CN109999904A - A kind of catalyzing iso-butane alkene or the tert-butyl alcohol prepare catalyst of methacrolein and the preparation method and application thereof - Google Patents
A kind of catalyzing iso-butane alkene or the tert-butyl alcohol prepare catalyst of methacrolein and the preparation method and application thereof Download PDFInfo
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- CN109999904A CN109999904A CN201910355955.1A CN201910355955A CN109999904A CN 109999904 A CN109999904 A CN 109999904A CN 201910355955 A CN201910355955 A CN 201910355955A CN 109999904 A CN109999904 A CN 109999904A
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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
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- 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
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- 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
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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
- 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 present invention discloses a kind of catalyzing iso-butane alkene or the tert-butyl alcohol prepares catalyst of methacrolein and its preparation method and application, and the catalyst has the following structure general formula: MoaVbBicCodAgeXfYgOh/ Z, wherein any one in X Rb, Cs；Y is any one in Fe, Mn, Sb, Sn, Ni, Nb；A, b, c, d, e, f, g, h are respectively the atomicity of Mo, V, Bi, Co, Ag, X, Y, O element in the catalyst, and 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, and the value of e is 1-2, and the value of f is 1-2, the value of g is 2-3, and h is oxygen atomicity needed for meeting other elements oxidation state；Z is Titanium Sieve Molecular Sieve.The catalyst can carry out catalysis reaction at 180-200 DEG C, and reaction condition is milder.
Description
Technical field
The invention belongs to catalyzing iso-butane alkene or the tert-butyl alcohol to prepare methacrolein technical field, and in particular to a kind of catalysis
Isobutene or the tert-butyl alcohol prepare catalyst of methacrolein and the preparation method and application thereof.
Background technique
For a long time, the isobutene of refinery's by-product produces first mainly for the production of methyl tertiary butyl ether(MTBE) (MTBE), isobutene
Not only method is convenient for base tertbutyl ether, simple process, but also economic benefits.But now, country, which advocates, uses automobile-used second
Alcohol gasoline, this means that refinery's not reproduction mogas production, switchs to produce vehicle-use alcohol gasoline blend component oil
(GB22030—2017).Since ethanol petrol standard (GB18351-2017) is pressure standard, it is desirable that remove second in ethanol petrol
Other oxygenatedchemicals outside alcohol must not exceed 0.5%, and must not artificially add.This means that MTBE etc. cannot continue to make
For the use of gasoline high-octane rating blend component.It is reported that China has at present covers MTBE process units more 180, annual capacity is about
17000000 tons, with the popularization and use of vehicle-use alcohol gasoline, isobutene used in mass production MTBE will face and need high added value
The awkward situation of conversion.
So improving the high added value conversion of isobutene used in MTBE will be of great significance.In the prior art, have and pass through
The oxidation of catalyzing iso-butane alkene or the tert-butyl alcohol prepares methacrolein, but catalyst used in the reaction, in catalysis oxygen
When changing reaction, reaction temperature is higher, lower also at 390 DEG C or so generally at 800-900 DEG C, if reaction temperature can be reduced, one
Aspect can improve operational safety, on the other hand will also reduce the reaction cost.
Summary of the invention
In view of the drawbacks of the prior art, the present invention provides a kind of catalyzing iso-butane alkene or the tert-butyl alcohol prepares methacrolein
Catalyst and preparation method thereof, while the application that the catalyst is used to prepare methacrolein being also provided, it is being used to prepare
When methacrolein, reaction condition is mild, and reaction temperature can be reduced to 180 DEG C or so.
A kind of catalyzing iso-butane alkene or the tert-butyl alcohol prepare the catalyst of methacrolein, and the catalyst has the following structure
General formula: MoaVbBicCodAgeXfYgOh/ Z,
Wherein, any one in X Rb, Cs；
Y is any one in Fe, Mn, Sb, Sn, Ni, Nb；
A, b, c, d, e, f, g, h are respectively the atomicity of Mo, V, Bi, Co, Ag, X, Y, O element in the catalyst, and a
The value range that value is 12, b is 4-5, and the value range of the value range 2-3, d of c are 3-5, and the value range of e is 1-2, f
Value range be 1-2, the value range of g is 2-3, and h is oxygen atomicity needed for meeting other elements oxidation state；
Z is Titanium Sieve Molecular Sieve；Preferably, Z is titanium-silicon molecular sieve TS-1.
