CN102850359B - The preparation method of polynuclear metal phthalocyanine alkane oxidation catalyst - Google Patents
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Abstract
The present invention relates to the preparation method of polynuclear metal phthalocyanine alkane oxidation catalyst, its preparation process is: using the Tetra hydro Phthalic anhydride of certain mol proportion or replacement Tetra hydro Phthalic anhydride, urea, pyromellitic dianhydride, source metal etc. as raw material, react in high boiling solvent, then boil through peracid, soda boiling, washing, suction filtration, surname extraction, drying, obtain multi-nuclear metal phthalocyanine.The preparation method of the multi-nuclear metal phthalocyanine that the present invention relates to, compared with the preparation method of published multi-nuclear metal phthalocyanine, flow process is comparatively easy, and finished catalyst yield is generally more than 60%, and volatile solvent and solid waste discharge less; This catalyst application is in the catalytic oxidation process of butane, hexanaphthene etc., and feed stock conversion is not less than 10%, has very wide application prospect in catalysis oxidation of alkanes field.
Description
Technical field
The present invention relates to a kind of method preparing polynuclear metal phthalocyanine alkane oxidation catalyst.
Background technology
Multi-nuclear metal phthalocyanine has very wide application prospect in catalysis low-carbon alkanes oxidation field, just because of this, has general meaning for the research preparing multi-nuclear metal phthalocyanine.
The preparation method of disclosed multi-nuclear metal phthalocyanine mainly contains single stage method and two-step approach two class at present, specifically there are following three kinds of methods: (1) urea-phthalic anhydride scorification, the method is for main raw material with Tetra hydro Phthalic anhydride, urea, pyromellitic dianhydride and source metal, carry out solid state reaction, obtain multi-nuclear metal phthalocyanine.The temperature of reaction general higher (being generally more than 250 DEG C) of the method, the large usage quantity (usually wanting excessive about 10 times) of urea, can produce more solid waste, and the yield of product is general lower by (40 ~ 50%, in source metal, lower same).(2) phthalic nitrile scorification, the method for main raw material with phthalic nitrile, all benzene four formonitrile HCN and source metal, is carried out solid state reaction, obtain multi-nuclear metal phthalocyanine.The method raw materials cost is higher.(3) diiminoisoindole solvent synthesis method, the method is first that raw material carries out liquid phase reaction in high boiling solvent with 1,3-diiminoisoindole, all benzene four isoindoline, obtained multinuclear metal-free phthalocyanine, and then and reacting metal salt, obtain multi-nuclear metal phthalocyanine.The method flow process is longer, and cost of material is higher, and product yield is lower.
Chinese patent CN200910116643.1 discloses a kind of to replace Tetra hydro Phthalic anhydride, pyromellitic dianhydride, urea etc. for raw material, the method for Solid phase synthesis substituted binuclear/tri-core phthalocyanine cobalt sulfonate desulfurization catalyst.The method simple flow, raw materials cost is low, but the temperature of solid-phase synthesis higher (being generally 220 ~ 250 DEG C), severe reaction conditions, catalyzer yield is not high.
It is raw material that Chinese patent CN201110205664.8 discloses with substituted phthalic mitrile, take carbon nanotube as template, the method for synthesis binuclear metal phthalocyanine coordination compound.The yield of the method products obtained therefrom is higher, but preparation flow is complicated, and raw materials cost is higher.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of preparation method of polynuclear metal phthalocyanine alkane oxidation catalyst.
