CN106881103A - The application method of composite oxide catalysts - Google Patents
The application method of composite oxide catalysts Download PDFInfo
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- CN106881103A CN106881103A CN201510941004.4A CN201510941004A CN106881103A CN 106881103 A CN106881103 A CN 106881103A CN 201510941004 A CN201510941004 A CN 201510941004A CN 106881103 A CN106881103 A CN 106881103A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- 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
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
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Abstract
The invention discloses a kind of application method of composite oxide catalysts; the catalyst is Mo Bi Fe Co O systems metal composite oxide; unsaturated aldehyde and unsaturated acids can be generated with high activity, with high selectivity by olefin oxidation; by inert gas is passed through before parking or when stopping in emergency in beds, can effectively guard catalyst performance without deteriorating.This method makes catalyst damage and keeps its stable performance constant when parking pause is needed using catalyst because of a variety of causes, so that it is guaranteed that device smoothly drive again and catalyst reaction performance stablizes constant.
Description
Technical field
The present invention relates to a kind of application method of composite oxide catalysts, the catalyst can be with high activity, Gao Xuan
Olefin oxidation is generated into selecting property unsaturated aldehyde and unsaturated acids.It is more particularly related to described compound
The stop-working protection method of oxide catalyst, so as to effective guard catalyst, being allowed to property when reaction system stops
Can not be decreased obviously.
Background technology
The unsaturated acids such as acrylic acid and methacrylic acid is important organic chemical industry's intermediate, is had in numerous areas
Extensive purposes, is industrially mainly prepared by alkene two-step penetration method.In order to improve the production capacity of process units, work
It is general in industry production to use the method for density of propylene in raising unstripped gas or improve propylene air speed or expand reaction
The method of device capacity, wherein the above two be undoubtedly more economic and convenient method.
The method that prior art proposes various raising catalyst performances.For example CN 100354042C are disclosed and urged
Influence of the specific surface area, halogen and manufacture method of agent to acrylic acid selectivity and yield.
Known catalyst in some cases can be inactivated.Such as Chen Xiao treasure etc.《The deactivation cause analysis of catalyst》
(Industrial CatalysisIn September, 2001 the 5th phase of volume 9) disclose three kinds of main Types that catalyst is inactivated, i.e.,
Catalyst carbon deposition etc. blocks inactivation, catalyst poisoning inactivation and sintering of catalyst and heat inactivation and inactivation.This article
Sintering of catalyst and heat inactivation are defined as " change of catalyst structure and performance that high temperature causes ".This article enters
One step is mentioned：High temperature can cause other to change in addition to the sintering for causing catalyst, also, mainly include：Chemistry
Composition and the change of phase composition, fritting, crystal grain are grown up, the embedding of active component loaded body, active component is due to life
Be lost in into volatile materials or sublimable material etc..
In industrial processes, can run into needs to stop because of plant modification, maintenance or technique adjustment and emergency case
The situation that only consersion unit runs.Consersion unit out of service can decline the peripheral temperature of catalyst, so as to have
Effect suppresses or slows down the sintering deactivation that may occur.However, it was found that weight after stopping consersion unit operation a period of time
The performance of catalyst can still decline during new startup consersion unit.Therefore, stopping needing to seek when consersion unit runs
The catalyst for looking for a kind of effective method to come in protection equipment, is allowed to that performance is unaffected, from the practicality of catalyst
This is very important for angle.
In view of the above problems, this area stills need to provide such a catalyst stop-working protection method, because various
It is former to suspend during using catalyst so that stopping, make catalyst damage and keep its stable performance constant,
So that it is guaranteed that device smoothly drive again and catalyst reaction performance stablizes constant.
The content of the invention
A goal of the invention of the invention is to provide such a catalyst stop-working protection method, because of a variety of causes
And when needing parking pause using catalyst, make catalyst damage and keep its stable performance constant, so that
Ensure device smoothly drive again and catalyst reaction performance stablizes constant.
