CN109999904B - Catalyst for preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol and preparation method and application thereof - Google Patents

Catalyst for preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol and preparation method and application thereof Download PDF

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CN109999904B
CN109999904B CN201910355955.1A CN201910355955A CN109999904B CN 109999904 B CN109999904 B CN 109999904B CN 201910355955 A CN201910355955 A CN 201910355955A CN 109999904 B CN109999904 B CN 109999904B
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catalyst
isobutene
methylacrolein
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CN109999904A (en
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刘俊霞
陈景润
王军峰
张伟
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Shaanxi Yanchang Petroleum Group Co Ltd
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    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • 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
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself

Abstract

The invention discloses a catalyst for preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol, a preparation method and application thereof, wherein the catalyst has the following structural general formula: moaVbBicCodAgeXfYgOhThe formula is shown in the specification, wherein X is any one of Rb and Cs; y is any one of Fe, Mn, Sb, Sn, Ni and Nb; a. b, c, d, e, f, g and h are the atomic numbers of Mo, V, Bi, Co, Ag, X, Y and O elements in the catalyst respectively, the value of a is 12, the value of b is 4-5, the value of c is 2-3, the value of d is 3-5, the value of e is 1-2, the value of f is 1-2, the value of g is 2-3, and h is the oxygen atomic number required by meeting the oxidation state of other elements; z is a titanium silicalite molecular sieve. The catalyst can perform catalytic reaction at 180-200 ℃, and the reaction condition is milder.

