CN108201894A - A kind of oxidation catalyst for preparing 2- nitryl-4-thiamphenicol benzoic acids - Google Patents
A kind of oxidation catalyst for preparing 2- nitryl-4-thiamphenicol benzoic acids Download PDFInfo
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- CN108201894A CN108201894A CN201611180978.6A CN201611180978A CN108201894A CN 108201894 A CN108201894 A CN 108201894A CN 201611180978 A CN201611180978 A CN 201611180978A CN 108201894 A CN108201894 A CN 108201894A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
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Abstract
The present invention relates to a kind of oxidation catalyst for preparing 2 nitro, 4 thiamphenicol benzoic acid, to state, to form the element of the carbon monoxide-olefin polymeric and its composition formula of molar content be Mg0‑0.3·Mo0‑0.02·V0.03‑0.3·Cu0.004‑0.4·Zn0.002‑0.07·Al0‑0.7·K0.009‑0.4·Na0‑0.03·O0.1‑3.0·S0‑0.9, preparation method is：The vanadic anhydride or/and aluminium oxide for taking requirement are raw material, take the sulfate of the sodium salt of requirement molybdenum element, other metallic elements of requirement that raw material mixing ball milling 1h is obtained required catalyst for raw material respectively.Catalyst prepared by the present invention, catalytic activity is high, reaction condition is easily controllable, production cost is low, shortens the reaction time.
Description
Technical field
The present invention relates to a kind of oxidations for preparing mesotrione important intermediate 2- nitryl-4-thiamphenicol benzoic acids to urge agent.
Background technology
2- nitryl-4-thiamphenicol benzoic acids are important organic synthesis intermediate, in producers such as dyestuff, medicine and pesticides
Face has larger application value.It is to synthesize the important intermediate of mesotrione especially in terms of pesticide.Mesotrione belongs to three
Type herbicides are a kind of efficient herbicide specially for corn field, are used widely in developed country.The country is due to 2- nitre
The synthesis technology of base -4- thiamphenicol benzoic acids is immature, limits the application of mesotrione at home.Therefore, 2- nitros -4- first
The improvement of the synthesis technology of sulfuryl benzoic acid seems very urgent.
The method for oxidation that 2- nitro -4- methylsulfonyltoluenes directly prepare 2- nitryl-4-thiamphenicol benzoic acids can be divided into：Change
Learn oxidizing process and liquid-phase air oxidation.
CN201010258725 provides a kind of production method of 2- nitryl-4-thiamphenicol benzoic acids, using sulfuric acid as anti-
It answers medium molten, is nitrified 2- nitro -4- methylsulfonyltoluenes into 2- nitro -4- methylsulfonyls with nitration mixture (concentrated nitric acid and the concentrated sulfuric acid form)
Toluene；Potassium permanganate oxidation 2- nitro -4- methylsulfonyltoluenes are finally used into 2- nitryl-4-thiamphenicol benzoic acids.The method institute
With oxidant costliness, the thinner MnO of generation2Post processing is difficult, and waste residue amount is big.To avoid using expensive catalyst,
CN104557639A uses a kind of oxidation reaction apparatus of self-absorbing type stirrer, using 2- nitro -4- methylsulfonyltoluenes as raw material, sulphur
Acid is reaction medium, and transition-metal oxide is catalyst, is passed through oxygen in reaction process, prepares target product.The method pair
Equipment requirement is higher, and cost is higher, gas-liquid phase reaction, is unfavorable for realizing industrialization.
In conclusion liquid-phase air oxidation is difficult to use in industrialized production at present at present.Chemical oxidization method reaction condition
It is relatively mild easily controllable, but catalyst post processing is more difficult in actual production, and the oxidation reaction period is longer.Therefore, it prepares a kind of
Suitable catalyst is prepared the production of 2- nitryl-4-thiamphenicol benzoic acids extremely important.
Invention content
It is an object of the invention to overcome the shortcomings of the prior art, provide a kind of active selectable it is preferable, can
The oxidation catalyst for being suitable for nitric acid oxidation method and preparing 2- nitryl-4-thiamphenicol benzoic acids that is molten, easily filtering.