The preparation method of the catalyst, comprising the following steps:
(1) ammonium molybdate, ammonium metavanadate are dissolved in 70-80 DEG C of water, are then added titanium-silicon molecular sieve TS-1 thereto, at ultrasound
1.5-2h is managed, ingredient I is formed；
(2) metal salt of bismuth nitrate, cobalt nitrate, silver nitrate and X, Y or oxide are dissolved in the dust technology of 10 wt %, shape
At ingredient II；
(3) under agitation, ingredient II is added in ingredient I, stands 36-72h at 70-90 DEG C, be filtered, washed, dry
Dry, roasting, obtains the catalyzing iso-butane alkene or the tert-butyl alcohol prepares the catalyst of methacrolein.
Preferably, the temperature of the drying is 110-130 DEG C.
Preferably, the temperature of the roasting be 450-600 DEG C, time 4-8h.
The application of the catalyst, specifically: the catalyst is prepared into 2- methyl to catalyzing iso-butane alkene or the tert-butyl alcohol
The reaction of methacrylaldehyde.
Preferably, the application specifically: the reaction carries out in fixed bed reactors, loads the catalyst, with
Oxygen is oxidant, and using isobutene or the tert-butyl alcohol as raw material, the air speed of raw material is 1000 h-1, preparation is reacted at 180-200 DEG C
Methacrolein.
Advantages of the present invention:
Catalyst provided by the invention, by the synergistic effect of metal composite oxide and TS-1 molecular sieve, so that catalysis preparation
The reaction condition milder of methacrolein, can be reacted at 180-200 DEG C, reduced reaction cost, mentioned simultaneously
High operational safety；But also it is able to achieve the high conversion rate of catalyzing iso-butane alkene or the tert-butyl alcohol, methacrolein is selectively good,
The service life of the catalyst is long, has good prospects for commercial application.
Specific embodiment
Embodiment 1
A kind of catalyzing iso-butane alkene or the tert-butyl alcohol prepare the catalyst of methacrolein, the catalyst are as follows:
Mo12V5Bi2Co3Ag2Cs1Fe2O58/TS-1；
The preparation method of the catalyst, comprising the following steps:
(1) by 21.19g (NH4)6Mo7O24·4H2O and 5.85g NH4VO3·4H2O is dissolved in the 70 of 500goIn C water, stirring, so
200g carrier titanium-silicon molecular sieve TS-1 is added thereto afterwards, is ultrasonically treated 2h, forms ingredient I；
(2) by 9.7gBi (NO3)3·5H2O、8.73g Co(NO3)2·6H2O、3.4g AgNO3、1.95g CsNO3、8.08g
Fe(NO3)3·9H2O is dissolved in formation ingredient II in the dust technology of 10 wt %；
(3) under agitation, ingredient II is added in ingredient I, stands 48h at 70 DEG C, be filtered, washed, dried at 110 DEG C
It does, roast 4h at 550 DEG C, obtain the catalyzing iso-butane alkene or the tert-butyl alcohol prepares the catalyst of methacrolein
Mo12V5Bi2Co3Ag2Cs1Fe2 O58/TS-1。
Embodiment 2
A kind of catalyzing iso-butane alkene or the tert-butyl alcohol prepare the catalyst of methacrolein, the catalyst are as follows: Mo12V5Bi2.2Co4
Ag1Rb1.5Mn2.5O58.45/TS-1；
The preparation method of the catalyst, comprising the following steps:
(1) by 21.19 g (NH4)6Mo7O24·4H2O and 5.85 g NH4VO3·4H2O is dissolved in the 80 of 500 goIn C water, stir
It mixes, 200 g carrier titanium-silicon molecular sieve TS-1s is then added thereto, be ultrasonically treated 1.5h, form ingredient I；
(2) by 10.67 gBi (NO3)3·5H2O、11.64 g Co(NO3)2·6H2O、1.7 g AgNO3、2.21 gRbNO3、