Description

Catalyst for preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol, and particularly relates to a catalyst for preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol, and a preparation method and application thereof.
Background
For a long time, the byproduct isobutene of a refinery is mainly used for producing methyl tert-butyl ether (MTBE), and the production of the methyl tert-butyl ether by the isobutene is convenient and fast in method, simple in process and considerable in economic benefit. However, at present, the country advocates the use of ethanol gasoline for vehicles, which means that refineries do not produce gasoline products for vehicles any more, but instead produce ethanol gasoline blend component oils for vehicles (GB 22030-2017). Since the ethanol gasoline standard (GB 18351-2017) is a mandatory standard, the oxygen-containing compounds in the ethanol gasoline except ethanol are required not to exceed 0.5 percent and cannot be artificially added. This means that MTBE and the like will not continue to be useful as a gasoline high octane blending component. As is known, more than 180 MTBE production devices exist in China at present, the annual capacity is about 1700 million tons, and with the popularization and the use of the ethanol gasoline for vehicles, the isobutene used for the mass production of the MTBE faces the dilemma that high added value conversion is needed.
Therefore, the improvement of the high value-added conversion of the isobutene used by the MTBE is of great significance. In the prior art, 2-methylacrolein is prepared by catalyzing oxidation of isobutene or tertiary butanol, but the catalyst used in the reaction has higher reaction temperature, generally 800-.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst for preparing 2-methylacrolein by catalyzing isobutene or tert-butyl alcohol and a preparation method thereof, and also provides an application of the catalyst for preparing 2-methylacrolein, when the catalyst is used for preparing 2-methylacrolein, the reaction condition is mild, and the reaction temperature can be reduced to about 180 ℃.
A catalyst for preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol, wherein the catalyst has the following structural general formula: moaVbBicCodAgeXfYgOh/Z，
Wherein, X is any one of Rb and Cs;
y is any one of Fe, Mn, Sb, Sn, Ni and Nb;
a. b, c, d, e, f, g and h are the atomic numbers of Mo, V, Bi, Co, Ag, X, Y and O elements in the catalyst respectively, the value of a is 12, the value range of b is 4-5, the value range of c is 2-3, the value range of d is 3-5, the value range of e is 1-2, the value range of f is 1-2, the value range of g is 2-3, and h is the oxygen atomic number required by meeting the oxidation state of other elements;
z is a titanium silicalite molecular sieve; preferably, Z is titanium silicalite TS-1.
The preparation method of the catalyst comprises the following steps:
(1) dissolving ammonium molybdate and ammonium metavanadate in water at 70-80 ℃, adding a titanium silicalite TS-1 into the water, and carrying out ultrasonic treatment for 1.5-2h to form a mixture I;
(2) dissolving bismuth nitrate, cobalt nitrate, silver nitrate and metal salt or oxide of X, Y in 10 wt% of dilute nitric acid to form a mixture II;
(3) adding the ingredient II into the ingredient I under the stirring condition, standing for 36-72h at 70-90 ℃, filtering, washing, drying and roasting to obtain the catalyst for catalyzing isobutene or tert-butanol to prepare 2-methylacrolein.
Preferably, the drying temperature is 110-.
Preferably, the roasting temperature is 450-600 ℃ and the roasting time is 4-8 h.
The application of the catalyst specifically comprises the following steps: the catalyst is used for catalyzing the reaction of preparing 2-methylacrolein from isobutene or tertiary butanol.
Preferably, the application is specifically: the reaction is carried out in a fixed bed reactor, the catalyst is filled, oxygen is used as an oxidant, isobutene or tertiary butanol is used as a raw material, and the space velocity of the raw material is 1000h-1And reacting at 180-200 ℃ to prepare the 2-methylacrolein.
The invention has the advantages that:
the catalyst provided by the invention has the advantages that the reaction conditions for preparing 2-methylacrolein by catalysis are milder under the synergistic action of the composite metal oxide and the TS-1 molecular sieve, the reaction can be carried out at the temperature of 180-; but also can realize high conversion rate of catalyzing isobutene or tertiary butanol, good selectivity of 2-methylacrolein, long service life of the catalyst and good industrial application prospect.
Detailed Description
Example 1
Preparation of catalytic isobutene or tertiary butanolA catalyst for 2-methacrolein, the catalyst being: mo12V5Bi2Co3Ag2Cs1Fe2O58/TS-1；
The preparation method of the catalyst comprises the following steps:
(1) 21.19g (NH)4)6Mo7O24·4H2O and 5.85g NH4VO3·4H2O dissolved in 500g of 70oC, stirring in water, adding 200g of carrier titanium silicalite TS-1, and carrying out ultrasonic treatment for 2 hours to form a mixture I;
(2) 9.7gBi (NO)3)3·5H2O、8.73g Co(NO3)2·6H2O、3.4g AgNO3、1.95g CsNO3、8.08g Fe(NO3)3·9H2Dissolving O in 10 wt% dilute nitric acid to form a material II;
(3) adding the ingredient II into the ingredient I under the stirring condition, standing for 48h at 70 ℃, filtering, washing, drying at 110 ℃, and roasting for 4h at 550 ℃ to obtain the catalyst Mo for catalyzing isobutene or tert-butanol to prepare 2-methylacrolein12V5Bi2Co3Ag2Cs1Fe2 O58/TS-1。
Example 2
A catalyst for preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol, wherein the catalyst is as follows: mo12V5Bi2. 2Co4Ag1Rb1.5Mn2.5O58.45/TS-1；
The preparation method of the catalyst comprises the following steps:
(1) 21.19g (NH)4)6Mo7O24·4H2O and 5.85g NH4VO3·4H2O dissolved in 500g of 80oC, stirring in water, adding 200g of carrier titanium silicalite TS-1, and carrying out ultrasonic treatment for 1.5h to form a mixture I;
(2) 10.67 gBi (NO)3)3·5H2O、11.64 g Co(NO3)2·6H2O、1.7 g AgNO3、2.21 gRbNO3、6.13 gMn(CH3COO)2·4H2Dissolving O in 10 wt% dilute nitric acid to form a material II;
(3) adding the ingredient II into the ingredient I under the stirring condition, standing for 36h at 80 ℃, filtering, washing, drying at 120 ℃, and roasting at 600 ℃ for 4h to obtain the catalyst Mo for catalyzing isobutene or tert-butanol to prepare 2-methylacrolein1 2V5Bi2.2Co4Ag1Rb1.5Mn2.5O58.45/TS-1。
Example 3
A catalyst for preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol, wherein the catalyst is as follows: mo12V4Bi2Co3.5Ag1.5Cs1.5Nb2.5O59.25/TS-1；
