CN102240558B - Composite oxide catalyst for oxidizing isobutylaldehyde into butanedione as well as preparation method and application thereof - Google Patents
Composite oxide catalyst for oxidizing isobutylaldehyde into butanedione as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a composite oxide catalyst for oxidizing isobutylaldehyde into butanedione as well as a preparation method and application thereof. The chemical composition of elements contained in the composite oxide catalyst is as follows: AaBbCcDdMoeZnfCugOx. The preparation method of the composite oxide catalyst comprises the following steps of: sequentially weighing elements A, elements B, elements C, elements D, Mo, Zn and Cu according to the proportions of the elements in a general formula, and then mixing; adding water, and heating for dissolution; and sufficiently stirring to obtain slurry, evaporating to dryness, carrying out extrusion forming, and roasting so as to finally obtain the composite oxide catalyst for oxidizing the isobutylaldehyde into the butanedione. The composite oxide catalyst disclosed by the invention can effectively enhance the efficiency of the butanedione by being applied to oxidation of the isobutylaldehyde into the butanedione and has the final yield of 35-45 percent; in addition, the composite oxide catalyst disclosed by the invention can keep high activity level within a longer time, that is to say, the composite oxide catalyst disclosed by the invention still enables the butanedione to keep stable high yield in 1000 hours after the reaction of oxidizing the isobutylaldehyde into the butanedione.
Description
Technical field
The present invention relates to the isobutyraldehyde oxidation catalyst, especially about the composite oxide catalysts of the isobutyraldehyde oxidation system diacetyl that contains molybdenum, zinc and copper.
Background technology
Diacetyl is the material that a kind of yellow to light green color has strong cream fragrance.It is important Organic Chemicals, can be used as the raw material of cyclisation compound, also can be used as the curing agent of gelatin and the binding agent of photograph, the intermediate that medicine, agricultural chemicals and fine chemicals are synthetic.In dairy products, diacetyl also is a kind of important flavor substance in cream, cheese, cheese and the many non-dairy products of distinguishing the flavor of of need suckling.The suitability for industrialized production of diacetyl receives people's attention.
Although diacetyl also exists in natural essential oil, from natural goods, to extract and can not satisfy people for the requirement on the diacetyl consumption, it is the main path that market obtains diacetyl that chemical method prepares diacetyl.The raw material of chemical production diacetyl has multiple.
MEK is the raw material that traditional chemical method synthesizes diacetyl; In this technology; MEK makes diacetyl through processes such as hydrolysis and distillations after the oxidation of oxidant natrium nitrosum, the maximum shortcoming of this technology is to consume a large amount of natrium nitrosums in producing; Discharge a large amount of nitrogen oxide and acid-bearing wastewater, seriously polluted.
MEK oximate method is another method of the synthetic diacetyl of chemical method.This method is under the acid effect, to carry out oximation reaction with MEK and nitrites, prepares diacetyl through processes such as crystallization, hydrolysis, distillations, and there is pollution problem equally in this technology; And nitrites toxicity is big, boiling point is low; Need in situ preparation, the preparation process produces a large amount of sulfuric acid (hydrogen) sodium, is difficult to reclaim.
With ethylene methacrylic ketone is raw material, also can adopt chemical oxidization method to prepare diacetyl.In the method, oxidant is hydrogen peroxide solution or ferric iron.The yield of the synthetic diacetyl of this method is very high, but raw material is not easy to obtain, and complex process domesticly is difficult to industrialization.
People such as the Zhu Fugen of East China University of Science are in patent " preparation process of butanedione ", and disclosing a kind of is the method for the gaseous oxidation production diacetyl of raw material with the isobutanol.The catalyst that this method adopts is argentiferous, zinc and copper metal and hopcalite thereof, and this method can be produced continuously, but yield lower (15-16%) causes production cost higher, is unfavorable for suitability for industrialized production.
Isobutylaldehyde also can be used as the raw material of synthetic diacetyl, because isobutylaldehyde is the main accessory substance of fourth octanol, and the market wide material sources, cost is lower, and research is that the synthetic diacetyl of raw material has the advantage that raw material is easy to get, cost is low with the isobutylaldehyde.Japan Patent clear with 43-6201 and clear and 49-28171 be technology about the synthetic diacetyl of isobutylaldehyde, but its catalyst is of low quality, the yield of diacetyl is on the low side, is merely about 10%, is unfavorable for suitability for industrialized production.