6.13 gMn(CH3COO)2·4H2O is dissolved in formation ingredient II in the dust technology of 10 wt %；
(3) under agitation, ingredient II is added in ingredient I, stands 36h at 80 DEG C, be filtered, washed, dried at 120 DEG C
It does, roast 4h at 600 DEG C, obtain the catalyzing iso-butane alkene or the tert-butyl alcohol prepares the catalyst Mo of methacrolein12V5
Bi2.2Co4Ag1Rb1.5Mn2.5O58.45/TS-1。
Embodiment 3
A kind of catalyzing iso-butane alkene or the tert-butyl alcohol prepare the catalyst of methacrolein, the catalyst are as follows: Mo12V4Bi2Co3.5
Ag1.5Cs1.5Nb2.5O59.25/TS-1；
The preparation method of the catalyst, comprising the following steps:
(1) by 21.19g (NH4)6Mo7O24·4H2O and 4.68 g NH4VO3·4H2O is dissolved in the 80 of 500 goIn C water, stirring,
Then 200 g carrier titanium-silicon molecular sieve TS-1s are added thereto, are ultrasonically treated 1.5h, form ingredient I；
(2) by 9.7 gBi (NO3)3·5H2O、10.19 g Co(NO3)2·6H2O、2.55 g AgNO3、2.92 g CsNO3、
3.32 gNb2O5It is dissolved in formation ingredient II in the dust technology of 10 wt %；
(3) under agitation, ingredient II is added in ingredient I, stands 36h at 80 DEG C, be filtered, washed, dried at 120 DEG C
It does, roast 8h at 600 DEG C, obtain the catalyzing iso-butane alkene or the tert-butyl alcohol prepares the catalyst Mo of methacrolein12V4Bi2Co3.5Ag1.5Cs1.5Nb2.5O59.25/TS-1。
Embodiment 4
A kind of catalyzing iso-butane alkene or the tert-butyl alcohol prepare the catalyst of methacrolein, the catalyst are as follows: Mo12V5Bi2.5Co4
Ag1Rb1.5Ni2.5O58.75/TS-1；
The preparation method of the catalyst, comprising the following steps:
(1) by 21.19g (NH4)6Mo7O24·4H2O and 5.85 g NH4VO3·4H2O is dissolved in the 80 of 500 goIn C water, stirring,
Then 200 g carrier titanium-silicon molecular sieve TS-1s are added thereto, are ultrasonically treated 2h, form ingredient I；
(2) by 12.13 gBi (NO3)3·5H2O、11.64 g Co(NO3)2·6H2O、1.7 g AgNO3、2.21 gRbNO3、
7.27 g Ni(NO3)2·6H2O is dissolved in formation ingredient II in the dust technology of 10 wt %；
(3) under agitation, ingredient II is added in ingredient I, stands 36h at 70 DEG C, be filtered, washed, dried at 110 DEG C
It does, roast 4h at 580 DEG C, obtain the catalyzing iso-butane alkene or the tert-butyl alcohol prepares the catalyst Mo of methacrolein12V5
Bi2.5Co4Ag1Rb1.5Ni2.5O58.75/TS-1。
Embodiment 5
A kind of catalyzing iso-butane alkene or the tert-butyl alcohol prepare the catalyst of methacrolein, the catalyst are as follows:
Mo12V4Bi2.5Co5Ag2Cs2Sb3O63/TS-1；
The preparation method of the catalyst, comprising the following steps:
(1) by 21.19g (NH4)6Mo7O24·4H2O and 4.68 g NH4VO3·4H2O is dissolved in the 80 of 500 goIn C water, stirring,
Then 200 g carrier titanium-silicon molecular sieve TS-1s are added thereto, are ultrasonically treated 2h, form ingredient I；
(2) by 12.13 gBi (NO3)3·5H2O、14.55 g Co(NO3)2·6H2O、3.4 g AgNO3、3.9 g CsNO3、
4.85 gSb2O5It is dissolved in formation ingredient II in the dust technology of 10 wt %；
(3) under agitation, ingredient II is added in ingredient I, stands 48h at 80 DEG C, be filtered, washed, dried at 110 DEG C
It does, roast 4h at 600 DEG C, obtain the catalyzing iso-butane alkene or the tert-butyl alcohol prepares the catalyst of methacrolein
Mo12V4Bi2.5Co5Ag2Cs2Sb3O63/TS-1。
Embodiment 6