Therefore, the present invention provides the application method of a kind of propylene or isobutylene oxidation catalyst, the catalyst tool
There is general formula：
Mo12BibFecCodXeYfZgOh,
Wherein, X is at least one element selected from W, Sb, As, P, Ni, Sn, Ce and Pb；
Y is at least one element selected from Zn, Cr, Mn, Ru, Ag, Pd and La；
Z is at least one element selected from Na, K, Li, Rb, Cs, Ca, Mg, Sr and Ba；
B is 0.1-7；
C is 0.5-8；
D is 1-10；
E is 0.1-3；
F is 0-1；
G is 0-2；
H is the numeral determined by the oxidation state of above-mentioned each element；
The catalyst is prepared with the following method：The presoma of above-mentioned each element is provided, by mixing, in advance
Coating or straight forming, obtain preformed catalyst in roasting, inert carrier；The preformed catalyst that will be obtained exists
In atmosphere containing 21%~50% molecular oxygen, in being calcined 3~20 hours at 450~540 DEG C, roasting gas are relative
The volume space velocity of catalyst is 50~2000h-1；
The application method includes：
I () carries out propylene or isobutylene oxidation manufacture (methyl) methacrylaldehyde and/or (first using the catalyst
Base) acrylic acid reaction；With
(ii) reaction is stopped, being passed through inert gas makes the catalyst be in inert atmosphere.
Specific embodiment
The present invention provides the application method of a kind of propylene or isobutylene oxidation catalyst, and the catalyst has following
Formula：
Mo12BibFecCodXeYfZgOh,
Wherein, X is at least one element selected from W, Sb, As, P, Ni, Sn, Ce and Pb, preferably
W、Sb、Ce、Sn；
Y is at least one element selected from Zn, Cr, Mn, Ru, Ag, Pd and La, preferably Zn, Cr；
Z is at least one element selected from Na, K, Li, Rb, Cs, Ca, Mg, Sr and Ba, preferably
Na、K、Cs；
B is 0.1~7, preferably 0.2~4；
C is 0.5~8, preferably 0.8~5；
D is 1~10, preferably 4~9；
E is 0.1~3, preferably 0.5~2；
F is 0~1, preferably 0.05~0.5；
G is 0~2, preferably 0.05~1.5；
H is the numeral determined by the oxidation state of above-mentioned each element.
Catalyst of the present invention is prepared with the following method：The presoma of above-mentioned each element is provided, by mixed
Conjunction, preroast, coating or straight forming on inert carrier, obtain preformed catalyst；The shaping that will be obtained is urged
Agent, in being calcined 3~20 hours at 450~540 DEG C, is calcined gas in the atmosphere containing 21%~50% molecular oxygen
The volume space velocity of body relative catalyst is 50~2000h-1。
In an example of the present invention, " the providing elemental precursor and blend step " includes providing each unit
The mixture of plain precursor, co-precipitation, and it is dried to obtain powder.In the present invention, term " elemental precursor "
Refer to the precursor that can form element oxide in composite oxides, it is typically the soluble-salt of the element.It is adapted to
It is without particular limitation in the elemental precursor of the inventive method, can be the solubility of the element known in the art
Salt etc..It is suitable for coprecipitation method of the invention without particular limitation, can is any routine known in the art
Method, such as by adjusting the pH value of mixture solution, oxidation state by changing element etc..It is suitable for this hair
Bright method drying means is without particular limitation, can be any of conventional drying methods of this area.
Preroast condition suitable for the inventive method is without particular limitation, can be preroast known in the art
Condition.In one of the invention preferable example, the preroast at 100-180 DEG C, 120-160 DEG C more fortunately
At a temperature of carry out 5-30 hours, it is preferable 8-26 hours, it is more preferable 10-24 hours.
In an example of the present invention, the manufacture method also includes, by the gross weight meter of final mixture,
Add the dilution thermal conducting agent of 5%-40wt%.The dilution thermal conducting agent is without particular limitation, can be known in the art
Any dilution thermal conducting agent, be selected from the dilution thermal conducting agent of Si powder, powdered graphite or its mixture.At this
In one example of invention, the particle diameter of the dilution thermal conducting agent is 70-220 μm, or is 100-200 μm.
In the present invention, the addition of the dilution thermal conducting agent preferably accounts for the 8-38 weight of final mixture gross weight
%, more preferably accounts for 10-35 weight %, preferably accounts for 12-32 weight %, preferably 15-30 weight %.
As preferably 70-210 microns of the particle diameter of dilution thermal conducting agent, preferably more preferably 70-200 microns, 70-180
Micron, preferably 70-160 microns.
The forming method of catalyst of the present invention is without particular limitation, can be forming method known in the art.
In an example of the present invention, by the gross weight meter of final mixture, 0.01%~10 weight % is added, preferably
0.1-8 weight %, more preferable 0.5-6 weight %, the preferably binding agent of 0.8-4 weight % are simultaneously well mixed, apply
It is overlying on the solid or hollow inert carriers such as spherical, cylindrical, cloverleaf pattern, bunge bedstraw herb shape, gear shape,
Or it is directly formed to above-mentioned given shape.In an example of the present invention, using ethyl cellulose as
The binding agent.