Its technical solution is:
The preparation method of polynuclear metal phthalocyanine alkane oxidation catalyst, comprises the following steps:
Be (n+2) by mol ratio: 3 (n+3) ~ 4 (n+3): (n+1) ~ 1.5 (n+1): source metal, the Tetra hydro Phthalic anhydride of 15 (n+2) ~ 20 (n+2) or replace Tetra hydro Phthalic anhydride, pyromellitic dianhydride, urea mixes with ammonium molybdate catalyst and ammonium chloride additive, in mixture, the massfraction of ammonium molybdate catalyst is 0.2% ~ 2%, and the massfraction of ammonium chloride additive is 1% ~ 5%; By mixture grinding evenly, add high boiling solvent, be warming up to 100 ~ 160 DEG C, reaction 30 ~ 50min, then continues the boiling point being warming up to high boiling solvent, and reaction 3 ~ 5h, is then cooled to 70 ~ 90 DEG C, obtains product mixture; Again product mixture is carried out aftertreatment, obtain bluish voilet to atropurpureus polynuclear metal phthalocyanine alkane oxidation catalyst finished product, its general structure is such as formula shown in (I), wherein, n be more than or equal to 0 integer, when n >=1, i=2,3 ... (n+1); M is the metal as active centre; X is peripheric substitution base; Y is non-circumferential substituting group; L is axial ligand;
Above-mentioned aftertreatment comprises following operation steps:
The first step: by product mixture suction filtration, solvent recuperation, obtains a filter cake; With distilled water, dilute hydrochloric acid, dilute NaOH solution, a filter cake is boiled 5 ~ 30min respectively, then filter, operate 2 ~ 3 times before repetition, obtain secondary filter cake; With hot wash secondary filter cake to filtrate in neutral, obtain three filter cakes; Three filter cakes are dried at 80 ~ 100 DEG C, obtains the thick product of polynuclear metal phthalocyanine alkane oxidation catalyst;
Second step: thick for polynuclear metal phthalocyanine alkane oxidation catalyst product is carried out surname extraction, until extracting liquid colourless, dries remaining solid, obtains bluish voilet to atropurpureus polynuclear metal phthalocyanine alkane oxidation catalyst finished product.
Above-mentioned source metal be selected from metal chlorination salt, metal oxide, metal acetate salt or metal sulfate one or more.
The solvent that the preferred boiling point of above-mentioned high boiling solvent is greater than 180 DEG C, being more preferably boiling point is solvent within the scope of 180 ~ 210 DEG C, concrete preferred high boiling alkane (as perhydronaphthalene, naphthane or dodecane etc.) or alkylbenzene (as n-butylbenzene, tert.-butylbenzene or dodecylbenzene etc.) or its mixture.
In formula (I), catalyst active center's metal M
1... M
i... M
n+2be respectively the one in aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, palladium, tin, platinum.
In formula (I), peripheric substitution base X, non-circumferential substituting group Y be respectively in hydrogen atom, alkyl, alkoxyl group, halogen, acid group or hydroxyl one or both.
In formula (I), axial substituted base L
1, L
2... L
(2i-1), L
2i... L
(2n+3), L
(2n+4)be respectively one in halogen, Sauerstoffatom or hydroxyl or be nothing.
Using one or more in low boiling point organic solvent as extraction agent in above-mentioned surname extraction step, described low boiling point organic solvent particular methanol, ethanol, acetone or ethyl acetate.
The inventive method, compared with the preparation method of existing multi-nuclear metal phthalocyanine, has following beneficial effect:
(1) because the inventive method adopts one-step synthesis, simplify preparation flow largely, reduce unnecessary raw material and the loss of intermediate product;
(2) be using urea, Tetra hydro Phthalic anhydride due to the inventive method or replace Tetra hydro Phthalic anhydride, pyromellitic dianhydride etc. as main raw material, avoid the problem that the preparation cost that in the past uses the raw material such as isoindoline, phthalic nitrile to bring is higher;
(3) because the inventive method is that various raw material reacts in solvent, this not only lowers the temperature (being only 180 ~ 210 DEG C) needed for reaction, and decrease the consumption (excessive about 2 times) of urea, thus reduce the quantity discharged of solid waste, alleviate the pollution to environment;
(4) because the inventive method have employed liquid phase method technique, decrease the generation of by product, the yield of finished product is higher (being generally not less than 60%);
(5) due to the inventive method use solvent be the organic solvent such as high boiling alkane or alkylbenzene, be not only convenient to the recycling of solvent, and due to such solvent toxicity less, further reduce the pollution to environment.
The multi-nuclear metal phthalocyanine that the inventive method is prepared for original technique with urea-phthalic anhydride-liquid phase method technology generations, product yield is higher, preparation cost is lower, of reduced contamination, and this epoxidation agent has comparatively active catalytic oxidation activity.In view of These characteristics, the multi-nuclear metal phthalocyanine prepared in the process of the present invention can be widely used in the reaction of catalysis oxidation of alkanes.
Below by several groups of experimental examples polynuclear metal phthalocyanine alkane oxidation catalyst illustrated prepared by the inventive method, there is good catalysis oxidation of alkanes effect.
