CN103801408A - Surface modified carrier, catalyst prepared by utilizing modified carrier as well as application of catalyst - Google Patents
Surface modified carrier, catalyst prepared by utilizing modified carrier as well as application of catalyst Download PDFInfo
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- CN103801408A CN103801408A CN201410000383.2A CN201410000383A CN103801408A CN 103801408 A CN103801408 A CN 103801408A CN 201410000383 A CN201410000383 A CN 201410000383A CN 103801408 A CN103801408 A CN 103801408A
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Abstract
The invention discloses a surface modified carrier. The carrier is an inorganic substance carrier; compound metal oxide expressed by a general formula of X1aX2bOx is loaded on the surface of the inorganic substance carrier; in the general formula, X1 is at least one of zinc and cadmium in group II B elements, titanium, zirconium, hafnium, vanadium, niobium, chromium, molybdenum and tungsten in group IV B-VI B element, and iron, cobalt, nickel and copper in group VIII B elements; X2 is at least one of lithium, sodium, potassium, rubidium and cesium in group IA elements, boron, aluminum, silicon and tin in group IIIA-IV A elements; O is oxygen; a, b and c are atomic ratios of various elements; 1<=a<=10, and 0.01<=b<=6; x is a numerical value determined by the oxidation degree of metal elements. A compound metal oxide catalyst is prepared by adopting the surface modified carrier and is used for converting low-carbon olefins into unsaturated aldehyde and/or unsaturated carboxylic acids, and an uncontrolled reaction caused by hot spots or peroxidatic reaction can be avoided.
Description
Technical field
The present invention relates to catalyst preparation technical field, the catalyst and the application of described catalyst in low-carbon alkene transforms thereof that are specifically related to a kind of surface modified carrier and utilize described surface modified carrier to prepare.
Background technology
Utilizing low-carbon alkene to carry out selective catalytic oxidation prepares method and the catalyst thereof of unsaturated aldehyde and unsaturated carboxylic acid and in industry, has obtained application.But, this type of chemical reaction belongs to strong exothermal reaction, except main reaction has heat release, also can there is side reaction and emit a large amount of heat, therefore, in pipe reaction fixed bed, the simple catalyst that uses easily forms focus, can cause catalysqt deactivation, bed sintering when heat release is serious, finally causes reaction to carry out.To this, existing way is to avoid the aggravation of catalyst hot-spot and side reaction heat release by effective elimination reaction heat.But the deficiency of doing is like this: the catalyst of use mostly is active component extrusion modling, the use amount of catalyst is large, cost is high; Easily in course of reaction, form heat spot, that is, occur local abnormal intensification phenomenon.At present, it has been recognized that: a large amount of reaction heat that strong exothermal reaction produces can make the lost of life, the overreact of catalyst, finally causes runaway reaction.
In order to make full use of the service life of active material energy extending catalyst, need to adjust the structure of catalyst, meet and can make reactant quick adsorption react and can make product hightail the requirement of catalyst surface, can make heat derive rapidly reflecting point.To this, people have developed loaded catalyst.Described loaded catalyst can be avoided the generation of hot localised points, and it shortens the diffusion length of gas reactant in relatively thin catalyst coat by temperature-compensating.Deutsche Bundespatent (DE-PS 3125061) discloses " a kind of method that uses housing Catalyst Production methacrylaldehyde "; Chinese patent (97104224.1) also discloses this type of load unsaturated aldehyde catalyst.
Still there are some problems in traditional supported catalyst at present, and for example, mechanical strength and stability are slightly poor, and the caking property between catalytic component and carrier is poor, and the activity of catalyst is declined comparatively fast, and the life-span is slightly short.Chinese patent (00137347.1) discloses the technology with alkali-earth metal modified carrier surface, still, its preparation condition harshness, the extreme temperatures needing, even reaches 1700 ℃, is not suitable for large-scale industrialization and produces.Therefore, good stability, loaded catalyst that mechanical strength is high be market in the urgent need to.
