CN1218780C - Catalyst for synthesizing para-hydroxybenzenemethylal by using paracresol, preparation and use - Google Patents
Catalyst for synthesizing para-hydroxybenzenemethylal by using paracresol, preparation and use Download PDFInfo
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- CN1218780C CN1218780C CN 02144897 CN02144897A CN1218780C CN 1218780 C CN1218780 C CN 1218780C CN 02144897 CN02144897 CN 02144897 CN 02144897 A CN02144897 A CN 02144897A CN 1218780 C CN1218780 C CN 1218780C
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Abstract
The present invention relates to a loaded catalyst for synthesizing p-Hydroxybenzaldehyde. Cobalt and copper are taken as active constituent host crystals, and the atomic ratio of the cobalt to the copper is 1: 0.05 to 1: 10. One kind or several kinds of iron, manganese, nickel, vanadium, zinc and cerium are taken as an active constituent assistant, and the atomic ratio of the total assistant to the cobalt is 0: 1 to 0.5: 1, and one of silica gel, titanium oxide and aluminum oxide or a complex material thereof or activated carbon is taken as a carrier, and the weight ratio of the active constituent to the carrier is 0.01 to 0.3. The carrier is dipped in solution containing the active constituent, and is dried, burnt, activated, etc. Thereby, the catalyst is obtained. Under the action of the catalyst, p-cresol is directly oxidized to synthesize the p-Hydroxybenzaldehyde. When the conversion rate of the p-cresol is 98.5%, the selectivity of the p-Hydroxybenzaldehyde is 95.6%. The catalyst has the characteristics of easy separation, periodic duty, low cost, few side product, high selectivity, etc., and is friendly to the environment. The catalyst has a broad industrial application prospect.
Description
Technical field
The present invention relates to the synthetic parahydroxyben-zaldehyde of paracresol catalytic oxidation, specifically a kind of catalyst and preparation and purposes that is used for the synthetic parahydroxyben-zaldehyde of paracresol.
Background technology
Parahydroxyben-zaldehyde is the important intermediate of organic synthesis, is widely used in industries such as medicine, spices, liquid crystal and agricultural chemicals.As oral antibiotic trimethoprim (TMP) T.M.P of new generation, oxyammonia benzylpenicillin and oxyammonia benzyl cephalosporin etc., and heart disease new drug phydroxybenzeneactamide and hydroxyphenylglycine is synthetic; Vanillic aldehyde, syringaldehyde, anise alcohol, anisaldehyde and raspberry ketone etc. is synthetic in the perfume industry; Novel liquid crystal material 4`-isopropyl-4-cyanobiphenyl, 1,2-two (2-cyano-benzene oxygen) ethane etc. synthetic; New pesticides in the agricultural chemicals, herbicide intermediate synthetic etc.
The route of producing parahydroxyben-zaldehyde has Reimer-Tiemann method (Chemical Reviews, 1960,60,169), para-nitrotoluene method, phenol formaldehyde (PF) method, electrochemistry synthetic method etc., and above method exists yield low, and equipment has high input, problems such as contaminated environment.
Parahydroxyben-zaldehyde production can be adopted the method for paracresol chlorination-hydrolysis; But this method adopts chemical chlorination synthetic, and accessory substance is more, and equipment corrosion is serious, produces the chlorine-contained wastewater contaminated environment, is mingled with the difficult separation of a small amount of chloride impurity in the product, can not reach the requirement of fields such as medicine, food to the raw material quality.
(JP 62155236,1987 for the existing report of the route of the synthetic parahydroxyben-zaldehyde of paracresol catalytic oxidation; CN1143066 A, 1997; US 4929766,1999; WO 2001009072 A1,2001), adopting the inorganic matter such as acetate, nitrate, halide or the organo-metallic compounds such as schiff bases, phthalocyanine of cobalt, copper, manganese, iron, nickel etc. is major catalyst, and adding sodium bromide, KBr or ammonium bromide etc. is auxiliary agent.This method is used is homogeneous catalyst, exists to be difficult for recycling and costing an arm and a leg, and selectivity of product is poor, and segregational load is big, problems such as environmental pollution.
