CN103861608A - Inorganic fiber modified catalyst - Google Patents
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- CN103861608A CN103861608A CN201410000327.9A CN201410000327A CN103861608A CN 103861608 A CN103861608 A CN 103861608A CN 201410000327 A CN201410000327 A CN 201410000327A CN 103861608 A CN103861608 A CN 103861608A
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Abstract
The invention discloses an inorganic fiber modified catalyst which is a catalyst used in producing unsaturated aldehyde and/or unsaturated acid, wherein the mean length of an inorganic fiber is 10-800; the mean diameter is 1-25; the inorganic fiber is at least one of a glass fiber, a ceramic fiber, a metal fiber, a mineral fiber, a carbon fiber, a silicon carbide fiber, a silicon nitride fiber, an aluminum oxide fiber and various crystal whiskers; the total content of the inorganic fiber is 0.1-25wt.% of that of an active component of the catalyst. By adopting the inorganic fiber modified catalyst, propylene, isobutene, tertiary butanol or methyl tertiary butyl ether can be subjected to contact gas-phase oxidation under existence of molecular state oxygen to generate respective corresponding unsaturated aldehyde and/or unsaturated acid, and the inorganic fiber modified catalyst has the excellent mechanical strength and pulverization degree, and can keep the high catalyst activity and selectivity within a long period of time.
Description
Technical field
The present invention relates to catalyst preparation technical field, relate to a kind of inorfil modified catalyst for the production of unsaturated aldehyde and/or unsaturated acids, specifically, relate under the existence of molecular oxygen, propylene, isobutene, the tert-butyl alcohol or methyl tertiary butyl ether(MTBE) are carried out to catalytic gas phase oxidation manufacture corresponding unsaturated aldehyde and/or the inorfil modified catalyst of unsaturated carboxylic acid separately.
Background technology
Current general production method by the unsaturated gas catalytic gas phase oxidation manufacture unsaturated aldehyde such as propylene, isobutene, the tert-butyl alcohol or methyl tertiary butyl ether(MTBE) and/or unsaturated carboxylic acid, that is: above-mentioned reactant is mixed with steam with molecular oxygen precursor after, enter the reactor that suitable catalyst is housed, generate unsaturated aldehyde and/or unsaturated carboxylic acid.In this process, the mechanical performance of anti-applications catalyst is very important, is also one of important content of industry research.
Acrylic acid is as the important source material of water-absorbing resins, and market just further increases its demand.At present, acrylic acid reaches millions of tons in global annual production, considers the factor of rising in price of raw materials in recent years, and acrylic acid productive rate is even improve little by little, and also tool has very great significance economically.
Use catalyst in the production process of being manufactured unsaturated aldehyde and/or unsaturated carboxylic acid by the unsaturated gas catalytic gas phase oxidation such as propylene, isobutene, the tert-butyl alcohol or methyl tertiary butyl ether(MTBE) time, conventionally use shell and tube heat exchange fixed bed reactors, in the filling process of catalyst, catalyst need to be filled from the reaction tube top of several meters long, therefore, catalyst need to be except having high activity and target product selectivity, and also needing has enough mechanical strengths.
In order to improve mechanical strength and the catalyst activity of anti-applications catalyst, industry researcher can go from aspects such as strength improving agent, adhesive, carrier, forming techniques to consider conventionally.The disclosed catalyst of Chinese patent (200310114300.4) is that aqueous binder by selecting the pH=7.0-10.0 that contains ammonium free radical is for the preparation of coated catalysts.Catalyst in Chinese patent (200610073671.6) is that to select acid strength be-5.6≤H
0≤ 1.5 solid acid is as carrier.Chinese patent (201180044701.X) is selected fiber diameter 8
above inorfil matter and fiber diameter 6
following inorfil matter combines as strength improving agent, prepares molybdenum-bismuth catalyst series.