Summary of the invention
The object of the invention is to solve above-described problem, a kind of surface modified carrier is provided; The second object of the present invention is to utilize described surface modified carrier Kaolinite Preparation of Catalyst; The 3rd object of the present invention is to provide the catalyst of being prepared by surface modified carrier to be converted into the application in unsaturated aldehyde or unsaturated carboxylic acid at low-carbon alkene.
The present inventor has found a kind of composite metal oxide, it is by realizing the modification to carrier at common carrier surface recombination metal oxide, the carrier of this kind of surface modification can improve the load effect of catalyst, and the stability of catalyst and life-span can be increased.
For achieving the above object, the present invention has taked following technical scheme.
A kind of surface modified carrier, is characterized in that, described carrier is inanimate matter carrier, and at the area load composite metal oxide of described inanimate matter carrier, the general formula of described composite metal oxide is: X
1 ax
2 bo
x;
In general formula:
X
1for at least one of iron, cobalt, nickel and the copper of the titanium of the zinc of II B family element, cadmium, IV B-VI B family element, zirconium, hafnium, vanadium, niobium, chromium, molybdenum, tungsten, VIII B family element;
X
2for at least one of the boron of the lithium of I A family element, sodium, potassium, rubidium, caesium, III A-IV A family element, aluminium, silicon, tin;
O is oxygen;
A, b, x is the atomic ratio of each element, wherein 1≤a≤10,0.01≤b≤6, the numerical value that the degree of oxidation that x is metallic element determines.
Further, described inanimate matter carrier comprises at least one of silica, clay, kaolin, talcum, float stone, alumina silicate, magnesium silicate, carborundum, zirconium dioxide, thorium anhydride, titanium dioxide, silica, alumina, silicon alumina, aluminium oxide.
Further, described inanimate matter carrier be shaped as annular, spherical, cylindrical, hollow cylindrical or bar shaped.
For realizing above-mentioned the second object, the present invention has taked following technical scheme.
A kind of O composite metallic oxide catalyst, is characterized in that, adopts described surface modified carrier, contains the composite metal oxide of molybdenum, bismuth, iron at the area load of described surface modified carrier, and the general formula of described composite metal oxide is: Mo
abi
bfe
cm
1 dm
2 em
3 fo
x;
In general formula:
Mo is molybdenum, and Bi is bismuth, and Fe is iron;
M
1be selected from the cobalt of VIII B family element, at least one of nickel;
M
2be selected from least one of copper in I B family, IV B family-VI B family element, hafnium, scandium, vanadium, tungsten, zirconium;
M
3be selected from least one in I A family elements of Na, potassium, rubidium, caesium;
O is oxygen;
A to f is respectively the ratio of each element, in the time of a=12, and b=0.6～6, c=0.1～8, d=3～10, e=1～5, f=0.05～1;
X is a numerical value that meets other metallic element oxidation state in general formula.
For realizing above-mentioned the 3rd object, the present invention has taked following technical scheme.
Adopt O composite metallic oxide catalyst prepared by described surface modified carrier low-carbon alkene being converted into the application in unsaturated aldehyde and/or unsaturated carboxylic acid.
Further, described O composite metallic oxide catalyst is being converted into low-carbon alkene the application in unsaturated aldehyde and/or unsaturated carboxylic acid, it is characterized in that, the O composite metallic oxide catalyst that uses described surface modified carrier to prepare, by the gas of low-carbon alkene and oxygen molecule or oxygen-containing molecules is carried out to gas phase catalytic oxidation reaction, generate unsaturated aldehyde and/or unsaturated carboxylic acid.
Good effect of the present invention is:
(1) pass through the area load of inanimate matter carrier by general formula X
1 ax
2 bo
xthe composite metal oxide representing, forms a kind of surface modified carrier, and the connectivity between catalyst powder and carrier is strengthened, and has improved the stability of catalyst.