Summary of the invention
The object of the present invention is to provide a kind of loaded catalyst of easily separated, synthetic parahydroxyben-zaldehyde that cost is low.
For achieving the above object, the technical solution used in the present invention is: catalyst is an active component host with cobalt and copper, the atomic ratio of cobalt and copper is 1: 0.05～1: 10, with in the elements such as iron, manganese, nickel, vanadium, zinc or cerium one or more is the active component auxiliary agent, the atomic ratio of total auxiliary agent and cobalt is 0: 1～0.5: 1, with a kind of in silica gel, titanium oxide, the aluminium oxide or their composite or active carbon is carrier, and the weight ratio of active component and carrier is 0.01～0.3;
Wherein: the preferred proportion of the atomic ratio of cobalt and copper is 1: 0.1～1: 5, and optimal proportion is 1: 0.5～1: 2; The preferred proportion of the atomic ratio of total auxiliary agent and cobalt is 0.02: 1～0.2: 1, and optimal proportion is 0.05: 1～0.1: 1; Preferable ratio is 0.02～0.15 between active component in this catalyst (master, auxiliary agent are by element wt) and the catalyst total amount, and is best than being 0.05～0.1.
Another purpose of the present invention is to provide a kind of above-mentioned Preparation of catalysts method of high selectivity.
In the catalyst preparation process,, mix being made into maceration extract in proportion with the predecessors such as nitrate, acetate or chloride of cobalt and copper; When adding auxiliary agent, the predecessors such as nitrate, acetate or chloride with this auxiliary agent mix wiring solution-forming in proportion, mix use with the solution of catalyst host;
Using method be with this carrier impregnation in the solution that contains active component (master, auxiliary agent), processing such as drying, calcination activation, wherein calcination temperature is 300～800 ℃, the time is 1～10 hour, obtains catalyst of the present invention;
Carrier of the present invention before use, by inorganic or organic acid or the alkali that adopts varying strength and structure carrier is carried out preliminary treatment, this material is by entering duct modulation structure, forming surperficial key or molten except that modes of action such as impurity in the carrier with the carrier surface effect, realize the homogenization of carrier character, help the even distribution of active component on the surface, make the catalyst of preparation in course of reaction, help raw material and be easy to leave catalyst surface in catalyst surface absorption and product, the raising selectivity; Employed sour modifying agent has phosphoric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, tartaric acid etc., and employed alkali modification reagent has NaOH, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, ammoniacal liquor, pyridine, acetamide, triethylamine etc.
Another object of the present invention is the reaction that above-mentioned loaded catalyst is used for the synthetic parahydroxyben-zaldehyde of direct oxidation paracresol.
The present invention has following advantage:
1. the method that is different from the employing homogeneous catalyst of bibliographical information adopts the synthetic parahydroxyben-zaldehyde of the present invention, and its catalyst is a solid, is easy to separate, can be recycled.
2. selectivity height of the present invention, paracresol conversion ratio are 98.5% o'clock, and the selectivity of parahydroxyben-zaldehyde is 95.6%.
3. accessory substance of the present invention is few, the product purity height.
4. environmental friendliness of the present invention belongs to green building-up process, has stronger prospects for commercial application.
5. cost of the present invention is low, and additive is not used in reaction, separates simple; Active component and catalyst carrier have certain ratio, help forming the even dispersion of active component, improve the stability of catalyst, reduce production costs.
The specific embodiment
Embodiment 1～6, the preparation of A catalyst series and evaluation
Embodiment 1
Take by weighing 4.9g Co (NO
3)
2.6H
2O and 0.02g Cu (NO
3)
2.3H
2O is mixed with the 120mL maceration extract, with γ-Al in the 250mL beaker
2O
3The 100g carrier joins in the maceration extract, stirring and evenly mixing, and behind the static 24h, in 120 ℃ of oven dry 12h, 300 ℃ of calcination 3h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is A-1.The parameter of Preparation of Catalyst is listed in table 1.