The manufacture method of catalyst of the present invention also includes the above-mentioned preformed catalyst that will be obtained containing 21%~50% point
In the atmosphere of sub- oxygen, at a temperature of 450~540 DEG C, 3~20 are calcined at a temperature of 480-520 DEG C more fortunately
Hour, preferably roasting 6-15 hours, more preferably roasting 8-12 hours, the volume of roasting gas relative catalyst are empty
Speed is 50~2000h-1。
In a preferable example, catalyst of the present invention is selected from：
Mo12Fe1.84Co5.19Ni2.40Bi1.69K0.11Na0.05Ca0.09Sb0.10La0.76Oh；
Mo12W0.48Fe2.03Co5.62Ni2.40Bi1.28K0.12Na0.05Ca0.09Sb0.10La0.76Oh；
Mo12Fe1.88Co5.25Ni2.48Bi1.89K0.18Na0.07Ca0.10Sb0.12La0.86Oh；
Mo12W0.58Fe2.13Co5.42Ni2.30Bi1.30K0.15Na0.05Ca0.09Sb0.10La0.76Oh；
Mo12W0.50Fe1.93Co5.01Ni2.42Bi1.50K0.18Na0.15Ca0.09Sb0.18La0.92Oh；
Mo12Fe1.98Co4.95Ni2.32Bi1.85K0.08Na0.17Ca0.21Sb0.18La0.96Oh；Or the mixing of its two or more formation
Thing.
Application method of the present invention includes：
I () carries out propylene or isobutylene oxidation manufacture (methyl) methacrylaldehyde and/or (first using the catalyst
Base) acrylic acid reaction
Propylene of the present invention or isobutene catalysis oxidation manufacture (methyl) methacrylaldehyde and/or (methyl) acrylic acid step
It is rapid without particular limitation, can be conventional method known in the art.In an example of the present invention, this hair
Bright reaction includes for catalyst of the present invention being placed in reaction vessel, makes the original containing propylene, oxygen and optional vapor
Material mixture obtains required product by the reaction vessel.
(ii) reaction is stopped, being passed through inert gas makes the catalyst be in inert atmosphere
Catalyst of the present invention is suitable for propylene or isobutylene oxidation manufacture (methyl) methacrylaldehyde or (methyl)
Acrylic acid catalytic oxidation.It is found by the applicant that work as stopping the catalysis oxidation for reasons such as such as overhauls of the equipments
During reaction, inert gas is passed through in catalyst bed helps to maintain the activity of the catalyst and be basically unchanged.
In the methods of the invention, applicable inert gas refers to be not involved in propylene or isobutylene oxidation any
The mixture of gas or its any ratio, it can be such as nitrogen, helium or argon gas.From cost angle,
It is preferably nitrogen.
In an example of the present invention, the inert gas air speed being passed through in beds is 30~1500h-1,
It is preferred that 50~300h-1；The temperature for being passed through the catalyst bed during inert gas is without particular limitation, can be with
It is any temperature in the range of room temperature to catalyst reaction temperatures.
The present invention is further illustrated below by embodiment.
Embodiment 1
1. the preparation of catalyst
3000mL water is heated to 60 DEG C, ammonium molybdate 1421.6g, potassium nitrate 4.2g, sodium nitrate 2.9g is added,
Stirring and dissolving obtains solution (1), and temperature is maintained at 70 DEG C.
After 1300mL water is heated into 50 DEG C, cobalt nitrate 1003.1g, nickel nitrate 443.3g, nitre are sequentially added
Sour iron 358.0g, stirring and dissolving adds nitric acid 30ml, bismuth nitrate 450.0g stirring and dissolvings and obtains solution (2),
Temperature is maintained at 50~70 DEG C.
Solution (2) is instilled in solution (1) and stirred, pulpous state liquid is obtained.By the pulpous state liquid at 150 DEG C
Preroast 24 hours.Then, based on the weight of preroast sample, 3% graphite is added in the preroast sample
With 2% (SiO2Content) Ludox, compression molding is external diameter 5mm, internal diameter 2mm, length 3mm after being well mixed
Hollow cylindrical particles.Preformed catalyst is calcined 5 hours in 495 DEG C.