A is by 49.8mg double-core iron/copper phthalocyanine (general structure such as formula shown in (I), wherein, n=0; M
1=Fe, M
2=Cu; X=Y=H, H; L
1~ L
4=nothing) and three cores iron-iron/copper phthalocyanine (general structure such as formula shown in (I), wherein, n=1; M
1=M
2=Fe, M
3=Cu; X=H, Y=H; L
1~ L
6=nothing) mixed catalyst add in 250ml autoclave, quantitatively add 45.8g Trimethylmethane and 5.1g n-butane feedstock, take oxygen as oxygen source, in 110 DEG C, 2.8 ~ 3.0Mpa, rotating speed are react 6h under 300r/min condition, room temperature is cooled to, slowly by butane raw material unreacted in reactor and oxygen emptying after reacted.Weigh remaining product liquid in reactor and carry out compositional analysis by gas-chromatography to product liquid, calculating raw material butanes conversion is 43.5%.
B is by 52.3mg double-core iron/copper phthalocyanine (general structure such as formula shown in (I), wherein, n=0; M
1=Fe, M
2=Cu; X=Y=H, H; L
1~ L
4=nothing) and three cores iron-iron/copper phthalocyanine (general structure such as formula shown in (I), wherein, n=1; M
1=M
2=Fe, M
3=Cu; X=H, Y=H; L
1~ L
6=nothing) mixed catalyst add in 250ml autoclave, quantitatively add 48.7g normal butane and 2.8g isobutane feedstock, take air as oxygen source, in 135 DEG C, 3.6 ~ 3.8Mpa, rotating speed are react 6h under 300r/min condition, room temperature is cooled to, slowly by butane raw material unreacted in reactor and air emptying after reacted.Weigh remaining product liquid in reactor and carry out compositional analysis by gas-chromatography to liquid product, calculating raw material butanes conversion is 18.7%.
C is by 50.4mg double-core iron/copper phthalocyanine (general structure such as formula shown in (I), wherein, n=0; M
1=Fe, M
2=Cu; X=Y=H, H; L
1~ L
4=nothing) and three cores iron-iron/copper phthalocyanine (general structure such as formula shown in (I), wherein, n=1; M
1=M
2=Fe, M
3=Cu; X=H, Y=H; L
1~ L
6=nothing) mixed catalyst add in 250ml autoclave, quantitatively add 50.6g hexanaphthene raw material, in 140 DEG C, take oxygen as oxygen source, 1.0 ~ 1.2Mpa, rotating speed are react 6h under 300r/min condition, are cooled to room temperature, slowly by oxygen emptying remaining in reactor after reacted.Weigh remaining product liquid in reactor and carry out compositional analysis by gas-chromatography to liquid product, calculating raw material cyclohexane conversion is 10.5%.
In sum, the preparation method of multi-nuclear metal phthalocyanine of the present invention, difference with the prior art is, with Tetra hydro Phthalic anhydride or replace Tetra hydro Phthalic anhydride, urea, pyromellitic dianhydride is for main raw material, with high boiling alkane or alkylbenzene for solvent, liquid phase method synthesis multi-nuclear metal phthalocyanine.Method flow of the present invention is easy, product yield is higher, environmental pollution is less.The catalytic oxidation activity of gained catalyzer is higher, has very wide application prospect in catalysis oxidation of alkanes field.
Embodiment
The preparation method of multi-nuclear metal phthalocyanine carries out according to the following steps: in order to the urea of certain mol proportion, Tetra hydro Phthalic anhydride or replace Tetra hydro Phthalic anhydride, pyromellitic dianhydride, source metal be raw material, take ammonium molybdate as catalyzer, take ammonium chloride as synthetic additive, with high boiling alkane, alkylbenzene or its mixture etc. for solvent, with liquid phase reaction → suction filtration → boil (distilled water, diluted acid, diluted alkaline etc.) thick product → surname extraction → drying → finished catalyst of → catalyzer.
The general structure of above-mentioned multi-nuclear metal phthalocyanine such as formula shown in (I), wherein: n=0,1,2 As n=0, i=without, when n >=1, i=2,3 ... (n+1) all integers between 2 ~ (n+1), are namely got; M is the metal as active centre; X is peripheric substitution base; Y is non-circumferential substituting group; L is axial ligand.