Though the catalyst designing in above-mentioned patent has obtained improvement to a certain degree in mechanical strength, still, still Shortcomings of its effect.Improve catalyst strength and need to consider the factor of two aspects: on the one hand, mechanical strength need to improve catalyst and peel off in the face of self breakage or component in filling process time, on the other hand, need to reduce the friction such as the friction between catalyst, catalyst and wall, airflow scouring and the temperature contrast that catalyst occurs manufacturing, in filling, transportation and the situation (abbreviation " efflorescence degree ") of the catalyst surface efflorescence causing.In addition, containing the molybdenum in the O composite metallic oxide catalyst of molybdenum at high temperature with steam reaction, easily run off in the mode of distillation.And the loss of molybdenum can cause the activity of catalyst, selective, mechanical strength, service life to be reduced, and molybdenum can deposit in the downstream line of reaction system, causes the obstruction of pipeline.
Summary of the invention
The object of the invention is to address the above problem, a kind of inorfil modified catalyst for the production of unsaturated aldehyde and/or unsaturated acids is provided, and described catalyst can carry out propylene, isobutene, the tert-butyl alcohol or methyl tertiary butyl ether(MTBE) catalytic gas phase oxidation manufacture and in corresponding unsaturated aldehyde and/or unsaturated carboxylic acid, apply separately under the existence of molecular oxygen.
For achieving the above object, the present invention has taked following technical scheme.
A kind of inorfil modified catalyst, for the catalyst for the production of unsaturated aldehyde and/or unsaturated acids, is characterized in that, the average length of described inorfil is 10～800
, the average diameter of described inorfil is 1～25
.
Further, described inorfil is at least one of glass fibre, ceramic fibre, metallic fiber, mineral fibres, carbon fiber, silicon carbide fibre, silicon nitride fiber, alumina fibre, various whiskers.
Further, the total content of described inorfil is 0.1～25wt.%(mass percent of catalyst activity component).
Further, described catalyst contains by formula M o
aa
bb
cc
dd
ee
fo
xthe active component representing,
In formula:
Mo is molybdenum;
A is at least one of bismuth, vanadium;
B is at least one of iron, tungsten;
C is at least one of alkali metal, alkaline-earth metal;
D is at least one of IV family element, VIII family element;
E is at least one of titanium, zirconium, cerium, copper, zinc, niobium, tin, lead, antimony;
O is oxygen;
A, b, c, d, e, f and x represent the atomic ratio number of Mo, A, B, C, D, E and O, here, a=12,0 < b≤10,0 < c≤10,0 < d≤5.5,0 < e≤3,0 < f≤10;
X is by meeting the required number of each metallic element combined oxidation state.
Inorfil modified catalyst of the present invention, for the catalyst for the production of unsaturated aldehyde and/or unsaturated acids, is characterized in that, the average length of described inorfil is 20～300
, the average diameter of described inorfil is 5～20
.
Further, described inorfil is at least one of glass fibre, ceramic fibre, metallic fiber, mineral fibres, carbon fiber, silicon carbide fibre, silicon nitride fiber, alumina fibre, various whiskers.
Further, the total content of described inorfil is 1～15wt.% of catalyst activity component.
Further, described catalyst contains by formula M o
aa
bb
cc
dd
ee
fo
xthe active component representing, in formula: Mo is molybdenum; A is at least one of bismuth, vanadium; B is at least one of iron, tungsten; C is at least one of alkali metal, alkaline-earth metal; D is at least one of IV family element, VIII family element; E is at least one of titanium, zirconium, cerium, copper, zinc, niobium, tin, lead, antimony; O is oxygen; A, b, c, d, e, f and x represent the atomic ratio number of Mo, A, B, C, D, E and O, here, a=12,0 < b≤10,0 < c≤10,0 < d≤5.5,0 < e≤3,0 < f≤10; X is by meeting the required number of each metallic element combined oxidation state.
Described inorfil modified catalyst carries out propylene, isobutene, the tert-butyl alcohol or methyl tertiary butyl ether(MTBE) catalytic gas phase oxidation and manufactures the application in each self-corresponding unsaturated aldehyde and/or unsaturated carboxylic acid under the existence of molecular oxygen.
The good effect of inorfil modified catalyst of the present invention is:
By adding certain average length (10-800
) and average diameter (1-25
) inorfil as strength improving agent, producible effect is: (1) can suppress catalyst surface and form granular projection and cause efflorescence, can prevent the be full of cracks on catalyst activity component surface and damaged; (2) improve the bonding force between catalyst activity component and between catalyst activity component and carrier, obtained the catalyst of mechanical strength and anti-efflorescence degree excellence; (3) improved the selective of the conversion ratio of reactant in the reaction of carrying out with described catalyst and product; (4) improve the heat transfer property of catalyst, reduced the body phase temperature of catalyst, can prevent from generating focus, the life-span of extending catalyst.