Purpose to realize the present invention, the present invention use technical solution for：
A kind of nitric acid oxidation method prepares the oxidation catalyst of 2- nitryl-4-thiamphenicol benzoic acids, and to state composition, this is urged
The element of agent composition and its composition formula of molar content are：
(Mg)a·(Mo)b·(V)c·(Cu)d·(Zn)e·(Al)f·(K)g·(Na)h·(O)x·(S)y
In formula, a, b, c, d, e, f, g, h, x and y are respectively mole containing for Mg, Mo, V, Cu, Zn, Al, K, Na, O and S element
Amount, wherein,
It is 0-0.02 c values is 0.03-0.3 that a values, which are 0-0.3 b values,
It is 0.002-0.07 f values is 0-0.7 that d values, which are 0.004-0.4 e values,
It is 0-0.03 x values is 0.1-3.0 that g values, which are 0.009-0.4 h values,
Y values are 0-0.9
The preparation method of the catalyst is as follows：
It is chosen any one kind of them from the vanadic anhydride or/and aluminium oxide of requirement as raw material (1)；Take the Mo of requirement respectively again
The sulfate of the sodium salt of element and other required metallic elements of requirement is raw material (2)；Raw material (1) and (2) are sufficiently mixed
Uniformly, ball milling 1h in Special ball mill is then added to again, and required oxidation catalyst is made.
Oxidation catalyst according to claim 1, it is characterised in that the molar content of each element point in the catalyst
It is not:
It is 0.003-0.015 c values is 0.04-0.25 that a values, which are 0.02-0.15 b values,
It is 0.003-0.05 f values is 0-0.3 that d values, which are 0.006-0.035 e values,
It is 0.006-0.02 x values is 0.2-2.5 that g values, which are 0.01-0.3 h values,
Y values are 0.09-0.5
The preparation for the catalyst that the present invention uses：Take the vanadic anhydride (V of requirement2O5) or/and aluminium oxide (Al2O3)
In it is any be raw material (1)；Take the sulfuric acid of sodium (Na) salt of molybdenum (Mo) element of requirement and other metallic elements of requirement
Salt is raw material (2)；Behind raw material (1) and (2) fully mixing, be added to ball mill (volume 20L, 120 revs/min,Ball 15
It is a,30, ball) interior ball milling 1h, abrading-ball is separated, collects product, required catalyst is made.
Oxidation catalyst of the present invention has the following advantages that：
(1) oxidation catalyst practical application of the invention shows that its 2- nitryl-4-thiamphenicol benzoic acid oxidization-hydrogenation ratio is higher than
Existing MnO2Type catalyst.
(2) reaction condition is easily, post processing is simple, three wastes yield is few, greatly shortens the reaction time, and there is larger industry to make
With value.
Specific embodiment
The following examples are used to the present invention be further described, but do not form limitation of the invention.
Embodiment 1
(1) catalyst preparation
Take 2g vanadic anhydrides (V2O5) it is raw material (1)；Weigh 1.17g potassium sulfates (K2SO4), 1.17g anhydrous cupric sulfates
(CuSO4), 1.03g zinc sulfate (ZnSO4·7H2O it is) raw material (2), is mixed and is uniformly added into ball mill (volume 20L, 120
Rev/min,15, ball,30, ball) interior ball milling 1h, abrading-ball is separated, collects product, required catalysis is made
Agent, the carbon monoxide-olefin polymeric composition formula are：
V0.08·Cu0.007·Zn0.004·K0.01·O0.49·S0.11
(2) catalyst application
20g2- nitro -4- methylsulfonyltoluenes are added in 500mL four-hole bottles, load onto thermometer, constant pressure funnel,
Reflux condensate device and device for absorbing tail gas add in the above-mentioned catalyst of 0.2g under mechanical agitation into four-hole bottle, add in 140g matter
Amount score is 70% sulfuric acid.Heating makes temperature of reaction system rise to 145 DEG C ± 2 DEG C, and it is 65-68%'s that 60g mass fractions, which are added dropwise,
Nitric acid, 16h are dripped off, and 6h is stirred to react after being added dropwise.When analyzing 2- nitro -4- methylsulfonyltoluene content ＜ 0.1% through HPLC,
Reaction terminates.Reaction solution is cooled to 20 DEG C, filtering, elution, drying obtain 2- nitryl-4-thiamphenicol benzoic acids, content ＞
98%, filtrated stock recovery, 2- nitryl-4-thiamphenicol benzoic acid yields reach 80%.