In the reactor of 2.0L, inventory is: 5.0g catalyst, 160.0g paracresol, 500mL methyl alcohol, 230g NaOH; Still is pushed up airtight, be heated with stirring to 65 ℃, logical oxygen reacts, and temperature rises, and the control reaction temperature is 75 ℃, reaction time 120min.Supplemental oxygen intermittently, keeping the still internal pressure is 0.08～0.12MPa.After reaction finishes, reaction system is reduced to room temperature, open kettle cover, sample analysis.The analysis of parahydroxyben-zaldehyde adopts internal standard method to carry out on HP 4890 gas chromatographs in the product, and acid analysis adopts internal standard method to carry out on the body fluid chromatography of island.Calculate conversion ratio, aldehyde selectivity and product and distribute, reaction result is listed in table 1.
Embodiment 2
Take by weighing 100g γ-Al
2O
3Carrier is in the 500mL beaker, and adding concentration is the potassium hydroxide solution 300mL of 0.01mol/L.Soak after 24 hours, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 22.3g Co (NO
3)
2.6H
2O and 1.3g CuCl
2.2H
2O is mixed with the 120mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 500 ℃ of calcination 2h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is A-2.The parameter of Preparation of Catalyst is listed in table 1.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 3
Take by weighing 100g γ-Al
2O
3Carrier is in the 500mL beaker, and adding concentration is the salpeter solution 300mL of 0.01mol/L.Soak after 24 hours, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 26.2g CoCl
2.6H
2O and 13.3g Cu (NO
3)
2.3H
2O is mixed with the 120mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 700 ℃ of calcination 1h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is A-3.The parameter of Preparation of Catalyst is listed in table 1.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 4
Take by weighing 100g γ-Al
2O
3Carrier is in the 500mL beaker, and adding concentration is the ammonia spirit 300mL of 0.01mol/L.Soak after 24 hours, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 39.1g Co (NO
3)
2.6H
2O and 35.5g Cu (NO
3)
2.3H
2O is mixed with the 120mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 300 ℃ of calcination 10h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is A-4.The parameter of Preparation of Catalyst is listed in table 1.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 5
Take by weighing 100g γ-Al
2O
3Carrier is in the 500mL beaker, and adding concentration is the oxalic acid solution 300mL of 0.01mol/L.Soak after 24 hours, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 42.8g Co (NO
3)
2.6H
2O and 64.9g Cu (NO
3)
2.3H
2O is mixed with the 120mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 400 ℃ of calcination 8h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is A-5.The parameter of Preparation of Catalyst is listed in table 1.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 6
Take by weighing 100g γ-Al
2O
3Carrier is in the 500mL beaker, and adding concentration is the tartaric acid solution 300mL of 0.01mol/L.Soak after 24 hours, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 8.1g CoCl
2.6H
2O and 34.8g CuCl
2.2H
2O is mixed with the 120mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 400 ℃ of calcination 6h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is A-6.The parameter of Preparation of Catalyst is listed in table 1.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 7-12, the preparation of B catalyst series and evaluation
Embodiment 7