The constitutional features of this molecule is: phthalocyanine ring is with phenyl ring bridging; M
1~ M
n+2in arbitrary catalyst active center metal can be one in aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, palladium, tin, platinum.X, Y substituting group can be respectively in hydrogen atom, alkyl, alkoxyl group, halogen, acid group, hydroxyl etc. one or both, specifically determine according to reaction raw materials; As reaction raw materials be Tetra hydro Phthalic anhydride time, two peripheric substitution bases in formula (I) on phenyl ring are H, and two non-circumferential substituting groups are also H, i.e. X=Y=H, H; As reaction raw materials be a chloro-phthalic anhydride time, one, two peripheric substitution bases in formula (I) on phenyl ring are Cl, and one is H, and two non-circumferential substituting groups are H, i.e. X=Cl, H; Y=H, H, due to when reaction raw materials is a chloro-phthalic anhydride, two peripheric substitution bases in formula (I) on phenyl ring are that the possibility of Cl is almost equal, therefore inconvenience further limits the position of Cl on phenyl ring, and only use X=Cl, H represents.L
1~ L
(2n+4)in arbitrary axial substituted base can be one in halogen, Sauerstoffatom, hydroxyl etc. also can be nothing.
Embodiment 1
Double-core iron-iron-phthalocyanine alkane oxidation catalyst (general structure such as formula shown in (I), wherein, n=0; M
1=M
2=Fe; X=Y=H, H; L
1~ L
4=nothing) preparation process as follows:
The first step: by Tetra hydro Phthalic anhydride 15g, urea 19g, four water and iron protochloride 3.7g, pyromellitic dianhydride 2.7g and 0.5g ammonium molybdate catalyst, 2.1g ammonium chloride additive mixes and grinding is even, add 100ml perhydronaphthalene solvent, obtain reaction mixture.First reaction mixture is warming up to 150 DEG C, reaction 30min, is then warming up to solvent boiling point, maintains boiling temperature reaction 4h, is then cooled to 80 DEG C, obtains product mixture.
Second step: by product mixture suction filtration, solvent recuperation, obtains a filter cake.With distilled water, dilute hydrochloric acid, dilute NaOH solution, a filter cake is boiled 15min respectively, then filter, repeat aforesaid operations 2 times, obtain secondary filter cake.With hot wash secondary filter cake to filtrate in neutral, obtain three filter cakes.Three filter cakes are dried at 80 DEG C, obtains the thick product of catalyzer.
3rd step: thick for catalyzer product is carried out surname extraction, until extracting liquid colourless, dried by remaining solid, obtain atropurpureus pulverulent solids double-core iron-iron-phthalocyanine alkane oxidation catalyst finished product, yield is 70.3%.
Embodiment 2
Three core iron-iron-iron-phthalocyanine alkane oxidation catalysts (general structure such as formula shown in (I), wherein, n=1; M
1=M
2=M
3=Fe; X=Y=H, H; L
1~ L
6=nothing) preparation process as follows:
The first step: by Tetra hydro Phthalic anhydride 18g, urea 29g, four water and iron protochloride 5.6g, pyromellitic dianhydride 5.4g and 0.8g ammonium molybdate catalyst, 2.1g ammonium chloride additive mixes and grinding is even, add 100ml perhydronaphthalene solvent, obtain reaction mixture.First reaction mixture is warming up to 150 DEG C, reaction 30min, is then warming up to solvent boiling point, maintains boiling temperature reaction 4h, is then cooled to 80 DEG C, obtains product mixture.
Second step: by product mixture suction filtration, solvent recuperation, obtains a filter cake.With distilled water, dilute hydrochloric acid, dilute NaOH solution, a filter cake is boiled 15min respectively, then filter, repeat to operate 2 times before this, obtain secondary filter cake.With hot wash secondary filter cake to filtrate in neutral, obtain three filter cakes.Three filter cakes are dried at 80 DEG C, obtains the thick product of catalyzer.
3rd step: thick for catalyzer product is carried out surname extraction, until extracting liquid colourless, dried by remaining solid, obtain atropurpureus pulverulent solids three core iron-iron-iron-phthalocyanine alkane oxidation catalyst finished product, catalyzer yield is 69.3%.