(2) the area load formula M o adopting at described surface modified carrier
abi
bfe
cm
1 dm
2 em
3 fo
xthe composite metal oxide representing has obtained a kind of O composite metallic oxide catalyst, the mechanical strength of loaded catalyst is obviously improved, increase the service life of catalyst, made long-time stable, high efficiency production unsaturated aldehyde and unsaturated carboxylic acid become possibility.
(3) the present invention adopt composite metal oxide the catalytic action of catalyst activity component is had to obvious facilitation, make catalyst activity, selectively all increase.
(4) O composite metallic oxide catalyst that prepared by employing surface modified carrier of the present invention can be used within the longer production cycle, carry out the conversion of unsaturated low-carbon alkene with continuous, high yield, stable mode, can avoid the runaway reaction because focus produces or peroxidization causes, and can carry out for a long time stable operation, therefore, the present invention adopts O composite metallic oxide catalyst prepared by surface modified carrier in production unsaturated aldehyde and/or insatiable hunger carboxylic acid, actively to apply.
The specific embodiment
Below specifically introduce the specific embodiment of the present invention, 24 embodiment and 2 comparative examples are provided.But it may be noted that enforcement of the present invention is not limited to following embodiment.
embodiment 1
A preparation for surface modified carrier, oxide on surface for inanimate matter carrier (Ti-Si-O) is carried out to modification:
188g titanium tetrachloride (Shanghai examination, CP) is added in 1000ml frozen water, strong agitation, then add 20% Ludox 100g, stir;
The alumina support that is 4.5mm by 500g average diameter is placed in above-mentioned mixed solution, at 80 ℃ of temperature, maintains 1 hour, then takes out dry;
500 ℃ of roasting temperatures 30 minutes, be then down to room temperature, obtaining load has general formula Ti
0.99si
0.33o
xthe surface modified carrier of the composite metal oxide representing.
embodiment 2
A preparation for surface modified carrier, oxide on surface for inanimate matter carrier (Mo-Al-O) is carried out to modification:
340g ammonium molybdate is dissolved in the 2000ml aqueous solution, then adds 50g alchlor, stir;
The alumina support that is 4.5mm by 500g average diameter is placed in above-mentioned mixed solution, at 80 ℃ of temperature, maintains 1 hour, then takes out dry;
450 ℃ of roasting temperatures 30 minutes, be then down to room temperature, obtaining load has formula M o
5.2al
1.0o
xthe surface modified carrier of the composite metal oxide representing.
embodiment 3
A preparation for surface modified carrier, oxide on surface for inanimate matter carrier (Cu-Sr-O) is carried out to modification:
120g copper nitrate is dissolved in 1500ml water, then adds 2.2g strontium nitrate, stir;
The alumina support that is 4.5mm by 500g average diameter is placed in above-mentioned mixed solution, at 80 ℃ of temperature, maintains 1 hour, then takes out dry;
420 ℃ of roasting temperatures 30 minutes, be then down to room temperature, obtaining load has general formula Cu
2sr
0.01o
xthe surface modified carrier of the composite metal oxide representing.
embodiment 4
A preparation for surface modified carrier, oxide on surface for inanimate matter carrier (Zn-Sn-O) is carried out to modification:
272g zinc chloride and 280g stannous chloride are dissolved in the 1000ml dilute hydrochloric acid solution of dilution;
The alumina support that is 4.5mm by 500g average diameter is placed in above-mentioned mixed solution, at 80 ℃ of temperature, maintains 1 hour, then takes out dry;
550 ℃ of roasting temperatures 30 minutes, be then down to room temperature, obtaining load has general formula Zn
10sn
6o
xthe surface modified carrier of the composite metal oxide representing.
embodiment 5
A preparation for surface modified carrier, oxide on surface for inanimate matter carrier (Fe-K-O) is carried out to modification:
160g ferric nitrate and 10g potassium nitrate are dissolved in 1500ml water, treat that it dissolves completely;
The alumina support that is 4.5mm by 500g average diameter is placed in above-mentioned mixed solution, at 80 ℃ of temperature, maintains 1 hour, then takes out dry;
450 ℃ of roasting temperatures 30 minutes, be then down to room temperature, obtaining load has general formula Fe
8k
2o
xthe surface modified carrier of the composite metal oxide representing.