Take by weighing the 100g absorbent charcoal carrier in the 500mL beaker, adding concentration is the sulfuric acid solution 300mL of 0.01mol/L.Soak after 24 hours, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 70.3g Co (NO
3)
2.6H
2O, 11.7g Cu (NO
3)
2.3H
2O and 19.5gFe (NO
3)
3.9H
2O is mixed with the 150mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 300 ℃ of vacuum calcination 4h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is B-1.The parameter of Preparation of Catalyst is listed in table 1.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 8
Take by weighing the 100g absorbent charcoal carrier in the 500mL beaker, adding concentration is the salpeter solution 300mL of 0.01mol/L.Soak after 24 hours, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 5.8g Co (NO
3)
2.6H
2O, 1.9g Cu (NO
3)
2.3H
2O and 1.5gMn (CH
3COO)
2.4H
2O is mixed with the 150mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 450 ℃ of vacuum calcination 2h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is B-2.The parameter of Preparation of Catalyst is listed in table 1.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 9
Take by weighing the 100g absorbent charcoal carrier in the 500mL beaker, adding concentration is the sodium hydroxide solution 300mL of 0.01mol/L.Soak after 24 hours, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 31.5g Co (NO
3)
2.6H
2O, 20.9g Cu (NO
3)
2.3H
2O and 0.5g NiCl
2.6H
2O is mixed with the 150mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 350 ℃ of vacuum calcination 3.5h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is B-3.The parameter of Preparation of Catalyst is listed in table 1.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 10
Take by weighing the 100g absorbent charcoal carrier in the 500mL beaker. adding concentration is the triethylamine solution 300mL of 0.01mol/L.Soak after 24 hours, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 55.2g Co (NO
3)
2.6H
2O, 68.7g Cu (NO
3)
2.3H
2O and 1.8g NH
4VO
3In the 250mL beaker, be mixed with the 150mL maceration extract, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 400 ℃ of vacuum calcination 4h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is B-4.The parameter of Preparation of Catalyst is listed in table 1.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 11
Take by weighing the 100g absorbent charcoal carrier in the 500mL beaker, adding concentration is the acetic acid solution 300mL of 0.01mol/L.Soak after 24 hours, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 11.7g Co (NO
3)
2.6H
2O, 24.2g Cu (NO
3)
2.3H
2O and 0.9gZn (CH
3COO)
2.2H
2O is mixed with the 150mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 400 ℃ of vacuum calcination 5h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is B-5.The parameter of Preparation of Catalyst is listed in table 1.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 12
Take by weighing 22.2g Co (NO
3)
2.6H
2O, 64.5g Cu (NO
3)
2.3H
2O and 1.7g Ce (NO
3)
3.6H
2O is mixed with the 150mL maceration extract in the 250mL beaker, the 100g absorbent charcoal carrier is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 400 ℃ of vacuum calcination 6h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is B-6.The parameter of Preparation of Catalyst is listed in table 1.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 13～19, the preparation of C catalyst series and evaluation
Embodiment 13
Take by weighing the 100g titanium dioxide carrier in the 500mL beaker, adding concentration is the phosphoric acid solution 300mL of 0.01mol/L.After soaking 24h, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 8.2g Co (NO
3)
2.6H
2O, 8.1g Cu (NO
3)
2.3H
2O, 0.6g Fe (NO
3)
3.9H
2O and 0.6g Mn (CH
3COO)
2.4H