Embodiment 3
Double-core chlordene iron/copper phthalocyanine alkane oxidation catalyst (general structure such as formula shown in (I), wherein, n=0; M
1=Fe, M
2=Cu; X=Cl, H; Y=H, H; L
1~ L
4=nothing) preparation process as follows:
The first step: by a chloro-phthalic anhydride 35g, urea 19g, four water and iron protochloride 1.8g, cuprous chloride 1.0g, pyromellitic dianhydride 2.7g and 0.5g ammonium molybdate catalyst, 2.1g ammonium chloride additive mixes and grinding is even, add 100ml dodecane, obtain reaction mixture.First reaction mixture is warming up to 160 DEG C, reaction 40min, is then warming up to solvent boiling point, maintains boiling temperature reaction 4h, is then cooled to 70 DEG C, obtains product mixture.
Second step: by product mixture suction filtration, solvent recuperation, obtains a filter cake.With distilled water, dilute hydrochloric acid, dilute NaOH solution, a filter cake is boiled 20min respectively, then filter, repeat aforesaid operations 2 times, obtain secondary filter cake.With hot wash secondary filter cake to filtrate in neutral, obtain three filter cakes.Three filter cakes are dried at 90 DEG C, obtains the thick product of catalyzer.
3rd step: thick for catalyzer product is carried out surname extraction, until extracting liquid colourless, dried by remaining solid, obtain bluish voilet pulverulent solids double-core chlordene iron/copper phthalocyanine alkane oxidation catalyst finished product, catalyzer yield is 75.3%
Embodiment 4
Three core iron-iron/copper phthalocyanine alkane oxidation catalyst (general structure such as formula shown in (I), wherein, n=1; M
1=M
2=Fe, M
3=Cu; X=Y=H, H; L
1~ L
6=nothing) preparation process as follows:
The first step: by Tetra hydro Phthalic anhydride 18g, urea 23g, four water and iron protochloride 3.7g, cuprous chloride 1.0g, pyromellitic dianhydride 5.4g and 0.5g ammonium molybdate catalyst, 2.1g ammonium chloride additive mixes and grinding is even, add 100ml perhydronaphthalene solvent, obtain reaction mixture.First reaction mixture is warming up to 150 DEG C, reaction 30min, is then warming up to solvent boiling point, maintains boiling temperature reaction 5h, is then cooled to 80 DEG C, obtains product mixture.
Second step: by product mixture suction filtration, solvent recuperation, obtains a filter cake.With distilled water, dilute hydrochloric acid, dilute NaOH solution, a filter cake is boiled 30min respectively, then filter, repeat to operate 2 times before this, obtain secondary filter cake.With hot wash secondary filter cake to filtrate in neutral, obtain three filter cakes.Three filter cakes are dried at 80 DEG C, obtains the thick product of catalyzer.
3rd step: thick for catalyzer product is carried out surname extraction, until extracting liquid colourless, dried by remaining solid, obtain bluish voilet pulverulent solids three core iron-iron/copper phthalocyanine alkane oxidation catalyst finished product, yield is 72.3%.
Embodiment 5
Binuclear Cobalt-cobalt phthalocyanine alkane oxidation catalyst (general structure such as formula shown in (I), wherein, n=0; M
1=M
2=Co; X=Y=H, H; L
1~ L
4=nothing) preparation process as follows:
The first step: by Tetra hydro Phthalic anhydride 15g, urea 19g, six water and cobalt chloride 5.4g, pyromellitic dianhydride 2.7g and 0.5g ammonium molybdate catalyst, 2.1g ammonium chloride additive mixes and grinding is even, adds 100ml tert.-butylbenzene, obtains reaction mixture.First reaction mixture is warming up to 130 DEG C, reaction 50min, is then warming up to solvent boiling point, maintains boiling temperature reaction 3h, is then cooled to 90 DEG C, obtains product mixture.
Second step: by product mixture suction filtration, solvent recuperation, obtains a filter cake.With distilled water, dilute hydrochloric acid, dilute NaOH solution, a filter cake is boiled 10min respectively, then filter, repeat aforesaid operations 2 times, obtain secondary filter cake.With hot wash secondary filter cake to filtrate in neutral, obtain three filter cakes.Three filter cakes are dried at 100 DEG C, obtains the thick product of catalyzer.
3rd step: thick for catalyzer product is carried out surname extraction, until extracting liquid colourless, dried by remaining solid, obtain black blue powders shape solid Binuclear Cobalt-cobalt phthalocyanine alkane oxidation catalyst finished product, catalyzer yield is 80.6%.