A kind of catalyzing iso-butane alkene or the tert-butyl alcohol prepare the catalyst of methacrolein, the catalyst are as follows:
Mo12V4Bi3Co4Ag2Rb1Sn2.5O59.5/TS-1；
The preparation method of the catalyst, comprising the following steps:
(1) by 21.19g (NH4)6Mo7O24·4H2O and 4.68 g NH4VO3·4H2O is dissolved in the 80 of 500 goIn C water, stirring,
Then 200 g carrier titanium-silicon molecular sieve TS-1s are added thereto, are ultrasonically treated 2h, form ingredient I；
(2) by 14.55 gBi (NO3)3·5H2O、11.64 g Co(NO3)2·6H2O、3.4 g AgNO3、1.47 g RbNO3、
6.51 gSnCl4It is dissolved in formation ingredient II in the dust technology of 10 wt %；
(3) under agitation, ingredient II is added in ingredient I, stands 48h at 80 DEG C, be filtered, washed, dried at 110 DEG C
It does, roast 4h at 600 DEG C, obtain the catalyzing iso-butane alkene or the tert-butyl alcohol prepares the catalyst of methacrolein
Mo12V4Bi3Co4Ag2Rb1Sn2.5O59.5/TS-1。
Comparative example 1
Metal Ag is not added in catalyst, other are represented by Mo with embodiment 1, i.e. catalyst12V5Bi2Co3Cs1Fe2O57/TS-
1。
Comparative example 2
Catalyst carrier-free titanium-silicon molecular sieve TS-1, other are represented by with embodiment 1, i.e. catalyst
Mo12V5Bi2Co3Ag2Cs1Fe2O58, the preparation method is as follows:
(1) by 21.19g (NH4)6Mo7O24·4H2O and 5.85g NH4VO3·4H2O is dissolved in the 70 of 500goIt in C water, stirs, surpasses
Sonication 2h forms ingredient I；
(2) by 9.7gBi (NO3)3·5H2O、8.73g Co(NO3)2·6H2O、3.4g AgNO3、1.95g CsNO3、8.08g
Fe(NO3)3·9H2O is dissolved in formation ingredient II in 10% dust technology；
(3) under agitation, ingredient II is added in ingredient I, stands 48h at 70 DEG C, dried at 110 DEG C, 550
4h is roasted at DEG C, obtains the catalyzing iso-butane alkene or the tert-butyl alcohol prepares the catalyst of methacrolein
Mo12V5Bi2Co3Ag2Cs1Fe2 O58。
Comparative example 3
Metal Ag is not added in catalyst, does not contain carrier titanium-silicon molecular sieve TS-1, other can with embodiment 1, i.e. catalyst yet
It is expressed as Mo12V5Bi2Co3Cs1Fe2 O57, the preparation method is as follows:
(1) by 21.19g (NH4)6Mo7O24·4H2O and 5.85g NH4VO3·4H2O is dissolved in the 70 of 500goIn C water, stirring, so
200g carrier titanium-silicon molecular sieve TS-1 is added thereto afterwards, is ultrasonically treated 2h, forms ingredient I；
(2) by 9.7gBi (NO3)3·5H2O、8.73g Co(NO3)2·6H2O、3.4g AgNO3、1.95g CsNO3、8.08g
Fe(NO3)3·9H2O is dissolved in formation ingredient II in 10% dust technology；
(3) under agitation, ingredient II is added in ingredient I, stands 48h at 70 DEG C, dried at 110 DEG C, 550
4h is roasted at DEG C, obtains the catalyzing iso-butane alkene or the tert-butyl alcohol prepares the catalyst Mo of methacrolein12V5Bi2Co3Cs1Fe2
O57。
The detection of one, catalytic performance
The catalyst of each embodiment and comparative example is prepared to the reaction of methacrolein to catalyzing iso-butane alkene or the tert-butyl alcohol,
The application specifically: the reaction carries out in fixed bed reactors, loads the catalyst, using oxygen as oxidant, with
Isobutene or the tert-butyl alcohol are raw material, and the air speed of raw material is 1000 h-1, 4 h test preparation 2- methyl-prop is reacted at 180-200 DEG C
The conversion ratio and selectivity of olefine aldehydr；For each embodiment when participating in reaction, reaction condition is specifically shown in Table 1.