Detailed description of the invention
The detailed description of the invention that below continues to explain inorfil modified catalyst of the present invention, it is pointed out that enforcement of the present invention is not limited to following embodiment.
A kind of inorfil modified catalyst, its preparation method comprises the following steps and Attention Points:
(1) prepare active component
1. by the presomas such as the oxide of each component element, hydroxide, nitrate, ammonium salt, carbonate or their aqueous solution, colloidal sol or containing the compound of multiple element in water, the mode of mixing can adopt existing mode, and order by merging, temperature, pressure, pH are had no particular limits; Manufacture formula M o
aa
bb
cc
dd
ee
fo
xthe aqueous solution or water paste that the active component representing is raw material.
2. the aqueous solution 1. step being obtained or water paste obtain being dried thing through heating, being dried, here, heating and dry method are had no particular limits, can use spray dryer or blowing-type drying machine to be dried, also can use mould drying machine, tunnel type drying machine to heat in air-flow and obtain block or lepidiod dry thing.
Described dry thing can be directly by the aqueous solution or the dry dry thing (containing the volatile ingredient being produced by the decomposition of various salt) of water paste, also can be the dry thing (volatile ingredient not producing containing the decomposition by various salt) of processing by high-temperature roasting, it is had no particular limits, in way preferably the former.
3. described dry thing fragmentation is sieved and made by formula M o
aa
bb
cc
dd
ee
fo
xrepresent the catalyst fines of active component, in formula: Mo is molybdenum; A is at least one of bismuth, vanadium; B is at least one of iron, tungsten; C is at least one of alkali metal, alkaline-earth metal, IV family element, VIII family element; E is at least one of titanium, zirconium, cerium, copper, zinc, niobium, tin, lead, antimony; O is oxygen; A, b, c, d, e, f and x represent the atomic ratio number of Mo, A, B, C, D, E and O, here, and a=12,0 < b≤10,0 < c≤10,0 < d≤5,0 < e≤3,0 < f≤10; X is by meeting the required number of each metallic element combined oxidation state.
(2) catalyst activity component powders step (1) being obtained is mixed with a certain amount of inorfil, obtains the catalyst precarsor of mixed powder shape.The average length of described inorfil is 10～800
, preferably 30～300
; The average diameter of described inorfil is 1～25
, preferably 5～20
; Described inorfil is at least one of glass fibre, ceramic fibre, metallic fiber, mineral fibres, carbon fiber, silicon carbide fibre, silicon nitride fiber, alumina fibre, various whiskers; The total content of described inorfil is 0.1～25wt.% of catalyst activity component, preferably 1～15wt.%.
(3) catalyst precarsor step (2) being obtained adopts aqueous binder to be coated on inert carrier, and described painting method can adopt extrusion moulding, rotate comminution granulation or centrifugal flow coating method; That the shape of described catalyst can be selected is cylindrical, annular, ball-type or arbitrary shape, and catalyst precarsor is carried on inert carrier.
The present invention is not particularly limited the adhesive using, and still, preferably catalyst performance is not had to dysgenic material, does not 1. remain in binder aqueous solution in catalyst or the mixture with water after roasting that is:; For example, even if 2. remain in after roasting in catalyst and also can not produce dysgenic binder aqueous solution or the mixture with water, the organic compound of ethylene glycol, glycerine, propionic acid, maleic acid, propyl alcohol and nitric acid, ammonium nitrate, ammonium carbonate to the performance of catalyst.
Described inert carrier can adopt at least one of aluminium oxide, silica, titanium oxide, magnesia, steatite, silicon nitride.The present invention is not particularly limited the shape of described inert carrier, can be the effigurate any inert carrier of tool.
(4) load step (3) being obtained the inert carrier of catalyst precarsor calcine, obtain inorfil modified catalyst, described catalyst has formula M o
aa
bb
cc
dd
ee
fo
xthe active component composition representing.