2. the use of catalyst
50 grams of catalyst obtained above are taken to be fitted into fixed-bed tube reactor, be passed through preheating after propylene,
Air, the gaseous mixture of vapor are reacted, and the mol ratio of propylene/oxygen/water is 1:1.6:1.5, total air speed is
1200h-1, reaction temperature is 315 DEG C, propylene conversion ratio 98.4%, methacrylaldehyde and acrylic acid total recovery 94.7%,
Carbonoxide total recovery 3.5%.
Reaction stops the entrance of propylene, air and vapor after 100 hours, it is 90h to switch to air speed-1Nitrogen,
And holding is passed through nitrogen 7 days, reaction is then again turned on, that is, is passed through propylene, air, vapor after preheating
Gaseous mixture reacted, the mol ratio of propylene/oxygen/water is 1:1.6:1.5, total air speed is 1200h-1, reaction
Temperature is 315 DEG C.As a result propylene conversion ratio 98.5%, methacrylaldehyde and acrylic acid total recovery 94.3%, carbonoxide is total
Yield 3.4%.
After above-mentioned result of the test shows through parking 7 days, catalyst performance does not have significant change.
Embodiment 2
Catalyst is prepared using method same as Example 1 and carry out propylene oxidation reaction.
Reaction stops the entrance of propylene, air and vapor after 100 hours, it is 180h to switch to air speed-1Nitrogen,
And holding is passed through nitrogen 15 days, reaction is then again turned on, that is, is passed through propylene, air, vapor after preheating
Gaseous mixture reacted, the mol ratio of propylene/oxygen/water is 1:1.6:1.5, total air speed is 1200h-1, reaction
Temperature is 315 DEG C.As a result propylene conversion ratio 98.3%, methacrylaldehyde and acrylic acid total recovery 94.4%, carbonoxide is total
Yield 3.5%.
After above-mentioned result of the test shows through parking 15 days, catalyst performance does not have significant change.
Embodiment 3
Catalyst is prepared using method same as Example 1 and carry out propylene oxidation reaction.
Reaction stops the entrance of propylene, air and vapor after 100 hours, it is 100h to switch to air speed-1Nitrogen,
And holding is passed through nitrogen 7 days, reaction is then again turned on, that is, is passed through propylene, air, vapor after preheating
Gaseous mixture reacted, the mol ratio of propylene/oxygen/water is 1:1.6:1.5, total air speed is 1200h-1, reaction
Temperature is 315 DEG C.As a result propylene conversion ratio 98.2%, methacrylaldehyde and acrylic acid total recovery 94.5%, carbonoxide is total
Yield 3.3%.
After above-mentioned result of the test shows through parking 7 days, catalyst performance does not have significant change.
Embodiment 4
1. the preparation of catalyst
Catalyst is obtained using method same as Example 1.
2. the use of catalyst
50 grams of catalyst obtained above are taken to be fitted into fixed-bed tube reactor, be passed through preheating after propylene,
Air, the gaseous mixture of vapor are reacted, and the mol ratio of propylene/oxygen/water/add nitrogen is 1:1.7:1.0/2.4,
Total air speed is 1500h-1, reaction temperature is 325 DEG C, and propylene conversion ratio 98.5%, methacrylaldehyde and acrylic acid are total
Yield 95.3%, carbonoxide total recovery 3.0%.
Reaction stops the entrance of propylene, air and vapor after 1000 hours, it is 100h to switch to air speed-1Nitrogen
Gas, and holding is passed through nitrogen 7 days, is then again turned on reaction, that is, be passed through propylene, oxygen gas and water after preheating
The gaseous mixture of steam is reacted, and the mol ratio of propylene/oxygen/water/add nitrogen is 1:1.7:1.0/2.4, total air speed
It is 1500h-1, reaction temperature is 325 DEG C.As a result propylene conversion ratio 98.4%, methacrylaldehyde and acrylic acid total recovery
94.3%, carbonoxide total recovery 3.2%.
After above-mentioned result of the test shows through parking 7 days, catalyst performance does not have significant change.
Embodiment 5
Catalyst being prepared using method same as Example 4 and carrying out propylene oxidation reaction, reaction 3000 is small
When after stop reaction, switch to air speed be 210h-1Nitrogen, is again turned on reaction after being processed 20 days at 220 DEG C,
As a result propylene conversion ratio 98.5%, methacrylaldehyde and acrylic acid total recovery 94.4%, carbonoxide total recovery 3.3%.Table
Bright catalyst performance is not changed in.