Embodiment 2
(1) catalyst preparation
Take 10g aluminium oxide (Al2O3), 5g vanadic anhydrides (V2O5) it is raw material (1)；Take 1.2g sodium molybdates (Na2MoO4·
2H2) and 10g potassium sulfates (K O2SO4), 6g copper sulphate (CuSO4·5H2O), 10g zinc sulfate (ZnSO4·7H2O), containing Fe21%),
10.8g magnesium sulfate (MgSO4·7H2O) it is raw material (2)；Be mixed be uniformly added into ball mill (volume 20L, 120 revs/min,15, ball,30, ball) interior ball milling 1h, abrading-ball is separated, collects product, required catalyst is made, this is urged
Agent composition composition formula is：
V0.2·Cu0.02·Zn0.03·Mg0.04·Mo0.005·Al0.2·K0.1·Na0.009·O1.84·S0.36(2) catalyst
Using
30g2- nitro -4- methylsulfonyltoluenes are added in 1000mL four-hole bottles, load onto thermometer, constant pressure funnel,
Reflux condensate device and device for absorbing tail gas add in the above-mentioned catalyst of 0.25g under mechanical agitation into four-hole bottle, add in 210g matter
Amount score is 70% sulfuric acid.Heating makes temperature of reaction system rise to 145 DEG C ± 2 DEG C, and it is 65-68%'s that 90g mass fractions, which are added dropwise,
Nitric acid, 18h are dripped off, and 8h is stirred to react after being added dropwise.When analyzing 2- nitro -4- methylsulfonyltoluene content ＜ 0.1% through HPLC,
Reaction terminates.Reaction solution is cooled to 20 DEG C, filtering, elution, drying obtain 2- nitryl-4-thiamphenicol benzoic acids, content ＞
98%, filtrated stock recovery, 2- nitryl-4-thiamphenicol benzoic acid yields reach 83%.
Embodiment 3
(1) catalyst preparation
It is carried out according to 2 preparation process of embodiment.Take 1gV2O5For raw material (1)；10gK is weighed again2SO4、7.5gCuSO4·
5H2O、10gZnSO4·7H2O、10.8gMgSO4·7H2O、2gNa2MoO4·2H2O is raw material (2)；It is mixed and is uniformly added into ball
Grinding machine (volume 20L, 120 revs/min,15, ball,30, ball) interior ball milling 1h, abrading-ball is separated, collects production
Object, is made required catalyst, which is：
V0.1·Cu0.02·Zn0.03·Mg0.04·Mo0.008·K0.1·Na0.02·O1.49·S0.2
(2) catalyst application
60g2- nitro -4- methylsulfonyltoluenes are added in 2000mL four-hole bottles, load onto thermometer, constant pressure funnel,
Reflux condensate device and device for absorbing tail gas add in the above-mentioned catalyst of 0.6g under mechanical agitation into four-hole bottle, add in 420g matter
Amount score is 70% sulfuric acid.Heating makes temperature of reaction system rise to 145 DEG C ± 2 DEG C, and it is 65-68%'s that 180g mass fractions, which are added dropwise,
Nitric acid, 18h are dripped off, and 6h is stirred to react after being added dropwise.When analyzing 2- nitro -4- methylsulfonyltoluene content ＜ 0.1% through HPLC,
Reaction terminates.Reaction solution is cooled to 20 DEG C, filtering, elution, drying obtain 2- nitryl-4-thiamphenicol benzoic acids, content ＞
98%, filtrated stock recovery, 2- nitryl-4-thiamphenicol benzoic acid yields reach 84%.