embodiment 6
A preparation for surface modified carrier, oxide on surface for inanimate matter carrier (Co-Nb-B-O) is carried out to modification:
200g cabaltous nitrate hexahydrate, 80g niobium oxalate, 3g boric acid are joined in 1500ml water, fully stirring and dissolving;
The alumina support that is 4.5mm by 500g average diameter is placed in above-mentioned mixed solution, at 80 ℃ of temperature, maintains 2 hours, then takes out dry;
500 ℃ of roasting temperatures 30 minutes, be then down to room temperature, obtaining load has general formula Co
3.4nb
2.2b
0.24o
xthe surface modified carrier of the composite metal oxide representing.
embodiment 7
The preparation of O composite metallic oxide catalyst, basic preparation process is as follows:
Under the condition that adds thermal agitation, 420g ammonium molybdate is dissolved in 2500ml distilled water, obtain solution (A);
350g cobalt nitrate, 150g nickel nitrate and 130g ferric nitrate are dissolved in 1000ml distilled water, obtain solution (B);
180g bismuth nitrate is dissolved in the 250ml distilled water with the acidifying of 25ml red fuming nitric acid (RFNA), obtains solution (C);
Then, join in solution (A), then add 3.0g potassium nitrate after solution (B) and solution (C) are mixed, the solution obtaining is dry with spray dryer, and then precalcining 1～3 hour at 300～400 ℃, obtains catalyst precarsor;
Described catalyst precarsor is pulverized, crossed 60 order sample sifters, make its grain size be less than 250
.
The surface modified carrier 500g that embodiment 1 is obtained joins in rotary drum granulator, be 0.6 by the weight ratio of described catalyst precarsor 300g(catalyst precarsor and surface modified carrier), the glass fibre and 5% water that account for catalyst precarsor 10wt.% joins in rotary drum granulator simultaneously, the mixture of catalyst precarsor and glass fibre and water is loaded on described surface modified carrier, obtain the particle that catalyst load rate is 38wt.%;
Finally, described particle is dried, in air, at 460～510 ℃, calcines 2～5 hours, obtain described O composite metallic oxide catalyst.
O composite metallic oxide catalyst prepared by embodiment 7 carries out the test of oxidation reaction:
O composite metallic oxide catalyst prepared by embodiment 7 is placed in the single tube evaluating apparatus that propylene oxidation is prepared methacrylaldehyde, to the test result of catalyst in table 1.
embodiment 8
The preparation of O composite metallic oxide catalyst, basic preparation process is as follows:
Preparation method is with embodiment 7, and embodiment 8 with embodiment 7 differences is: the surface modified carrier that embodiment 2 is obtained joins in rotary drum granulator, obtains described O composite metallic oxide catalyst.
O composite metallic oxide catalyst prepared by embodiment 8 carries out the test of oxidation reaction with embodiment 7, to the test result of catalyst in table 1.
embodiment 9
The preparation of O composite metallic oxide catalyst, basic preparation process is as follows:
Preparation method is with embodiment 7, and embodiment 9 with embodiment 7 differences is: the surface modified carrier that embodiment 3 is obtained joins in rotary drum granulator, obtains described O composite metallic oxide catalyst.
O composite metallic oxide catalyst prepared by embodiment 9 carries out the test of oxidation reaction with embodiment 7, to the test result of catalyst in table 1.
embodiment 10
The preparation of O composite metallic oxide catalyst, basic preparation process is as follows:
Preparation method is with embodiment 7, and embodiment 10 with embodiment 7 differences is: the surface modified carrier that embodiment 4 is obtained joins in rotary drum granulator, obtains described O composite metallic oxide catalyst.