The preparation method of the catalyst comprises the following steps:
(1) 21.19g (NH)4)6Mo7O24·4H2O and 4.68 g NH4VO3·4H2O dissolved in 500g of 80oC, stirring in water, adding 200g of carrier titanium silicalite TS-1, and carrying out ultrasonic treatment for 1.5h to form a mixture I;
(2) 9.7gBi (NO)3)3·5H2O、10.19 g Co(NO3)2·6H2O、2.55 g AgNO3、2.92 g CsNO3、3.32 gNb2O5Dissolving in 10 wt% dilute nitric acid to form a material II;
(3) adding the ingredient II into the ingredient I under the stirring condition, standing for 36h at 80 ℃, filtering, washing, drying at 120 ℃, and roasting at 600 ℃ for 8h to obtain the catalyst Mo for catalyzing isobutene or tert-butanol to prepare 2-methylacrolein1 2V4Bi2Co3.5Ag1.5Cs1.5Nb2.5O59.25/TS-1。
Example 4
A catalyst for preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol, wherein the catalyst is as follows: mo12V5Bi2. 5Co4Ag1Rb1.5Ni2.5O58.75/TS-1；
The preparation method of the catalyst comprises the following steps:
(1) 21.19g (NH)4)6Mo7O24·4H2O and 5.85g NH4VO3·4H2O dissolved in 500g of 80oC, stirring in water, adding 200g of carrier titanium silicalite TS-1, and carrying out ultrasonic treatment for 2 hours to form a mixture I;
(2) 12.13 gBi (NO)3)3·5H2O、11.64 g Co(NO3)2·6H2O、1.7 g AgNO3、2.21 gRbNO3、7.27 g Ni(NO3)2·6H2Dissolving O in 10 wt% dilute nitric acid to form a material II;
(3) adding the ingredient II into the ingredient I under the stirring condition, standing for 36h at 70 ℃, filtering, washing, drying at 110 ℃, and roasting for 4h at 580 ℃ to obtain the catalyst Mo for catalyzing isobutene or tert-butanol to prepare 2-methylacrolein1 2V5Bi2.5Co4Ag1Rb1.5Ni2.5O58.75/TS-1。
Example 5
A catalyst for preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol, wherein the catalyst is as follows: mo12V4Bi2.5Co5Ag2Cs2Sb3O63/TS-1；
The preparation method of the catalyst comprises the following steps:
(1) 21.19g (NH)4)6Mo7O24·4H2O and 4.68 g NH4VO3·4H2O dissolved in 500g of 80oC, stirring in water, and then addingAdding 200g of carrier titanium silicalite molecular sieve TS-1, and carrying out ultrasonic treatment for 2h to form a mixture I;
(2) 12.13 gBi (NO)3)3·5H2O、14.55 g Co(NO3)2·6H2O、3.4 g AgNO3、3.9 g CsNO3、4.85 gSb2O5Dissolving in 10 wt% dilute nitric acid to form a material II;
(3) adding the ingredient II into the ingredient I under the stirring condition, standing for 48h at 80 ℃, filtering, washing, drying at 110 ℃, and roasting for 4h at 600 ℃ to obtain the catalyst Mo for catalyzing isobutene or tert-butanol to prepare 2-methylacrolein12V4Bi2.5Co5Ag2Cs2Sb3O63/TS-1。
Example 6
A catalyst for preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol, wherein the catalyst is as follows: mo12V4Bi3Co4Ag2Rb1Sn2.5O59.5/TS-1；
The preparation method of the catalyst comprises the following steps:
(1) 21.19g (NH)4)6Mo7O24·4H2O and 4.68 g NH4VO3·4H2O dissolved in 500g of 80oC, stirring in water, adding 200g of carrier titanium silicalite TS-1, and carrying out ultrasonic treatment for 2 hours to form a mixture I;
(2) 14.55 gBi (NO)3)3·5H2O、11.64 g Co(NO3)2·6H2O、3.4 g AgNO3、1.47 g RbNO3、6.51 gSnCl4Dissolving in 10 wt% dilute nitric acid to form a material II;
(3) adding the ingredient II into the ingredient I under the stirring condition, standing for 48h at 80 ℃, filtering, washing, drying at 110 ℃, and roasting for 4h at 600 ℃ to obtain the catalyst Mo for catalyzing isobutene or tert-butanol to prepare 2-methylacrolein12V4Bi3Co4Ag2Rb1Sn2.5O59.5/TS-1。
Comparative example 1
The catalyst is identical to example 1 except that Ag is not added, i.e., Mo represents the catalyst12V5Bi2Co3Cs1Fe2O57/TS-1。
Comparative example 2
The catalyst is a titanium silicalite TS-1 unsupported, the rest is the same as example 1, namely the catalyst can be represented by Mo12V5Bi2Co3Ag2Cs1Fe2O58The preparation method comprises the following steps:
(1) 21.19g (NH)4)6Mo7O24·4H2O and 5.85g NH4VO3·4H2O dissolved in 500g of 70oC, stirring and carrying out ultrasonic treatment on water for 2 hours to form a material I;
(2) 9.7gBi (NO)3)3·5H2O、8.73g Co(NO3)2·6H2O、3.4g AgNO3、1.95g CsNO3、8.08g Fe(NO3)3·9H2Dissolving O in 10% dilute nitric acid to form a material II;
(3) adding the ingredient II into the ingredient I under the stirring condition, standing for 48h at 70 ℃, drying at 110 ℃, and roasting at 550 ℃ for 4h to obtain the catalyst Mo for catalyzing isobutene or tert-butanol to prepare 2-methylacrolein12V5Bi2Co3Ag2Cs1Fe2 O58。
Comparative example 3
The catalyst does not contain Ag metal and titanium silicalite TS-1 as a carrier, and the catalyst can be expressed as Mo in the same way as in example 112V5Bi2Co3Cs1Fe2 O57The preparation method comprises the following steps:
(1) 21.19g (NH)4)6Mo7O24·4H2O and 5.85g NH4VO3·4H2O dissolved in 500g of 70oC, stirring in water, adding 200g of carrier titanium silicalite TS-1, and carrying out ultrasonic treatment for 2 hours to form a mixture I;
(2) 9.7gBi (NO)3)3·5H2O、8.73g Co(NO3)2·6H2O、3.4g AgNO3、1.95g CsNO3、8.08g Fe(NO3)3·9H2Dissolving O in 10% dilute nitric acid to form a material II;
(3) adding the ingredient II into the ingredient I under the stirring condition, standing for 48h at 70 ℃, drying at 110 ℃, and roasting at 550 ℃ for 4h to obtain the catalyst Mo for catalyzing isobutene or tert-butanol to prepare 2-methylacrolein12V5Bi2Co3Cs1Fe2 O57。
Catalytic performance detection
The catalysts of the respective examples and comparative examples are used for catalyzing the reaction of preparing 2-methylacrolein from isobutene or tertiary butanol, and the application is as follows: the reaction is carried out in a fixed bed reactor, the catalyst is filled, oxygen is used as an oxidant, isobutene or tertiary butanol is used as a raw material, and the space velocity of the raw material is 1000h-1The reaction is carried out at 180 ℃ and 200 ℃ for 4h to test the conversion rate and the selectivity of the prepared 2-methylacrolein; the reaction conditions of the various examples are shown in Table 1.
TABLE 1 reaction conditions and catalytic performances of different catalysts in the preparation of 2-methylacrolein
Figure DEST_PATH_IMAGE002
Second, detecting the cycle performance
The service life of the catalyst described in example 1 was evaluated under the same reaction conditions as in example 1, and the results are shown in table 2.
TABLE 2 Recycling Performance of the catalyst described in example 1
Figure DEST_PATH_IMAGE004
As can be seen from Table 2, the catalyst prepared by the present invention has a long service life, and can still maintain a high product selectivity and a high raw material conversion rate after 120 hours of use.