2O is mixed with the 120mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 800 ℃ of vacuum calcination 2h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is C-1.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 14
Take by weighing the 100g titanium dioxide carrier in the 500mL beaker, adding concentration is the aqua calcis 300mL of 0.01mol/L.After soaking 24h, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 700 ℃ of calcination 6h cool off standby.Take by weighing 37.5g Co (NO
3)
2.6H
2O, 9.3g Cu (NO
3)
2.3H
2O, 1.3gMn (CH
3COO)
2.4H
2O and 2.8g NiCl
2.6H
2O is mixed with the 120mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 700 ℃ of vacuum calcination 6h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is C-2.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 15
Take by weighing the 100g titanium dioxide carrier in the 500mL beaker, adding concentration is the sodium carbonate liquor 300mL of 0.01mol/L.After soaking 24h, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 38.6g Co (NO
3)
2.6H
2O, 19.2g Cu (NO
3)
2.3H
2O, 1.9g NiCl
2.6H
2O and 1.5g NH
4VO
3In the 250mL beaker, be mixed with the 120mL maceration extract, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 500 ℃ of vacuum calcination 10h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is C-3.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 16
Take by weighing the 100g titanium dioxide carrier in the 500mL beaker, adding concentration is the ammonia spirit 300mL of 0.01mol/L.After soaking 24h, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 4h cool off standby.Take by weighing 18.4g Co (NO
3)
2.6H
2O, 10.7g Cu (NO
3)
2.3H
2O, 0.9g NH
4VO
3And 0.3Zn (CH
3COO)
2.2H
2O is mixed with the 120mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 400 ℃ of vacuum calcination 4h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is C-4.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 17
Take by weighing the 100g titanium dioxide carrier in the 500mL beaker, adding concentration is the pyridine solution 300mL of 0.01mol/L.After soaking 24h, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 5.7g Co (NO
3)
2.6H
2O, 5.2g Cu (NO
3)
2.3H
2O, 0.3g Zn (CH
3COO)
2.2H
2O and 1.2g Ce (NO
3)
3.6H
2O is mixed with the 120mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 400 ℃ of vacuum calcination 6h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is C-5.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 18
Take by weighing the 100g titanium dioxide carrier in the 500mL beaker, adding concentration is the salpeter solution 300mL of 0.01mol/L.After soaking 24h, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 12.1g Co (NO
3)
2.6H
2O, 13.0g Cu (NO
3)
2.3H
2O, 0.2g Ce (NO
3)
3.6H
2O and 0.5g Fe (NO
3)
3.9H
2O is mixed with the 120mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 600 ℃ of vacuum calcination 2h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is C-6.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 19
Take by weighing 14.8g Co (NO
3)
2.6H
2O, 17.2g Cu (NO
3)
2.3H
2O, 1.4g Fe (NO
3)
3.9H
2O and 0.7g NH
4VO
3In the 250mL beaker, be mixed with the 120mL maceration extract, the 100g titanium dioxide carrier is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 400 ℃ of vacuum calcination 3 h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is C-7.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 20～26, the preparation of D catalyst series and evaluation
Embodiment 20
Take by weighing 36.9g Co (NO
3)
2.6H
2O, 27.5g Cu (NO
3)
2.3H
2O, 4.1g Fe (NO
3)
3.9H
2O, 0.9g Mn (CH
3COO)
2.4H
2O and 2.1g NiCl
2.6H