Clear and 54-46706 patent also discloses it and has adopted isobutylaldehyde to produce the patent of diacetyl; Its characteristics are to have developed with the mixture of metal oxide selecting one or more in zinc, zirconium, tungsten, copper and the silver and contain molybdenum as catalyst, have improved the yield of diacetyl.
Summary of the invention
The object of the present invention is to provide a kind of new isobutyraldehyde oxidation is the composite oxide catalysts of diacetyl, and this catalyst has lower production cost and higher diacetyl yield, and can in long-time, keep higher diacetyl yield.
Technical scheme of the present invention
A kind of isobutyraldehyde oxidation is the composite oxide catalysts of diacetyl, and the chemical composition of each element is pressed following general formula in the said composition:
A
aB
bC
cD
dMo
eZn
fCu
gO
x
In the formula: the A element is one or more elements that are selected from lithium, sodium, potassium, rubidium, the caesium;
The B element is at least a element that is selected from magnesium, the calcium;
The C element is one or more elements that are selected from nickel, cobalt, manganese, chromium, phosphorus, boron, tungsten, the vanadium;
The D element is at least a element that is selected from silicon, aluminium, titanium;
Wherein, 0≤a≤0.7,0≤b≤2,0＜c≤8,0≤d≤15,0＜e≤10,0＜f≤10,0＜g≤10, the x value is for satisfying the summation of other element valence requisite oxygen atomicity.
The shape that a kind of isobutyraldehyde oxidation of the present invention is the composite oxide catalysts of diacetyl does not have special demands, can they be shaped to annular, cylindricality, sphere, hollow tubular or sheet shape etc., and average grain diameter 1-15mm can be preferably 3-8mm.
Above-mentioned a kind of isobutyraldehyde oxidation is the preparation method of the composite oxide catalysts of diacetyl, promptly by logical
Formula A
aB
bC
cD
dMo
eZn
fCu
gO
xIn the ratio of each element mix after taking by weighing A element, B element, C element, D element, Mo, Zn and Cu successively; Add water and heat and dissolve; Fully stir slurry, with the slurry evaporate to dryness of processing, extrusion modling; At last in roaster in roasting, the composite oxide catalysts that promptly to get a kind of isobutyraldehyde oxidation of the present invention be diacetyl.
Above-mentioned a kind of isobutyraldehyde oxidation be the composite oxide catalysts of diacetyl when preparing the employed raw material of each element be preferably:
A, the most handy its nitrate of B element, hydroxide maybe can be decomposed into the salt of oxide.
Phosphorus in the C element, boron, tungsten, the most handy its corresponding acids of vanadium or its ammonium salt;
Mo, Zn and Cu element are used its oxide or are decomposed into the salt of oxide, the preferably water miscible nitrate of used salt.
The D element maybe can be decomposed into the salt of oxide with the oxide of nano-dispersed.
In preparation during catalyst, can add those and can improve catalyst strength and make catalyst have the additives known of regeneration properties, like inorfil, cellulose etc.
Catalyst of the present invention can be made into preformed catalyst separately and use, and also can on inert carrier such as aluminium oxide, silica, titanium dioxide, silica-alumina etc., use composite oxide supported.When under a kind of form in back, using, the content of composite oxides in the catalyst total amount is 10-90%, preferred 20-80%.
Above-mentioned a kind of isobutyraldehyde oxidation is that the composite oxide catalysts of diacetyl is to use in the diacetyl at isobutyraldehyde oxidation.
Beneficial effect of the present invention
Because the present invention, the method for preparing diacetyl from isobutylaldehyde can be carried out with any known method, importantly adopts one of the above composite oxides as catalyst, does not have particular restriction to preparing required instrument and operating condition.
In addition, a kind of isobutyraldehyde oxidation of the present invention is diacetyl composite oxide catalysts is a kind of high activity and the good catalyst of power of regeneration.At isobutyraldehyde oxidation is in the application of diacetyl, and the result shows can effectively improve the efficient that isobutylaldehyde is converted into diacetyl, and the yield of diacetyl is improved, and ultimate yield is 35～45%.
And; Composite oxide catalysts of the present invention can keep its high activity level in a long time; So use composite oxide catalysts of the present invention isobutyraldehyde oxidation be in the application of diacetyl in a long time, promptly react and still make diacetyl keep stable high yield after 1000 hours.
The specific embodiment
Through embodiment the present invention is done further elaboration below.It is pointed out that these embodiment have no restriction to scope of the present invention.
The detection method of diacetyl adopts gas chromatography among the present invention, and instrument is a GC102 type gas chromatograph, and Shanghai institute of computing technology produces;
The used isobutylaldehyde purity of the present invention is 99%, and Co., Ltd provides by the rich sugarcane chemical industry in Shanghai;
It is pure that other various chemicals are analysis, available from Shanghai medicine Group Co.,Ltd.