O composite metallic oxide catalyst prepared by embodiment 10 carries out the test of oxidation reaction with embodiment 7, to the test result of catalyst in table 1.
embodiment 11
The preparation of O composite metallic oxide catalyst, basic preparation process is as follows:
Preparation method is with embodiment 7, and embodiment 11 with embodiment 7 differences is: the surface modified carrier that embodiment 5 is obtained joins in rotary drum granulator, obtains described O composite metallic oxide catalyst.
O composite metallic oxide catalyst prepared by embodiment 11 carries out the test of oxidation reaction with embodiment 7, to the test result of catalyst in table 1.
embodiment 12
The preparation of O composite metallic oxide catalyst, basic preparation process is as follows:
Preparation method is with embodiment 7, and embodiment 12 with embodiment 7 differences is: the surface modified carrier that embodiment 6 is obtained joins in rotary drum granulator, obtains described O composite metallic oxide catalyst.
O composite metallic oxide catalyst prepared by embodiment 12 carries out the test of oxidation reaction with embodiment 7, to the test result of catalyst in table 1.
comparative example 1(being the comparison with embodiment 7)
Except not adopting the surface modified carrier that embodiment 1 obtains, other steps are with embodiment 7.
Composite metal catalyst prepared by comparative example 1 carries out the test of oxidation reaction with embodiment 7, to the test result of catalyst in table 1.
O composite metallic oxide catalyst prepared by table 1. embodiment 7～12 and comparative example 1 carries out the performance test results of oxidation reaction
embodiment 13
A preparation for surface modified carrier, the method for the modification to inanimate matter carrier is with embodiment 1, and still, embodiment 13 with embodiment 1 difference is: the carrier of use, for average diameter is 5.0mm silica sphere, obtains the carrier of surface modification.
embodiment 14
A preparation for surface modified carrier, the method for the modification to inanimate matter carrier is with embodiment 2, and still, embodiment 14 with embodiment 2 differences is: the carrier of use, for average diameter is 5.0mm silica sphere, obtains the carrier of surface modification.
embodiment 15
A preparation for surface modified carrier, the method for the modification to inanimate matter carrier is with embodiment 3, and still, embodiment 15 with embodiment 3 differences is: the carrier of use, for average diameter is 5.0mm silica sphere, obtains the carrier of surface modification.
embodiment 16
A preparation for surface modified carrier, the method for the modification to inanimate matter carrier is with embodiment 4, and still, embodiment 16 with embodiment 4 differences is: the carrier of use, for average diameter is 5.0mm silica sphere, obtains the carrier of surface modification.
embodiment 17
A preparation for surface modified carrier, the method for the modification to inanimate matter carrier is with embodiment 5, and still, embodiment 17 with embodiment 5 differences is: the carrier of use, for average diameter is 5.0mm silica sphere, obtains the carrier of surface modification.
embodiment 18
A preparation for surface modified carrier, the method for the modification to inanimate matter carrier is with embodiment 6, and still, embodiment 18 with embodiment 6 differences is: the carrier of use, for average diameter is 5.0mm silica sphere, obtains the carrier of surface modification.
embodiment 19
The preparation of O composite metallic oxide catalyst, basic preparation process is as follows:
Preparation method, with embodiment 7, with embodiment 7 differences is: the surface modified carrier that embodiment 13 is obtained joins in rotary drum granulator, obtains described O composite metallic oxide catalyst.
O composite metallic oxide catalyst prepared by embodiment 19 carries out the test of oxidation reaction:
O composite metallic oxide catalyst prepared by embodiment 19 is placed in the single tube evaluating apparatus of preparing MAL using isobutene as reaction raw materials, to the test result of catalyst in table 2.
embodiment 20
The preparation of O composite metallic oxide catalyst, basic preparation process is as follows:
Preparation method is with embodiment 19, and embodiment 20 with embodiment 19 differences is: the surface modified carrier that embodiment 14 is obtained joins in rotary drum granulator, obtains described O composite metallic oxide catalyst.