Embodiment 6
Three core chlorine aluminium-cobalts-oxygen molybdenum phthalocyanine alkane oxidation catalyst (general structure such as formula shown in (I), wherein, n=1; M
1=Al, M
2=Co, M
3=Mo; X=Y=H, H; L
1=Cl, L
5=O, L
2=L
3=L
4=L
6=nothing) preparation process as follows:
Change metal-salt addition in embodiment 2 into aluminum chloride 1.3g, six water and cobalt chloride 1.4g, molybdic oxide 0.9g, reaction solvent is dodecane, other are with embodiment 2, and obtain bluish voilet pulverulent solids three core chlorine aluminium-cobalt-oxygen molybdenum phthalocyanine alkane oxidation catalyst finished product, catalyzer yield is 75.4%.
Embodiment 7
Double-core chlorine aluminium phthalocyanine alkane oxidation catalyst (general structure such as formula shown in (I), wherein, n=0; M
1=M
2=Al; X=Y=H, H; L
1=L
3=Cl; L
2=L
4=nothing) preparation process as follows:
Change metal-salt addition in embodiment 1 into aluminum trichloride (anhydrous) 2.6g, maintain boiling temperature reaction 3h, other are with embodiment 1, and obtain black blue powders shape solid double-core chlorine aluminium phthalocyanine alkane oxidation catalyst finished product, catalyzer yield is 76.2%.
Embodiment 8
Three core chlorine aluminium phthalocyanine alkane oxidation catalysts (general structure such as formula shown in (I), wherein, n=1; M
1=M
2=M
3=Al, X=Y=H, H; L
1=L
3=L
5=Cl; L
2=L
4=L
6=nothing) preparation process as follows:
Change metal-salt addition in embodiment 2 into aluminum trichloride (anhydrous) 4.0g, high boiling solvent is n-butylbenzene, and other are with embodiment 2, and obtain black blue powders shape solid three core chlorine aluminium phthalocyanine alkane oxidation catalyst finished product, catalyzer yield is 70.1%.
Embodiment 9
Four core chlorine aluminium phthalocyanine alkane oxidation catalysts (general structure such as formula shown in (I), wherein, n=2; M
1=M
2=M
3=M
4=Al, X=Y=H, H; L
1=L
3=L
5=L
7=Cl; L
2=L
4=L
6=L
8=nothing) preparation process as follows:
Raw material dosage is: Tetra hydro Phthalic anhydride 26g, urea 41g, Aluminum chloride anhydrous 5.3g, pyromellitic dianhydride 8.5g, ammonium molybdate 0.8g, ammonium chloride 2.1g, reaction solvent is n-butylbenzene, other are with embodiment 1, obtain black blue powders shape solid four core chlorine aluminium phthalocyanine alkane oxidation catalyst finished product, catalyzer yield is 65.1%.
Embodiment 10
Double-core oxygen molybdenum-copper alkane oxidation catalyst (general structure such as formula shown in (I), wherein, n=0; M
1=Mo, M
2=Cu, X=Y=H, H; L
1=O; L
2~ L
4=nothing) preparation process as follows:
Change the metal-salt addition in embodiment 1 into molybdic oxide 1.6g, cupric chloride 1.2g, other are with embodiment 1, and obtain bluish voilet solid double-core oxygen molybdenum-copper alkane oxidation catalyst finished product, catalyzer yield is 64.7%.
Embodiment 11
Three core oxygen molybdenum phthalocyanine alkane oxidation catalysts (general structure such as formula shown in (I), wherein, n=1; M
1=M
2=M
3=Mo; X=Y=H, H; L
1=L
3=L
5=O; L
2=L
4=L
6=nothing) preparation process as follows:
Change metal-salt addition in embodiment 2 into molybdic oxide 2.5g, maintain boiling temperature reaction 5h, other are with embodiment 2, and obtain bluish voilet pulverulent solids three core oxygen molybdenum phthalocyanine alkane oxidation catalyst finished product, catalyzer yield is 63.0%.
Embodiment 12
Five core oxygen molybdenum phthalocyanine alkane oxidation catalysts (general structure such as formula shown in (I), wherein n=3; M
1=M
2=M
3=M
4=M
5=Mo; X=Y=H, H; L
1=L
3=L
5=L
7=L
9=O; L
2=L
4=L
6=L
8=L
10=nothing) preparation process as follows:
Raw material dosage is: Tetra hydro Phthalic anhydride 18g, urea 30g, molybdic oxide 4.2g, pyromellitic dianhydride 6.7g, ammonium molybdate 1.0g, ammonium chloride 2.1g, maintain boiling temperature reaction 5h, other are with embodiment 1, obtain bluish voilet pulverulent solids five core oxygen molybdenum phthalocyanine alkane oxidation catalyst finished product, catalyzer yield is 66.5%.