Mechanical strength to inorfil modified catalyst of the present invention, efflorescence degree, conversion ratio, definition selective and yield represent respectively as follows:
(1) assay method to catalyst mechanical strength
The stainless steel reaction pipe vertical direction of long 5000mm, internal diameter 25mm is arranged, clog the lower end of described reaction tube with the stainless steel receiver sheet of thick 1mm.The catalyst of 50g is filled in reaction tube from the upper end of described reaction tube, taken away the stainless steel receiver sheet that is arranged on described reaction tube lower end, from reaction tube, slowly take out catalyst.By the catalyst taking out, by the sieve screening of 4mm, by the intensity of following computing formula evaluate catalysts, numerical value is higher means that catalyst strength is higher.
Catalyst efflorescence degree (wt.%)=[(remaining in the quality of the catalyst on screen cloth)/(quality of the catalyst falling from the upper end of reaction tube)] × 100.
(2) assay method to catalyst efflorescence degree
Take 100g catalyst, add in the cylinder drum type stainless steel closed container of diameter 254mm, height 152mm, on the wall of described container one side, be provided with the baffle plate that 51mm is high, make described container centered by the central shaft of its horizontal direction, under 60 ± 5rpm/min, rotate 30 minutes, from described container, take out afterwards described catalyst, the catalyst taking out is sieved by the sieve of 4mm, by the intensity of following computing formula evaluate catalysts.Numerical value is higher means that catalyst strength is higher.
Catalyst efflorescence degree (wt.%)=[(catalyst quality adding in container)-(remaining in the quality of the catalyst on screen cloth)/(catalyst quality adding in container)] × 100.
(3) assay method to Catalyst Conversion
Conversion ratio (% by mole)=[(the initiation material molal quantity having reacted)/(reacting initial feed molar number used)] × 100.
(4) assay method to catalyst selectivity
Selectively (% by mole)=[(generating unsaturated aldehyde or unsaturated acids molal quantity)/(the initiation material molal quantity having reacted)] × 100.
Below provide 23 embodiment and 3 comparative examples to do more detailed description to enforcement of the present invention.
embodiment 1
A kind of inorfil modified catalyst, its preparation method comprises the following steps:
(1) preparation of I section catalyst
500 parts of ammonium molybdates are dissolved in 2000 parts of distilled water adding under thermal agitation, obtain A liquid;
357 parts of cobalt nitrates and 192 parts of nickel nitrates are dissolved in 500 parts of distilled water, obtain B liquid;
In 350 parts of distilled water, add 185 parts of 172 parts of 30 parts of formation acid leach solution ferric nitrates of red fuming nitric acid (RFNA) (65wt.%) and bismuth nitrates, obtain C liquid;
In described A liquid, drip B liquid and C liquid, and then add the liquid that is dissolved with 2.4 parts of potassium nitrate in 50 parts of distilled water;
The suspension obtaining is evaporated to solid shape pie solids;
The solids obtaining is crushed to 250
below, obtain catalyst activity component powders;
Be 25 to adding average diameter by the 10wt.% of active component in described catalyst activity component powders
, average length is 800
glass fibre, obtain the catalyst precarsor of mixed powder shape;
In drum granulating device, drop into the silica-alumina ball type carrier that 1000 parts of average grain diameters are 4.5mm, then pass into 90 DEG C of hot blasts on one side, drop into distilled water and the described catalyst precarsor as adhesive on one side, catalyst precarsor is carried on inert carrier;
By load the inert carrier of catalyst precarsor under air atmosphere, in 400 DEG C of temperature, calcine 8 hours, obtain catalyst, described catalyst contain except after deoxidation by formula M o
12bi
1.7fe
1.8co
5.2ni
2.8k
0.1the composite metal oxide representing.