Claims (6)

1. A catalyst for preparing 2-methylacrolein by catalyzing isobutene or tertiary butanol is characterized in that: the catalyst has the following structural general formula: moaVbBicCodAgeXfYgOh/Z，
Wherein, X is any one of Rb and Cs;
y is any one of Fe, Mn, Sb, Sn, Ni and Nb;
a. b, c, d, e, f, g and h are the atomic numbers of Mo, V, Bi, Co, Ag, X, Y and O elements in the catalyst respectively, the value of a is 12, the value range of b is 4-5, the value range of c is 2-3, the value range of d is 3-5, the value range of e is 1-2, the value range of f is 1-2, the value range of g is 2-3, and h is the oxygen atomic number required by meeting the oxidation state of other elements;
and Z is a titanium silicalite TS-1.
2. A process for preparing the catalyst of claim 1, wherein: the method comprises the following steps:
(1) dissolving ammonium molybdate and ammonium metavanadate in water at 70-80 ℃, adding a titanium silicalite TS-1 into the water, and carrying out ultrasonic treatment for 1.5-2h to form a mixture I;
(2) dissolving bismuth nitrate, cobalt nitrate, silver nitrate and metal salt or oxide of X, Y in 10 wt% of dilute nitric acid to form a mixture II;
(3) adding the ingredient II into the ingredient I under the stirring condition, standing for 36-72h at 70-90 ℃, filtering, washing, drying and roasting to obtain the catalyst for catalyzing isobutene or tert-butanol to prepare 2-methylacrolein.
3. The method of claim 2, wherein: the drying temperature is 110-130 ℃.
4. The method of claim 2, wherein: the roasting temperature is 450-600 ℃, and the roasting time is 4-8 h.
5. Use of the catalyst according to claim 1, characterized in that: the catalyst is used for catalyzing the reaction of preparing 2-methylacrolein from isobutene or tertiary butanol.
6. Use according to claim 5, characterized in that: the reaction is carried out in a fixed bed reactor, the catalyst is filled, oxygen is used as an oxidant, isobutene or tertiary butanol is used as a raw material, and the space velocity of the raw material is 1000h-1Reacting at 180-200 ℃ for 4h to prepare the 2-methylacrolein.
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Bi添加对MoVO/AlPO4催化剂异丁烯选择氧化反应性能的影响;王希涛等;《催化学报》;20110228;第32卷(第2期);352页左栏第1段、第353页右栏第3段、第356页右栏第2段 *

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