2O is in the 250mL beaker, be mixed with the 120mL maceration extract, take by weighing 100g carrier (wherein each 50g of silica and aluminium oxide grinds evenly) in the 500mL beaker, stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 700 ℃ of calcination 2h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is D-1.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 21
Take by weighing 28.5g Co (NO
3)
2.6H
2O, 37.8g Cu (NO
3)
2.3H
2O, 1.7g NH
4VO
3, 0.4gZn (CH
3COO)
2.2H
2O and 1.3g Ce (NO
3)
3.6H
2O is in the 250mL beaker, be mixed with the 120mL maceration extract, take by weighing 100g carrier (wherein each 50g of silica and titanium oxide grinds evenly) in the 500mL beaker, stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 400 ℃ of calcination 5h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is D-2.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 22
Take by weighing 32.0g Co (NO
3)
2.6H
2O, 45.1g Cu (NO
3)
2.3H
2O, 1.3g Mn (CH
3COO)
2.4H
2O, 0.5g NiCl
2.6H
2O and 0.5g NH
4VO
3In the 250mL beaker, be mixed with the 120mL maceration extract, take by weighing 100g carrier (wherein each 50g of titanium oxide and aluminium oxide grinds evenly) in the 500mL beaker, stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 300 ℃ of calcination 6h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is D-3.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 23
Take by weighing 7.5g Co (NO
3)
2.6H
2O, 11.2g Cu (NO
3)
2.3H
2O, 0.2g Fe (NO
3)
3.9H
2O, 0.5gZn (CH
3COO)
2.2H
2O and 1.1g Ce (NO
3)
3.6H
2O is in the 250mL beaker, be mixed with the 120mL maceration extract, take by weighing 100g carrier (wherein each 50g of silica and titanium oxide grinds evenly) in the 500mL beaker, stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 700 ℃ of calcination 1h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is D-4.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 24
In the 500mL beaker, adding concentration is the sodium hydroxide solution 300mL of 0.01mol/L to take by weighing 100g carrier (wherein each 50g of titanium oxide and aluminium oxide grinds evenly).Soak after 24 hours, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 12.0g Co (NO
3)
2.6H
2O, 18.9g Cu (NO
3)
2.3H
2O, 0.2g Fe (NO
3)
3.9H
2O, 0.2g Mn (CH
3COO)
2.4H
2O, 0.5gZn (CH
3COO)
2.2H
2O and 1.3g Ce (NO
3)
3.6H
2O is mixed with the 120mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is D-5.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 25
In the 500mL beaker, adding concentration is the salpeter solution 300mL of 0.01mol/L to take by weighing 100g carrier (wherein each 50g of titanium oxide and aluminium oxide grinds evenly).Soak after 24 hours, suction filtration goes out carrier, and in 120 ℃ of oven dry 12h, 400 ℃ of calcination 3h cool off standby.Take by weighing 9.4g Co (NO
3)
2.6H
2O, 17.2gCu (NO
3)
2.3H
2O, 0.6g Mn (CH
3COO)
2.4H
2O, 0.6g NiCl
2.6H
2O, 0.2g NH
4VO
3With 0.7g Zn (CH
3COO)
2.2H
2O is mixed with the 120mL maceration extract in the 250mL beaker, the carrier after handling is joined in the maceration extract stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 800 ℃ of calcination 5h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is D-6.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Embodiment 26
Take by weighing 15.5g Co (NO
3)
2.6H
2O, 2.6g Cu (NO
3)
2.3H
2O, 0.2g Fe (NO
3)
3.9H
2O, 0.7gMn (CH
3COO)
2.4H
2O, 1.3g NiCl
2.6H
2O, 0.7g NH
4VO
3, 0.8g Zn (CH
3COO)
2.2H
2O and 3.5g Ce (NO
3)
3.6H
2O is respectively in 6 250mL beakers, be mixed with the 120mL maceration extract, take by weighing 100g carrier (wherein each 50g of silica and aluminium oxide grinds evenly) in the 500mL beaker, stirring and evenly mixing, behind the static 24h, in 120 ℃ of oven dry 12h, 500 ℃ of calcination 3h, cooling, porphyrize is got 60～150 order size particles and is estimated, and the catalyst label is D-7.Except that the catalyst difference, other reaction condition and analytical method are with embodiment 1.Reaction result sees Table 1.