(2) preparation of II section catalyst
In by 2000 parts of distilled water heating, dissolve therein 350 parts of ammonium molybdates, 58 parts of ammonium metavanadates and 53.5 parts of ammonium paratungstates;
In the distilled water of 200 parts of heating, dissolve 47.9 parts of copper nitrates and 15.9 parts of strontium nitrates;
By two kinds of aqueous solution that obtain, then add 12 parts of antimony trioxides, obtain suspension;
Described suspension is evaporated to solid shape pie solids;
The solids obtaining is crushed to 250
below, obtain catalyst activity component powders;
Be 25 to adding average diameter by the 10wt.% of active component in described catalyst activity component powders
, average length is 500
glass fibre, obtain mixed powder shape catalyst precarsor;
In drum granulating machine, drop into the silica-alumina ball type carrier of 1000 parts of average grain diameter 4.5mm, then pass into 90 DEG C of hot blasts on one side, drop into distilled water and the described catalyst precarsor as adhesive on one side simultaneously, catalyst precarsor is carried on inert carrier;
By load the inert carrier of catalyst precarsor under air atmosphere, in 380 DEG C of temperature, calcine 8 hours, obtain catalyst, described catalyst contain except after deoxidation by formula M o
12v
3w
1.2cu
1.2sr
0.3sb
0.5the composite metal oxide representing.
The mechanical strength of inorfil modified catalyst prepared by embodiment 1 and the measurement result of efflorescence degree are referring to table 1.
Being determined as of inorfil modified catalyst oxidation reaction prepared by embodiment 1
:
By the reaction tube of having filled respectively the I section catalyst of embodiment 1 and the II section catalyst of embodiment 1 with air speed 1500 hours
-1import the unstrpped gas being made up of the nitrogen mixture of 8% propylene, 13% oxygen, 6% steam and the capacity of participation, carry out PROPENE IN GAS PHASE OXIDATION reaction, the conversion ratio of inorfil modified catalyst prepared by embodiment 1 and optionally measurement result are referring to table 2.
embodiment 2～19
A kind of inorfil modified catalyst, its basic preparation method is with embodiment 1.But glass fibre kind, length, diameter, content and embodiment 1 that each embodiment uses are different, particular content is referring to table 1.
Mechanical strength and the efflorescence degree of the inorfil modified catalyst of the assay method of employing embodiment 1 to embodiment 2～19 preparations are measured, and measurement result is referring to table 1.
embodiment 20
A kind of inorfil modified catalyst, its basic preparation method is with embodiment 1.Embodiment 20 is as different from Example 1: the mode of shaping of catalyst is compression molding, and the catalyst obtaining is the graininess of external diameter 5mm, long 4mm.
Mechanical strength and the efflorescence degree of the inorfil modified catalyst that the assay method of employing embodiment 1 is prepared embodiment 20 are measured, and measurement result is referring to table 1.
The mensuration of inorfil modified catalyst oxidation reaction prepared by embodiment 20 is with embodiment 1.The conversion ratio of inorfil modified catalyst prepared by embodiment 20 and optionally measurement result are referring to table 2.
embodiment 21
A kind of inorfil modified catalyst, its basic preparation method is with embodiment 1.Embodiment 21 is as different from Example 1: the mode of shaping of catalyst is extruded for mediating, and the catalyst obtaining is the ring-type catalyst of external diameter 6mm, aperture 2mm, high 4.5mm.
Mechanical strength and the efflorescence degree of the inorfil modified catalyst that the assay method of employing embodiment 1 is prepared embodiment 21 are measured, and measurement result is referring to table 1.
The mensuration of inorfil modified catalyst oxidation reaction prepared by embodiment 21 is with embodiment 1.The conversion ratio of inorfil modified catalyst prepared by embodiment 21 and optionally measurement result are referring to table 2.
embodiment 22
A kind of inorfil modified catalyst, its basic preparation method is with embodiment 1.Embodiment 22 is as different from Example 1: in the preparation of (1) I section catalyst, add 120 parts of Ludox and replace potassium nitrate solutions, I section catalyst except the general formula of metallic element composition after deoxidation be Mo
12bi
1.7fe
1.8co
5.2ni
2.8si
1.
(2) antimony oxide in II section catalyst preparation changes zirconium nitrate into, II section catalyst except the general formula of metallic element composition after deoxidation be Mo
12v
6w
1.5cu
3sr
0.25zr
1.
Mechanical strength and the efflorescence degree of the inorfil modified catalyst that the assay method of employing embodiment 1 is prepared embodiment 22 are measured, and measurement result is referring to table 1.