1 different catalysts of table are in the reaction condition and catalytic performance for preparing methacrolein
The detection of two, cycle performances
Under reaction condition same as Example 1, the service life of catalyst described in embodiment 1 is evaluated, the results are shown in Table 2.
The recycling performance of catalyst described in 2 embodiment 1 of table
As shown in Table 2, catalyst long service life prepared by the present invention is still able to maintain higher product after using 120h
Selective and higher feed stock conversion.
Claims (7)
1. the catalyst that a kind of catalyzing iso-butane alkene or the tert-butyl alcohol prepare methacrolein, it is characterised in that: the catalyst tool
Just like flowering structure general formula: MoaVbBicCodAgeXfYgOh/ Z,
Wherein, any one in X Rb, Cs；
Y is any one in Fe, Mn, Sb, Sn, Ni, Nb；
A, b, c, d, e, f, g, h are respectively the atomicity of Mo, V, Bi, Co, Ag, X, Y, O element in the catalyst, and a
The value range that value is 12, b is 4-5, and the value range of the value range 2-3, d of c are 3-5, and the value range of e is 1-2, f
Value range be 1-2, the value range of g is 2-3, and h is oxygen atomicity needed for meeting other elements oxidation state；
Z is Titanium Sieve Molecular Sieve.
2. catalyst according to claim 1, it is characterised in that: the Z is titanium-silicon molecular sieve TS-1.
3. the preparation method of catalyst as claimed in claim 1 or 2, it is characterised in that: the following steps are included:
(1) ammonium molybdate, ammonium metavanadate are dissolved in 70-80 DEG C of water, are then added titanium-silicon molecular sieve TS-1 thereto, at ultrasound
1.5-2h is managed, ingredient I is formed；
(2) metal salt of bismuth nitrate, cobalt nitrate, silver nitrate and X, Y or oxide are dissolved in the dust technology of 10 wt %, shape
At ingredient II；
(3) under agitation, ingredient II is added in ingredient I, stands 36-72h at 70-90 DEG C, be filtered, washed, dry
Dry, roasting, obtains the catalyzing iso-butane alkene or the tert-butyl alcohol prepares the catalyst of methacrolein.
4. preparation method according to claim 3, it is characterised in that: the temperature of the drying is 110-130 DEG C.
5. preparation method according to claim 3, it is characterised in that: the temperature of the roasting is 450-600 DEG C, time 4-
8h。
6. the application of catalyst as claimed in claim 1 or 2, it is characterised in that: the catalyst is to catalyzing iso-butane alkene or tertiary fourth
Alcohol prepares the reaction of methacrolein.
7. applying according to claim 6, it is characterised in that: the reaction carries out in fixed bed reactors, described in filling
Catalyst, using oxygen as oxidant, using isobutene or the tert-butyl alcohol as raw material, the air speed of raw material is 1000h-1, at 180-200 DEG C
Reaction 4h prepares methacrolein.
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| CN111495422A (en) * | 2020-04-22 | 2020-08-07 | 陕西延长石油（集团）有限责任公司 | Method and catalyst for preparing epoxypropane and acetic acid by co-oxidation of ethane and propylene |
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