Table 1. catalyst parameter and response analysis result
| Embodiment | Catalyst | Atomic ratio (mol) | Active element/carrier (wt/w t) | Conversion ratio (%) | Aldehyde selectivity (%) | Product distribution (%) | |||||||||
| C o | Cu | Fe | Mn | Ni | V | Zn | Ce | Aldehyde | Acid | Other | |||||
| 1 | A-1 | 1 | 0.005 | 0 | 0 | 0 | 0 | 0 | 0 | 0.01 | 45.2 | 50.1 | 50.1 | 38.4 | 11.5 |
| 2 | A-2 | 1 | 0.1 | 0 | 0 | 0 | 0 | 0 | 0 | 0.05 | 37.9 | 54.8 | 54.8 | 27.2 | 18.0 |
| 3 | A-3 | 1 | 0.5 | 0 | 0 | 0 | 0 | 0 | 0 | 0.10 | 50.3 | 48.6 | 48.6 | 26.6 | 24.8 |
| 4 | A-4 | 1 | 1.0 | 0 | 0 | 0 | 0 | 0 | 0 | 0.18 | 68.2 | 61.8 | 61.8 | 14.6 | 23.6 |
| 5 | A-5 | 1 | 2.0 | 0 | 0 | 0 | 0 | 0 | 0 | 0.25 | 70.7 | 57.6 | 57.6 | 20.0 | 22.4 |
| 6 | A-6 | 1 | 6.0 | 0 | 0 | 0 | 0 | 0 | 0 | 0.15 | 80.7 | 64.9 | 64.9 | 15.8 | 19.3 |
| 7 | B-1 | 1 | 0.2 | 0.2 | 0 | 0 | 0 | 0 | 0 | 0.20 | 74.5 | 72.1 | 72.1 | 8.2 | 19.7 |
| 8 | B-2 | 1 | 0.4 | 0 | 0.3 | 0 | 0 | 0 | 0 | 0.02 | 85.2 | 61.1 | 61.1 | 15.5 | 23.4 |
| 9 | B-3 | 1 | 0.8 | 0 | 0 | 0.02 | 0 | 0 | 0 | 0.12 | 66.1 | 71.6 | 71.6 | 12.1 | 16.3 |
| 10 | B-4 | 1 | 1.5 | 0 | 0 | 0 | 0.08 | 0 | 0 | 0.30 | 60.4 | 67.9 | 67.9 | 14.5 | 17.6 |
| 11 | B-5 | 1 | 2.5 | 0 | 0 | 0 | 0 | 0.1 | 0 | 0.09 | 54.8 | 57.0 | 57.0 | 10.6 | 32.4 |
| 12 | B-6 | 1 | 3.5 | 0 | 0 | 0 | 0 | 0 | 0.05 | 0.22 | 90.7 | 61.2 | 61.2 | 8.8 | 30.0 |
| 13 | C-1 | 1 | 1.2 | 0.05 | 0.08 | 0 | 0 | 0 | 0 | 0.04 | 94.2 | 55.0 | 55.0 | 17.8 | 27.2 |
| 14 | C-2 | 1 | 0.3 | 0 | 0.04 | 0.09 | 0 | 0 | 0 | 0.11 | 80.4 | 89.2 | 89.2 | 8.1 | 2.7 |
| 15 | C-3 | 1 | 0.6 | 0 | 0 | 0.06 | 0.1 | 0 | 0 | 0.14 | 88.5 | 80.8 | 80.8 | 12.1 | 7.1 |
| 16 | C-4 | 1 | 0.7 | 0 | 0 | 0 | 0.12 | 0.02 | 0 | 0.07 | 94.5 | 87.9 | 87.9 | 2.8 | 9.3 |
| 17 | C-5 | 1 | 1.1 | 0 | 0 | 0 | 0 | 0.06 | 0.14 | 0.03 | 90.1 | 82.7 | 82.7 | 15.2 | 2.1 |
| 18 | C-6 | 1 | 1.3 | 0.03 | 0 | 0 | 0 | 0 | 0.01 | 0.06 | 98.5 | 95.6 | 95.6 | 2.6 | 1.8 |
| 19 | C-7 | 1 | 1.4 | 0.07 | 0 | 0 | 0.11 | 0 | 0 | 0.08 | 87.5 | 96.7 | 96.7 | 1.0 | 2.3 |
| 20 | D-1 | 1 | 0.9 | 0.08 | 0.03 | 0.07 | 0 | 0 | 0 | 0.16 | 88.3 | 97.1 | 97.1 | 2.4 | 0.5 |
| 21 | D-2 | 1 | 1.6 | 0 | 0 | 0 | 0.15 | 0.02 | 0.03 | 0.17 | 90.9 | 87.8 | 87.8 | 4.5 | 7.7 |
| 22 | D-3 | 1 | 1.7 | 0 | 0.05 | 0.02 | 0.04 | 0 | 0 | 0.19 | 89.5 | 86.4 | 86.4 | 8.9 | 4.7 |
| 23 | D-4 | 1 | 1.8 | 0.02 | 0 | 0 | 0 | 0.08 | 0.1 | 0.05 | 90.7 | 95.4 | 95.4 | 4.0 | 0.6 |
| 24 | D-5 | 1 | 1.9 | 0.01 | 0.02 | 0 | 0 | 0.05 | 0.07 | 0.08 | 99.4 | 85.7 | 85.7 | 10.7 | 3.6 |
| 25 | D-6 | 1 | 2.2 | 0 | 0.07 | 0.08 | 0.06 | 0.1 | 0 | 0.07 | 94.1 | 87.6 | 87.6 | 4.9 | 7.5 |
| 26 | D-7 | 1 | 0.2 | 0.01 | 0.05 | 0.1 | 0.12 | 0.07 | 0.15 | 0.06 | 97.6 | 90.5 | 90.5 | 7.7 | 1.8 |
Claims (9)
1. the application of the loaded catalyst of a synthetic parahydroxyben-zaldehyde is characterized in that: be used for the reaction of the synthetic parahydroxyben-zaldehyde of direct oxidation paracresol; Loaded catalyst is an active component host with cobalt and copper, the atomic ratio of cobalt and copper is 1: 0.05～1: 10, with in iron, manganese, nickel, vanadium, zinc and the Ce elements one or more is the active component auxiliary agent, the atomic ratio of total auxiliary agent and cobalt is 0: 1～0.5: 1, with a kind of in silica gel, titanium oxide, the aluminium oxide or their composite or active carbon is carrier, and the weight ratio of active component and carrier is 0.01～0.3.