Embodiment 4
(1) catalyst preparation
Preparation method weighs 2.0gV with technique described in embodiment 22O5And 5.1gAl2O3For raw material (1)；It weighs again
17.4gK2SO4、7.5gCuSO4·5H2O、11.5gZnSO4·7H2O、24.6gMgSO4·7H2O、2.4gNa2MoO4·2H2O is
Raw material (2)；Be mixed be uniformly added into ball mill (volume 20L, 120 revs/min,15, ball,30, ball)
Interior ball milling 1h separates abrading-ball, collects product, and required catalyst is made, which is：
V0.15·Cu0.03·Zn0.04·Mg0.1·Mo0.01·K0.2·Na0.02·Al0.1·O2.17·S0.39(2) catalyst
Using
30g2- nitro -4- methylsulfonyltoluenes are added in 1000mL four-hole bottles, load onto thermometer, constant pressure funnel,
Reflux condensate device and device for absorbing tail gas add in the above-mentioned catalyst of 0.2g under mechanical agitation into four-hole bottle, add in embodiment 2
Reaction mother liquor.Heating makes temperature of reaction system rise to 145 DEG C ± 2 DEG C, and the nitric acid that 90g mass fractions are 65-68% is added dropwise,
16h is dripped off, and 7h is stirred to react after being added dropwise.When analyzing 2- nitro -4- methylsulfonyltoluene content ＜ 0.1% through HPLC, reaction
Terminate.Reaction solution is cooled to 20 DEG C, it is filtering, elution, dry, obtain 2- nitryl-4-thiamphenicol benzoic acids, content ＞ 98%,
Filtrated stock recovery, 2- nitryl-4-thiamphenicol benzoic acid yields reach 88%.
Claims (2)
1. a kind of oxidation catalyst for preparing 2- nitryl-4-thiamphenicol benzoic acids forms the carbon monoxide-olefin polymeric to state
Element and its composition formula of molar content are：
(Mg)a·(Mo)b·(V)c·(Cu)d·(Zn)e·(Al)f·(K)g·(Na)h·(O)x·(S)y
In formula, a, b, c, d, e, f, g, h, x and y are respectively the molar content of Mg, Mo, V, Cu, Zn, Al, K, Na, O and S element,
Wherein,
It is 0-0.02c values is 0.03-0.3 that a values, which are 0-0.3b values,
It is 0.002-0.07 f values is 0-0.7 that d values, which are 0.004-0.4 e values,
It is 0-0.03 x values is 0.1-3.0 that g values, which are 0.009-0.4 h values,
Y values are 0-0.9
The preparation method of the catalyst is as follows：
It is chosen any one kind of them from the vanadic anhydride or/and aluminium oxide of requirement as raw material (1)；Take the Mo elements of requirement respectively again
Sodium salt and requirement other required metallic elements sulfate be raw material (2)；Raw material (1) and (2) are sufficiently mixed uniformly,
Then ball milling 1h in Special ball mill is added to again, and required oxidation catalyst is made.
2. oxidation catalyst according to claim 1, it is characterised in that the molar content difference of each element in the catalyst
For
It is 0.003-0.015 c values is 0.04-0.25 that a values, which are 0.02-0.15 b values,
It is 0.003-0.05 f values is 0-0.3 that d values, which are 0.006-0.035 e values,
It is 0.006-0.02 x values is 0.2-2.5 that g values, which are 0.01-0.3 h values,
Y values are 0.09-0.5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110229088A (en) * | 2019-07-09 | 2019-09-13 | 湖北广富林生物制剂有限公司 | Preparation method of mesotrione intermediate |
| CN113402429A (en) * | 2021-06-21 | 2021-09-17 | 辽宁龙田化工科技有限公司 | Synthetic method for generating 2-nitro-4-methylsulfonylbenzoic acid by oxidizing 2-nitro-4-methylsulfonyltoluene with oxygen |
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| CN113402429A (en) * | 2021-06-21 | 2021-09-17 | 辽宁龙田化工科技有限公司 | Synthetic method for generating 2-nitro-4-methylsulfonylbenzoic acid by oxidizing 2-nitro-4-methylsulfonyltoluene with oxygen |
| CN113402429B (en) * | 2021-06-21 | 2022-06-03 | 辽宁龙田化工科技有限公司 | Synthetic method for generating 2-nitro-4-methylsulfonylbenzoic acid by oxidizing 2-nitro-4-methylsulfonyltoluene with oxygen |
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