Claims (4)
1. the preparation method of the polynuclear metal phthalocyanine alkane oxidation catalyst as shown in formula I, is characterized in that comprising the following steps:
Source metal, Tetra hydro Phthalic anhydride or replacement Tetra hydro Phthalic anhydride, pyromellitic dianhydride, urea are mixed with ammonium molybdate catalyst and ammonium chloride additive, source metal, Tetra hydro Phthalic anhydride or to replace the mol ratio of Tetra hydro Phthalic anhydride, pyromellitic dianhydride and urea be (n+2): 3 (n+3) ~ 4 (n+3): (n+1) ~ 1.5 (n+1): 15 (n+2) ~ 20 (n+2), in mixture, the massfraction of ammonium molybdate catalyst is 0.2% ~ 2%, and the massfraction of ammonium chloride additive is 1% ~ 5%; By mixture grinding evenly, add high boiling solvent, be warming up to 100 ~ 160 DEG C, reaction 30 ~ 50min, then continues the boiling point being warming up to high boiling solvent, and reaction 3 ~ 5h, is then cooled to 70 ~ 90 DEG C, obtains product mixture; Again product mixture is carried out aftertreatment, obtains bluish voilet to atropurpureus polynuclear metal phthalocyanine alkane oxidation catalyst finished product, its general structure such as formula shown in (I), wherein, n >=1, i=2,3 ... (n+1);
Described source metal be selected from metal chlorination salt, metal oxide, metal acetate salt or metal sulfate one or more; Metal in described source metal is selected from the one in aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, palladium, tin, platinum;
Described Tetra hydro Phthalic anhydride or replacement Tetra hydro Phthalic anhydride are
x, Y be respectively in hydrogen atom, alkyl, alkoxyl group, halogen, acid group or hydroxyl one or both;
Described high boiling solvent be selected from perhydronaphthalene, naphthane, dodecane, n-butylbenzene or dodecylbenzene one or more;
M in formula (I)
1... M
i... M
n+2be respectively the one in aluminium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zirconium, molybdenum, ruthenium, rhodium, palladium, tin, platinum;
In formula (I), X, Y be respectively in hydrogen atom, alkyl, alkoxyl group, halogen, acid group or hydroxyl one or both;
L in formula (I)
1, L
2... L
(2i-1), L
2i... L
(2n+3), L
(2n+4)be respectively one in halogen, Sauerstoffatom or hydroxyl or be nothing.
2. the preparation method of polynuclear metal phthalocyanine alkane oxidation catalyst according to claim 1, is characterized in that, described aftertreatment comprises following operation steps:
The first step: by product mixture suction filtration, solvent recuperation, obtains a filter cake; With distilled water, dilute hydrochloric acid, dilute NaOH solution, a filter cake is boiled 5 ~ 30min respectively, then filter, operate 2 ~ 3 times before repetition, obtain secondary filter cake; With hot wash secondary filter cake to filtrate in neutral, obtain three filter cakes; Three filter cakes are dried at 80 ~ 100 DEG C, obtains the thick product of polynuclear metal phthalocyanine alkane oxidation catalyst;
Second step: thick for polynuclear metal phthalocyanine alkane oxidation catalyst product is carried out surname extraction, until extracting liquid colourless, dries remaining solid, obtains bluish voilet to atropurpureus polynuclear metal phthalocyanine alkane oxidation catalyst finished product.
3. the preparation method of polynuclear metal phthalocyanine alkane oxidation catalyst according to claim 2, is characterized in that: using one or more in low boiling point organic solvent as extraction agent in surname extraction.
4. the preparation method of polynuclear metal phthalocyanine alkane oxidation catalyst according to claim 3, is characterized in that: described low boiling point organic solvent is methyl alcohol, ethanol, acetone or ethyl acetate.
Priority Applications (1)
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| CN101058078A (en) * | 2006-04-18 | 2007-10-24 | 向松 | Addend preparation method and process for wet oxidation-desulfurizing catalyst |
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| CN102259027A (en) * | 2011-05-20 | 2011-11-30 | 山东省分析测试中心 | Method for preparing cobalt phthalocyanine sulfonamide desulfurization catalyst |
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