The mensuration of inorfil modified catalyst oxidation reaction prepared by embodiment 22:
By the reaction tube of having filled respectively the I section catalyst of embodiment 22 and the II section catalyst of embodiment 22 with air speed 1500 hours
-1import the unstrpped gas being formed by the nitrogen mixture of 8% isobutene, 16% oxygen, 10% steam and the capacity of participation, carry out isobutene gas phase oxidation.The conversion ratio of inorfil modified catalyst prepared by embodiment 22 and optionally measurement result are referring to table 2.
embodiment 23
A kind of inorfil modified catalyst, its basic preparation method is with embodiment 1.Embodiment 23 is as different from Example 1: in the preparation of (1) I section catalyst, add Ludox, ammonium tungstate, I section catalyst except the general formula of metallic element composition after deoxidation be Mo
12w
0.2bi
1.7fe
1.5co
4ni
3k
0.08si
1.
(2) antimony oxide in the preparation of II section catalyst changes magnesium nitrate into, and the general formula that II section catalyst removes the metallic element composition after deoxidation is Mo
12v
6w
2.5cu
3mg
0.5.
Mechanical strength and the efflorescence degree of the inorfil modified catalyst that the assay method of employing embodiment 1 is prepared embodiment 23 are measured, and measurement result is referring to table 1.
The mensuration of inorfil modified catalyst oxidation reaction prepared by embodiment 23:
By the reaction tube of having filled respectively the I section catalyst of embodiment 23 and the II section catalyst of embodiment 23 with air speed 1500 hours
-1import the unstrpped gas being formed by 8% tert-butyl alcohol, 16% oxygen, 10% steam, mixture that all the other are nitrogen, carry out tert-butyl alcohol gas phase oxidation.The conversion ratio of inorfil modified catalyst prepared by embodiment 23 and optionally measurement result are referring to table 2.
comparative example 1(being the comparison with embodiment 1)
A kind of catalyst, its basic preparation method is with embodiment 1.Comparative example 1 is as different from Example 1: comparative example 1 does not add inorfil in preparation.
Adopt mechanical strength and the efflorescence degree of the determination process comparison catalyst that prepared by example 1 of embodiment 1 to measure, measurement result is referring to table 1.
The conversion ratio of catalyst prepared by comparative example 1 and optionally measurement result are referring to table 2.
comparative example 2(being the comparison with embodiment 20)
A kind of catalyst, its basic preparation method is with embodiment 20.Comparative example 2 is as different from Example 20: comparative example 2 does not add inorfil in preparation.
Adopt mechanical strength and the efflorescence degree of the determination process comparison catalyst that prepared by example 2 of embodiment 1 to measure, measurement result is referring to table 1.
The conversion ratio of catalyst prepared by comparative example 2 and optionally measurement result are referring to table 2.
comparative example 3(being the comparison with embodiment 21)
A kind of catalyst, its basic preparation method is with embodiment 21.Comparative example 3 is as different from Example 21: comparative example 3 does not add inorfil in preparation.
Adopt mechanical strength and the efflorescence degree of the determination process comparison catalyst that prepared by example 3 of embodiment 1 to measure measurement result referring to table 1.
The conversion ratio of catalyst prepared by comparative example 3 and optionally measurement result are referring to table 2.
The inorfil modified catalyst of table 1. to embodiment 1～23 and the mechanical strength of catalyst and the measurement result of efflorescence degree of comparative example 1～3
The conversion ratio of the catalyst of the inorfil modified catalyst of table 2. to embodiment 1,20～23 and comparative example 1～3 and optionally measurement result
Claims (9)
1. an inorfil modified catalyst, for the catalyst for the production of unsaturated aldehyde and/or unsaturated acids, is characterized in that, the average length of described inorfil is 10～800
, the average diameter of described inorfil is 1～25
.
2. inorfil modified catalyst according to claim 1, it is characterized in that, described inorfil is at least one of glass fibre, ceramic fibre, metallic fiber, mineral fibres, carbon fiber, silicon carbide fibre, silicon nitride fiber, alumina fibre, various whiskers.
3. inorfil modified catalyst according to claim 1, is characterized in that, the total content of described inorfil is 0.1～25wt.% of catalyst activity component.