O composite metallic oxide catalyst prepared by embodiment 20 carries out the test of oxidation reaction with embodiment 19, to the test result of catalyst in table 2.
embodiment 21
The preparation of O composite metallic oxide catalyst, basic preparation process is as follows:
Preparation method is with embodiment 19, and embodiment 21 with embodiment 19 differences is: the surface modified carrier that embodiment 15 is obtained joins in rotary drum granulator, obtains described O composite metallic oxide catalyst.
O composite metallic oxide catalyst prepared by embodiment 21 carries out the test of oxidation reaction with embodiment 19, to the test result of catalyst in table 2.
embodiment 22
The preparation of O composite metallic oxide catalyst, basic preparation process is as follows:
Preparation method is with embodiment 19, and embodiment 22 with embodiment 19 differences is: the surface modified carrier that embodiment 16 is obtained joins in rotary drum granulator, obtains described O composite metallic oxide catalyst.
O composite metallic oxide catalyst prepared by embodiment 22 carries out the test of oxidation reaction with embodiment 19, to the test result of catalyst in table 2.
embodiment 23
The preparation of O composite metallic oxide catalyst, basic preparation process is as follows:
Preparation method is with embodiment 19, and embodiment 23 with embodiment 19 differences is: the surface modified carrier that embodiment 17 is obtained joins in rotary drum granulator, obtains described O composite metallic oxide catalyst.
O composite metallic oxide catalyst prepared by embodiment 23 carries out the test of oxidation reaction with embodiment 19, to the test result of catalyst in table 2.
embodiment 24
The preparation of O composite metallic oxide catalyst, basic preparation process is as follows:
Preparation method is with embodiment 19, and embodiment 24 with embodiment 19 differences is: the surface modified carrier that embodiment 18 is obtained joins in rotary drum granulator, obtains described O composite metallic oxide catalyst.
O composite metallic oxide catalyst prepared by embodiment 24 carries out the test of oxidation reaction with embodiment 19, to the test result of catalyst in table 2.
comparative example 2(being the comparison with embodiment 19)
Except not adopting the surface modified carrier that embodiment 19 obtains, other steps are with embodiment 19.
O composite metallic oxide catalyst prepared by comparative example 2 carries out the test of oxidation reaction with embodiment 19, to the test result of catalyst in table 2.
O composite metallic oxide catalyst prepared by table 2. embodiment 19～24 and comparative example 2 carries out the performance test results of oxidation reaction
。
In above embodiment and comparative example, the test mode of the intensity of effects on surface modified support and catalyst efflorescence degree is:
(1) dropping impact strength test
The O composite metallic oxide catalyst of the O composite metallic oxide catalyst of 100g embodiment 7～12 and comparative example 1 is fallen from the long 3.8m standing vertically, the stainless steel tube top of internal diameter 25mm, after stopping with the corrosion resistant plate of thick 2mm, the catalyst of pulverizing with 20 order sample sifter screenings, measures the catalyst weight remaining on sample sifter.
Drop strength is defined as follows:
Dropping impact strength (%)=(remaining in the catalyst weight of catalyst weight on sieve/fall) × 100.
(2) efflorescence degree test
The O composite metallic oxide catalyst of the O composite metallic oxide catalyst of 100g embodiment 7～12 and comparative example 1 is put into the stainless steel cylinder of long 152mm, diameter 250mm, making its rotating speed is 60 revs/min, continues 5 minutes; Sieve and remove residual powder with 20 order sample sifters, weigh.
Being expressed as of efflorescence degree test result:
Efflorescence degree (%)=(catalyst weight-remain in the catalyst weight on sieve)/catalyst weight × 100.
(3) conversion ratio of the reaction the present invention relates to, selective and productive rate are defined as follows
Propylene conversion (mol%)=(participating in the molal quantity of the propylene of reaction)/(molal quantity of the propylene of supply) × 100.
Selective (mol%)=(molal quantity of (methyl) methacrylaldehyde forming) of (methyl) methacrylaldehyde/(participating in the molal quantity of the propylene of reaction) × 100.
(methyl) methacrylaldehyde productive rate (mol%)=(molal quantity of (methyl) methacrylaldehyde forming)/(molal quantity of the propylene of supply) × 100.