2. according to the application of the loaded catalyst of the described synthetic parahydroxyben-zaldehyde of claim 1, it is characterized in that: the atomic ratio of described cobalt and copper is 1: 0.1～1: 5, and the atomic ratio of total auxiliary agent and cobalt is 0.02: 1～0.2: 1.
3. according to the application of the loaded catalyst of the described synthetic parahydroxyben-zaldehyde of claim 1, it is characterized in that: the atomic ratio of described cobalt and copper is 1: 0.5～1: 2, and the atomic ratio of total auxiliary agent and cobalt is 0.05: 1～0.1: 1.
4. according to the application of the loaded catalyst of the described synthetic parahydroxyben-zaldehyde of claim 1, it is characterized in that: the weight ratio of described active component and carrier is 0.02～0.15.
5. according to the application of the loaded catalyst of the described synthetic parahydroxyben-zaldehyde of claim 1, it is characterized in that: the weight ratio of described active component and carrier is 0.05～0.1.
6. according to the application of the loaded catalyst of the described synthetic parahydroxyben-zaldehyde of claim 1, it is characterized in that: the preparation process of described loaded catalyst is as follows, with infusion process with active constituent loading on carrier, carrier drying, calcination activation, obtain the catalyst finished product, wherein calcination temperature is 300～800 ℃, and the time is 1～10 hour.
7. according to the application of the loaded catalyst of the described synthetic parahydroxyben-zaldehyde of claim 6, it is characterized in that: the active component that described infusion process adopts is nitrate, acetate or chloride.
8. according to the application of the loaded catalyst of claim 6 or 7 described synthetic parahydroxyben-zaldehydes, it is characterized in that: carrier carries out preliminary treatment with acid or alkali before dipping.
9. according to the application of the loaded catalyst of the described synthetic parahydroxyben-zaldehyde of claim 8, it is characterized in that: described acid is phosphoric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid or tartaric acid; Alkali is NaOH, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, ammoniacal liquor, pyridine, acetamide or triethylamine.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02144897 CN1218780C (en) | 2002-11-22 | 2002-11-22 | Catalyst for synthesizing para-hydroxybenzenemethylal by using paracresol, preparation and use |
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| CN1876237B (en) * | 2005-06-10 | 2011-01-26 | 上海天丰环保科技有限公司 | Composite catalyst for catalytic and oxidized treatment of three-phase waste water |
| CN101417929B (en) * | 2008-11-26 | 2011-06-08 | 合肥工业大学 | Synthetic method of hydroxybenzaldehyde |
| CN102350359B (en) * | 2011-08-17 | 2013-03-13 | 西安交通大学 | Preparation method of load-type cobalt-based catalyst |
| CN106892801B (en) * | 2017-01-23 | 2020-09-15 | 杭州师范大学 | Synthesis method of resveratrol intermediate p-hydroxybenzaldehyde |
| CN111250162B (en) * | 2018-11-30 | 2023-01-31 | 中国科学院大连化学物理研究所 | Solid base catalyst, and preparation method and application thereof |
| CN111004096B (en) * | 2019-12-18 | 2022-07-12 | 大连奇凯医药科技有限公司 | Synthetic method of 2, 6-dichlorobenzaldehyde |
| CN113831228A (en) * | 2020-06-24 | 2021-12-24 | 中国石油化工股份有限公司 | Catalytic synthesis method of p-hydroxybenzaldehyde |
| CN115850043A (en) * | 2022-12-09 | 2023-03-28 | 浙江新化化工股份有限公司 | Synthetic method of p-hydroxybenzaldehyde |
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