4. inorfil modified catalyst according to claim 1, is characterized in that, described catalyst contains by formula M o
aa
bb
cc
dd
ee
fo
xthe active component representing,
In formula:
Mo is molybdenum;
A is at least one of bismuth, vanadium;
B is at least one of iron, tungsten;
C is at least one of alkali metal, alkaline-earth metal;
D is at least one of IV family element, VIII family element;
E is at least one of titanium, zirconium, cerium, copper, zinc, niobium, tin, lead, antimony;
O is oxygen;
A, b, c, d, e, f and x represent the atomic ratio number of Mo, A, B, C, D, E and O, here, a=12,0 < b≤10,0 < c≤10,0 < d≤5.5,0 < e≤3,0 < f≤10;
X is by meeting the required number of each metallic element combined oxidation state.
5. an inorfil modified catalyst, for the catalyst for the production of unsaturated aldehyde and/or unsaturated acids, is characterized in that, the average length of described inorfil is 20～300
, the average diameter of described inorfil is 5～20
.
6. inorfil modified catalyst according to claim 5, it is characterized in that, described inorfil is at least one of glass fibre, ceramic fibre, metallic fiber, mineral fibres, carbon fiber, silicon carbide fibre, silicon nitride fiber, alumina fibre, various whiskers.
7. inorfil modified catalyst according to claim 5, is characterized in that, the total content of described inorfil is 1～15wt.% of catalyst activity component.
8. according to the inorfil modified catalyst described in claim 5-7, it is characterized in that, described catalyst contains by formula M o
aa
bb
cc
dd
ee
fo
xthe active component representing,
In formula:
Mo is molybdenum;
A is at least one of bismuth, vanadium;
B is at least one of iron, tungsten;
C is at least one of alkali metal, alkaline-earth metal;
D is at least one of IV family element, VIII family element;
E is at least one of titanium, zirconium, cerium, copper, zinc, niobium, tin, lead, antimony;
O is oxygen;
A, b, c, d, e, f and x represent the atomic ratio number of Mo, A, B, C, D, E and O, here, a=12,0 < b≤10,0 < c≤10,0 < d≤5.5,0 < e≤3,0 < f≤10;
X is by meeting the required number of each metallic element combined oxidation state.
9. claim 1 or inorfil modified catalyst claimed in claim 5 carry out propylene, isobutene, the tert-butyl alcohol or methyl tertiary butyl ether(MTBE) the application in the catalytic gas phase oxidation each self-corresponding unsaturated aldehyde of manufacture and/or unsaturated carboxylic acid under the existence of molecular oxygen.
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|---|---|---|---|
| CN201410000327.9A CN103861608A (en) | 2014-01-02 | 2014-01-02 | Inorganic fiber modified catalyst |
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|---|---|---|---|
| CN201410000327.9A CN103861608A (en) | 2014-01-02 | 2014-01-02 | Inorganic fiber modified catalyst |
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ID=50900973
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108355721A (en) * | 2018-02-02 | 2018-08-03 | 上海东化环境工程有限公司 | Modified support, supported catalyst and its application |
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| CN1583261A (en) * | 2004-06-11 | 2005-02-23 | 谷育英 | Composite metal oxide for unsaturated aldehyde selective oxidation and preparing method thereof |
| CN101992093A (en) * | 2010-09-28 | 2011-03-30 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst for preparing unsaturated aldehyde and unsaturated acid in high selectivity |
-
2014
- 2014-01-02 CN CN201410000327.9A patent/CN103861608A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386579A (en) * | 2001-03-21 | 2002-12-25 | 株式会社日本触媒 | Catalyst for preparing unsaturated aldehyde and unsaturated carboxylic acid |
| CN1583261A (en) * | 2004-06-11 | 2005-02-23 | 谷育英 | Composite metal oxide for unsaturated aldehyde selective oxidation and preparing method thereof |
| CN101992093A (en) * | 2010-09-28 | 2011-03-30 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst for preparing unsaturated aldehyde and unsaturated acid in high selectivity |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108355721A (en) * | 2018-02-02 | 2018-08-03 | 上海东化环境工程有限公司 | Modified support, supported catalyst and its application |
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Application publication date: 20140618 |