The diacetyl yield calculates as follows in the present invention:
Embodiment 1
The preparation of catalyst 1
With 1.7 gram sodium nitrate, 128.2 gram magnesium nitrates and 42.2 gram manganese acetates mixing, add water 30 grams, the dissolving of heating back gets material (A);
88 gram ammonium molybdates are dissolved in 50～90 ℃ of hot water of 50 grams, get material (B);
After 145.4 gram zinc nitrates and 120.8 gram copper nitrates mixing, add water 50 grams, get material (C);
Fully stir after with material (A), (B) and (C) mixing slurry, with the slurry evaporate to dryness of processing, be squeezed into cylindricality by conventional method, at last in roaster in 500 ℃ of roastings 6 hours, the catalyst 1 ingredient formula of processing is: Na
0.2MgMn
0.5MoZnCuO
x
In a diameter is 25 millimeters, the stainless steel reaction pipe of high 500mm, pack into the catalyst 1 of gained above the 40ml, feeding proportioning raw materials (mole) is the admixture of gas of isobutylaldehyde: air=1:1.The control reaction temperature is 300 ℃, is 1200h in air speed
-1Condition under carry out oxidation reaction.
The yield of the diacetyl of catalyst 1 after the diacetyl yield of incipient stage is 35.3%, 1000 hour is 35.4%.
Embodiment 2
With 2.55 gram sodium nitrate, 64.1 gram magnesium nitrates, 72.7 gram nickel nitrates and 42.2 gram manganese acetates mixing, add water 30 grams, the dissolving of heating back gets material (A);
176 gram ammonium molybdates are dissolved in 50～90 ℃ of hot water of 50 grams, get material (B);
After 145.4 gram zinc nitrates and 120.8 gram copper nitrates mixing, add water 50 grams, get material (C);
Fully stir after with material (A), (B) and (C) mixing slurry, with the slurry evaporate to dryness of processing, be squeezed into cylindricality by conventional method, at last in roaster in 500 ℃ of roastings 6 hours, the catalyst 2 ingredient formulas of processing are: Na
0.3Mg
0.5Ni
0.5Mn
0.5Mo
2ZnCuO
x
In a diameter is 25 millimeters, the stainless steel reaction pipe of high 500mm, pack into the catalyst 2 of gained above the 40ml, feeding proportioning raw materials (mole) is the admixture of gas of isobutylaldehyde: air=1:1.The control reaction temperature is 300 ℃, is 1200h in air speed
-1Condition under carry out oxidation reaction.
The yield of the diacetyl of catalyst 2 after the diacetyl yield of incipient stage is 36.0%, 1000 hour is 36.2%.
Embodiment 3
With 1.7 gram sodium nitrate, 25.2 gram potassium nitrate, 128.2 gram magnesium nitrates and 84.4 gram manganese acetates mixing, add water 30 grams, the dissolving of heating back gets material (A);
88 gram ammonium molybdates are dissolved in 50～90 ℃ of hot water of 50 grams, get material (B);
After 218.1 gram zinc nitrates and 241.6 gram copper nitrates mixing, add water 50 grams, get material (C);
Fully stir after with material (A), (B) and (C) mixing slurry, with the slurry evaporate to dryness of processing, be squeezed into cylindricality by conventional method, at last in roaster in 500 ℃ of roastings 6 hours, the catalyst 3 ingredient formulas of processing are: Na
0.2K
0.5MgMnMoZn
1.5Cu
2O
x
In a diameter is 25 millimeters, the stainless steel reaction pipe of high 500mm, pack into the catalyst 3 of the above-mentioned gained of 40ml, feeding proportioning raw materials (mole) is the admixture of gas of isobutylaldehyde: air=1:1.The control reaction temperature is 300 ℃, is 1200h in air speed
-1Condition under carry out oxidation reaction.
The yield of the diacetyl of catalyst 3 after the diacetyl yield of incipient stage is 41.2%, 1000 hour is 41.2%.