Embodiment 6
1. the preparation of catalyst
1000g ammonium molybdates are dissolved in 3000ml distilled water.By 297.6g bismuth nitrates, 192.6g ferric nitrates,
755.5 cobalt nitrates, 27.5g nickel nitrates, 9.5g potassium nitrate, 5.5g cesium nitrates be dissolved in 2000ml distilled water.
This solution is gradually added drop-wise in the solution dissolved with ammonium molybdate, it is 1/1 to add with the mol ratio of metal ion
Citric acid, continuation stirs 6h at 60 DEG C, and the slurries for obtaining dry 24h, 250 DEG C of burning 10h at 100 DEG C, obtain
To active phase powder.By above-mentioned active phase powder and a diameter of 7~9 nanometers, the oxidation that length is 7~10 microns
Molybdenum nanotube is according to 96：4 ratio mixing, add 20% silicon, 2% graphite, extruded moulding for external diameter 5mm,
The cylindrical hollow particle of internal diameter 2mm, 4mm long, burns 5h and obtains finished catalyst at 500 DEG C.
2. the use of catalyst
50g catalyst is taken to be fitted into stainless steel continuous flow reactor, be passed through preheating after it is pre- fix, oxygen,
Water and nitrogen are reacted, and mol ratio is isobutene:Oxygen:Water:Nitrogen=1:2:1:14, the total air speed of material is
1500h-1, reaction temperature is 355 DEG C, and isobutene conversion 99.0%, MAL and methacrylic acid are total
Yield 93.1%, carbonoxide total recovery 5.5%.
Reaction stops the entrance of propylene, air and vapor after 500 hours, it is 90h to switch to air speed-1Nitrogen,
Reaction is again turned on after 7 days, as a result isobutene conversion 99.1%, MAL and methacrylic acid are always received
Rate 93.0%, carbonoxide total recovery 5.4%.Show that catalyst performance is not changed in.
Comparative example 1
Catalyst is prepared using method same as Example 1 and oxidation reaction is carried out, but be off propylene and
After water charging, continue to be passed through air, reaction is again turned on after 2 days, reaction temperature is 315 DEG C, propylene conversion ratio
98.8%, methacrylaldehyde and acrylic acid total recovery 93.4%, carbonoxide total recovery 4.6%.
With parking 7 days and be passed through the embodiment 1 of nitrogen (propylene conversion ratio 98.5%, methacrylaldehyde and acrylic acid be total
Yield 94.3%, carbonoxide total recovery 3.4%) to compare, its methacrylaldehyde and acrylic acid total recovery have dropped 0.9
%, and the yield of oxycarbide rises 1.2%, and propylene conversion is basically unchanged, and shows the performance of catalyst
Decline.
Comparative example 2
Catalyst is prepared using method same as Example 4 and propylene oxidation reaction is carried out, but stopped
After propylene and nitrogen feed, continue to be passed through air and water, reaction is again turned on after 3 days, reaction temperature is 325
DEG C, propylene conversion ratio 98.7%, methacrylaldehyde and acrylic acid total recovery 93.0%, carbonoxide total recovery 4.9%.
With embodiment 4 (propylene conversion ratio 98.4%, methacrylaldehyde and the acrylic acid total recovery that nitrogen is passed through after parking
94.3%, carbonoxide total recovery 3.2%) to compare, propylene conversion rises 0.7%, and total recovery have dropped 1.3
%, the amount of oxycarbide rises 1.7%, shows that the performance of catalyst has declined.
Comparative example 3
Catalyst is prepared using method same as Example 1 and propylene oxidation reaction is carried out, but be off propylene,
After air and water charging, any gas not being passed through, reaction being again turned on after placing 3 days, reaction temperature is 315
DEG C, propylene conversion ratio 98.6%, methacrylaldehyde and acrylic acid total recovery 93.5%, carbonoxide total recovery 4.5%.
With parking 7 days and be passed through the embodiment 1 of nitrogen (propylene conversion ratio 98.5%, methacrylaldehyde and acrylic acid be total
Yield 94.3%, carbonoxide total recovery 3.4%) to compare, its methacrylaldehyde and acrylic acid total recovery have dropped 0.9
%, and the yield of oxycarbide rises 1.1%, and propylene conversion is basically unchanged, and shows the performance of catalyst
Decline.
