating methyl isobutyl carbinol, comprising: contacting methyl isobutyl carbinol with the catalyst of any one of claims 1-6 and 10 in a reactor in the presence or absence of a carrier gas to effect dehydration;
preferably, the conditions of the dehydration reaction include: the temperature is 240-360 ℃, preferably 260-340 ℃; the pressure is 0.08-0.24MPa; the volume space velocity of the liquid phase is 0.15 to 0.75h -1 Preferably 0.2-0.5h -1 ；
Preferably, when the carrier gas is present, the flow rate of the carrier gas is 15-45mL min -1 Preferably 15-40mL min -1 。
12. The method of claim 11, wherein the reactor is selected from a fixed bed reactor, an autoclave reactor, or a tubular reactor; preferably a fixed bed reactor.
CN202111262302.2A 2021-10-28 2021-10-28 Catalyst and preparation method thereof, and method for preparing 4-methyl-1-pentene by dehydrating methyl isobutyl carbinol Pending CN116037128A (en)

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