Embodiment 4
1.7 gram sodium nitrate and 64.1 are restrained magnesium nitrates, add water 30 grams, the dissolving of heating back gets material (A);
264 gram ammonium molybdates are dissolved in 50～90 ℃ of hot water of 50 grams, get material (B);
After 145.4 gram zinc nitrates and 120.8 gram copper nitrates mixing, add water 50 grams, get material (C)
Fully stir after material (A), (B), (C) and 40.1 gram cobaltosic oxides are mixed slurry; By conventional method with the slurry evaporate to dryness of processing; Be squeezed into cylindricality, at last in roaster in 500 ℃ of roastings 6 hours, the catalyst 4 ingredient formulas of processing are: Na
0.2Mg
0.5Co
0.5Mo
3ZnCuO
x
In a diameter is 25 millimeters, the stainless steel reaction pipe of high 500mm, pack into the catalyst 3 of the above-mentioned gained of 40ml, feeding proportioning raw materials (mole) is the admixture of gas of isobutylaldehyde: air=1:1.The control reaction temperature is 300 ℃, is 1200h in air speed
-1Condition under carry out oxidation reaction.
The yield of the diacetyl of catalyst 3 after the diacetyl yield of incipient stage is 38.9%, 1000 hour is 38.8%.
Embodiment 5
With 1.7 gram sodium nitrate, 25.2 gram potassium nitrate, 128.2 gram magnesium nitrates and 84.4 gram manganese acetates mixing, add water 30 grams, the dissolving of heating back gets material (A);
88 gram ammonium molybdates are dissolved in 50～90 ℃ of hot water of 50 grams, get material (B);
After 218.1 gram zinc nitrates and 241.6 gram copper nitrates mixing, add water 50 grams, get material (C);
Fully stir after material (A), (B), (C) and 572 grams, 60% Ludox mixed slurry; Then by conventional method with the slurry evaporate to dryness of processing; Be squeezed into cylindricality, at last in roaster in 500 ℃ of roastings 6 hours, the catalyst 5 ingredient formulas of processing are: 50%Na
0.2K
0.5MgMnMoZn
1.5Cu
2O
x/ 50%SiO
2
In a diameter is 25 millimeters, the stainless steel reaction pipe of high 500mm, pack into the catalyst 3 of the above-mentioned gained of 40ml, feeding proportioning raw materials (mole) is the admixture of gas of isobutylaldehyde: air=1:1.The control reaction temperature is 300 ℃, is 1200h in air speed
-1Condition under carry out oxidation reaction.
The yield of the diacetyl of catalyst 3 after the diacetyl yield of incipient stage is 45%, 1000 hour is 44.8%.
Embodiment 6
With 0.85 gram sodium nitrate, 89.7 gram magnesium nitrates and 168.8 gram manganese acetates mixing, add water 30 grams, the dissolving of heating back gets material (A);
264 gram ammonium molybdates and 39.2 gram ammonium metavanadates are dissolved in 50～90 ℃ of hot water of 50 grams, get material (B);
After 145.4 gram zinc nitrates and 241.6 gram copper nitrates mixing, add water 50 grams, get material (C).
Fully stir after with material (A), (B) and (C) mixing slurry, with the slurry evaporate to dryness of processing, be squeezed into cylindricality by conventional method, at last in roaster in 500 ℃ of roastings 6 hours, the catalyst 6 ingredient formulas of processing are: Na
0.1Mg
0.7V
0.5Mn
2Mo
3ZnCu
2O
x
In a diameter is 25 millimeters, the stainless steel reaction pipe of high 500mm, pack into the catalyst 6 of the above-mentioned gained of 40ml, feeding proportioning raw materials (mole) is the admixture of gas of isobutylaldehyde: air=1:1.The control reaction temperature is 300 ℃, is 1200h in air speed
-1Condition under carry out oxidation reaction.
The yield of the diacetyl of catalyst 6 after the diacetyl yield of incipient stage is 40.2%, 1000 hour is 40.1%.
The contrast that the above embodiments 1～6 are carried out; Can find out that the catalyst formulation that combination is implemented according to general formula all can embody higher diacetyl yield; Particularly; With Mo, Zn, Cu is main element, and exogenously added alkali metal, alkaline-earth metal or transition metal etc. can suitably be regulated the yield that isobutylaldehyde is produced diacetyl, but whole all catalyst all embody good working stability.Therefore, adopt the prescription of catalyst provided by the present invention, the catalyst that obtains can reduce production costs when practical application and the number of times of catalyst changeout more greatly, to the management of suitability for industrialized production with reduce production costs highly beneficial.