Claims (6)
1. a surface modified carrier, is characterized in that, described carrier is inanimate matter carrier, and at the area load composite metal oxide of described inanimate matter carrier, the general formula of described composite metal oxide is: X
1 ax
2 bo
x;
In general formula:
X
1for at least one of iron, cobalt, nickel and the copper of the titanium of the zinc of II B family element, cadmium, IV B-VI B family element, zirconium, hafnium, vanadium, niobium, chromium, molybdenum, tungsten, VIII B family element;
X
2for at least one of the boron of the lithium of I A family element, sodium, potassium, rubidium, caesium, III A-IV A family element, aluminium, silicon, tin;
O is oxygen;
A, b, x is the atomic ratio of each element, wherein 1≤a≤10,0.01≤b≤6, the numerical value that the degree of oxidation that x is metallic element determines.
2. surface modified carrier according to claim 1, it is characterized in that, described inanimate matter carrier comprises at least one of silica, clay, kaolin, talcum, float stone, alumina silicate, magnesium silicate, carborundum, zirconium dioxide, thorium anhydride, titanium dioxide, silica, alumina, silicon alumina, aluminium oxide.
3. surface modified carrier according to claim 2, is characterized in that, being shaped as of described inanimate matter carrier is annular, spherical, cylindrical, hollow cylindrical or bar shaped.
4. an O composite metallic oxide catalyst, it is characterized in that, adopt surface modified carrier claimed in claim 1, contain the composite metal oxide of molybdenum, bismuth, iron at the area load of surface modified carrier claimed in claim 1, the general formula of described composite metal oxide is: Mo
abi
bfe
cm
1 dm
2 em
3 fo
x;
In general formula:
Mo is molybdenum, and Bi is bismuth, and Fe is iron;
M
1be selected from the cobalt of VIII B family element, at least one of nickel;
M
2be selected from least one of copper in I B family, IV B family-VI B family element, hafnium, scandium, vanadium, tungsten, zirconium;
M
3be selected from least one in I A family elements of Na, potassium, rubidium, caesium;
O is oxygen;
A to f is respectively the ratio of each element, in the time of a=12, and b=0.6～6, c=0.1～8, d=3～10, e=1～5, f=0.05～1;
X is a numerical value that meets other metallic element oxidation state in general formula.
5. adopt the O composite metallic oxide catalyst that prepared by surface modified carrier described in claim 1 low-carbon alkene being converted into the application in unsaturated aldehyde and/or unsaturated carboxylic acid.
6. O composite metallic oxide catalyst according to claim 5 is being converted into low-carbon alkene the application in unsaturated aldehyde and/or unsaturated carboxylic acid, it is characterized in that, right to use requires the O composite metallic oxide catalyst that described in 1 prepared by surface modified carrier, by the gas of low-carbon alkene and oxygen molecule or oxygen-containing molecules is carried out to gas phase catalytic oxidation reaction, generate unsaturated aldehyde and/or unsaturated carboxylic acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104841434A (en) * | 2015-04-09 | 2015-08-19 | 中国科学院山西煤炭化学研究所 | Modified silica and cobalt loading catalyst, preparation method and application thereof |
| CN108325533A (en) * | 2018-02-01 | 2018-07-27 | 上海东化环境工程有限公司 | Modified support, O composite metallic oxide catalyst and method for producing acrylic acid |
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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 |
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| CN1099024A (en) * | 1993-06-25 | 1995-02-22 | 住友化学工业株式会社 | Process for production of unsaturated aldehyde and unsaturated carboxylic acid |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841434A (en) * | 2015-04-09 | 2015-08-19 | 中国科学院山西煤炭化学研究所 | Modified silica and cobalt loading catalyst, preparation method and application thereof |
| CN108325533A (en) * | 2018-02-01 | 2018-07-27 | 上海东化环境工程有限公司 | Modified support, O composite metallic oxide catalyst and method for producing acrylic acid |
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Application publication date: 20140521 |