Claims (7)
1. a kind of application method of propylene or isobutylene oxidation catalyst, the catalyst has general formula：
Mo12BibFecCodXeYfZgOh,
Wherein, X is at least one element selected from W, Sb, As, P, Ni, Sn, Ce and Pb；
Y is at least one element selected from Zn, Cr, Mn, Ru, Ag, Pd and La；
Z is at least one element selected from Na, K, Li, Rb, Cs, Ca, Mg, Sr and Ba；
B is 0.1-7；
C is 0.5-8；
D is 1-10；
E is 0.1-3；
F is 0-1；
G is 0-2；
H is the numeral determined by the oxidation state of above-mentioned each element；
The application method includes：
I () carries out propylene or isobutylene oxidation manufacture (methyl) methacrylaldehyde and/or (methyl) acrylic acid reaction using the catalyst；With
(ii) reaction is stopped, being passed through inert gas makes the catalyst be in inert atmosphere.
2. application method as claimed in claim 1, it is characterised in that the catalyst is prepared with the following method：The presoma of above-mentioned each element is provided, by coating or straight forming on mixing, preroast, inert carrier, preformed catalyst is obtained；In the atmosphere containing 21%~50% molecular oxygen, in being calcined 3~20 hours at 450~540 DEG C, the volume space velocity of roasting gas relative catalyst is 50~2000h to the preformed catalyst that will be obtained-1。
3. application method as claimed in claim 1 or 2, it is characterised in that the catalyst is selected from：
Mo12Fe1.84Co5.19Ni2.40Bi1.69K0.11Na0.05Ca0.09Sb0.10La0.76Oh；
Mo12W0.48Fe2.03Co5.62Ni2.40Bi1.28K0.12Na0.05Ca0.09Sb0.10La0.76Oh；
Mo12Fe1.88Co5.25Ni2.48Bi1.89K0.18Na0.07Ca0.10Sb0.12La0.86Oh；
Mo12W0.58Fe2.13Co5.42Ni2.30Bi1.30K0.15Na0.05Ca0.09Sb0.10La0.76Oh；
Mo12W0.50Fe1.93Co5.01Ni2.42Bi1.50K0.18Na0.15Ca0.09Sb0.18La0.92Oh；
Mo12Fe1.98Co4.95Ni2.32Bi1.85K0.08Na0.17Ca0.21Sb0.18La0.96Oh；Or the mixture of its two or more formation.
4. application method as claimed in claim 2, it is characterised in that the manufacture method also includes, by the gross weight meter of final mixture, adds the dilution thermal conducting agent of 5%-40wt%.
5. application method as claimed in claim 4, it is characterised in that the dilution thermal conducting agent is selected from the dilution thermal conducting agent of Si powder, powdered graphite or its mixture, its particle diameter is 70-220 μm.
6. application method as claimed in claim 2, it is characterized in that the forming method includes, by the gross weight meter of final mixture, add the binding agent of 0.01%~10 weight % and be well mixed, be coated on the solid or hollow inert carriers such as spherical, cylindrical, cloverleaf pattern, bunge bedstraw herb shape, gear shape.
7. application method as claimed in claim 2, it is characterized in that the forming method includes, by the gross weight meter of final mixture, add the binding agent of 0.01%~10 weight % and be well mixed, be shaped to spherical, cylindrical, cloverleaf pattern, bunge bedstraw herb shape, the shape of gear shape.
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| CN109529862A (en) * | 2018-11-28 | 2019-03-29 | 中山大学 | A kind of nano-hollow microspherical catalyst prepares the application in methacrylaldehyde in propylene oxidation |
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| CN1781594A (en) * | 2004-11-22 | 2006-06-07 | 罗门哈斯公司 | Non-routine reactor shutdown method |
| CN101005892A (en) * | 2004-08-17 | 2007-07-25 | 旭化成化学株式会社 | Catalyst composed of complex oxide |
| CN103721722A (en) * | 2012-10-10 | 2014-04-16 | 上海华谊丙烯酸有限公司 | Composite oxide catalyst and preparation method thereof |
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| CN101005892A (en) * | 2004-08-17 | 2007-07-25 | 旭化成化学株式会社 | Catalyst composed of complex oxide |
| CN1781594A (en) * | 2004-11-22 | 2006-06-07 | 罗门哈斯公司 | Non-routine reactor shutdown method |
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| CN109529862A (en) * | 2018-11-28 | 2019-03-29 | 中山大学 | A kind of nano-hollow microspherical catalyst prepares the application in methacrylaldehyde in propylene oxidation |
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