The above content is merely the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (10)
1. composite oxide catalysts that isobutyraldehyde oxidation is a diacetyl, the chemical composition that it is characterized in that each element in this composite oxide catalysts composition are by as follows:
A
aB
bC
cD
dMo
eZn
fCu
gO
x
In the formula: A is one or more elements that are selected from lithium, sodium, potassium, rubidium, the caesium;
B is at least a element that is selected from magnesium, the calcium;
C is one or more elements that are selected from nickel, cobalt, manganese, chromium, phosphorus, boron, tungsten, the vanadium;
D is at least a element that is selected from silicon, aluminium, titanium;
Wherein, 0 < a≤0.7,0 <b≤2,0＜c≤8,0≤d≤15,0＜e≤10,0＜f≤10,0＜g≤10, the x value is for satisfying the summation of other each the element valence requisite oxygen atomicity beyond the deoxygenation.
2. a kind of isobutyraldehyde oxidation as claimed in claim 1 is the composite oxide catalysts of diacetyl, it is characterized in that the chemical composition of each element in this composite oxide catalysts composition is following:
Na
0.2MgMn
0.5MoZnCuO
x；
Wherein the x value is for satisfying the summation of other element valence requisite oxygen atomicity beyond the deoxygenation.
3. a kind of isobutyraldehyde oxidation as claimed in claim 1 is the composite oxide catalysts of diacetyl, it is characterized in that the chemical composition of each element in this composite oxide catalysts composition is following:
Na
0.3Mg
0.5Ni
0.5Mn
0.5Mo
2ZnCuO
x。
4. a kind of isobutyraldehyde oxidation as claimed in claim 1 is the composite oxide catalysts of diacetyl, it is characterized in that this is compound
The chemical composition of each element is following in the oxide catalyst composition:
Na
0.2K
0.5MgMnMoZn
1.5Cu
2O
x；
Wherein the x value is for satisfying the summation of other element valence requisite oxygen atomicity beyond the deoxygenation.
5. a kind of isobutyraldehyde oxidation as claimed in claim 1 is the composite oxide catalysts of diacetyl, it is characterized in that this is compound
The chemical composition of each element is following in the oxide catalyst composition:
Na
0.2Mg
0.5Co
0.5Mo
3ZnCuO
x；
Wherein the x value is for satisfying the summation of other element valence requisite oxygen atomicity beyond the deoxygenation.
6. a kind of isobutyraldehyde oxidation as claimed in claim 1 is the composite oxide catalysts of diacetyl, it is characterized in that the chemical composition of each element in this composite oxide catalysts composition is following: Na
0.1Mg
0.7V
0.5Mn
2Mo
3ZnCu
2O
x
Wherein the x value is for satisfying the summation of other element valence requisite oxygen atomicity beyond the deoxygenation.
7. a kind of isobutyraldehyde oxidation as claimed in claim 1 is the composite oxide catalysts of diacetyl, it is characterized in that the chemical composition of each element in this composite oxide catalysts composition is following:
Na
0.2K
0.5MgMnMoZn
1.5Cu
2O
x；
Wherein the x value is for satisfying the summation of other element valence requisite oxygen atomicity beyond the deoxygenation.
8. the preparation method who is the composite oxide catalysts of diacetyl like the described a kind of isobutyraldehyde oxidation of the arbitrary claim of claim 1～7 is characterized in that by general formula A
aB
bC
cD
dMo
eZn
fCu
gO
xIn the ratio of each element mix after taking by weighing A element, B element, C element, D element, Mo, Zn and Cu successively; Add water and heat and dissolve; Fully stir slurry, with the slurry evaporate to dryness of processing, extrusion modling; At the roasting kiln roasting, promptly get the composite oxide catalysts that a kind of isobutyraldehyde oxidation is a diacetyl at last;
Wherein:
A element and B element are selected its nitrate, hydroxide for use;
Phosphorus in the C element, boron, tungsten, vanadium are selected its corresponding acid or its ammonium salt for use;
The D element selects for use the oxide of its nano-dispersed maybe can be decomposed into the salt of oxide;
Mo, Zn and Cu select its oxide for use or are decomposed into the water miscible nitrate of oxide;
Described roasting was promptly calcined 6 hours down at 500 ℃.
9. a kind of isobutyraldehyde oxidation as claimed in claim 8 is the preparation method of the composite oxide catalysts of diacetyl; When it is characterized in that preparing catalyst, adding can improve catalyst strength and the inorfil or the cellulose that make catalyst have regeneration properties as additive.
10. the application that is the composite oxide catalysts of diacetyl like the described a kind of isobutyraldehyde oxidation of the arbitrary claim of claim 1～7 is characterized in that this composite oxide catalysts is made into separately that preformed catalyst uses or composite oxide catalysts loaded on the inert carrier using;
Described inert carrier is aluminium oxide, silica, titanium dioxide or silica-alumina.
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|---|---|---|---|
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