CN104557639A - Method of preparing 2-nitro-4-methylsulfonyl benzoic acid - Google Patents

Method of preparing 2-nitro-4-methylsulfonyl benzoic acid Download PDF

Info

Publication number
CN104557639A
CN104557639A CN201410808190.XA CN201410808190A CN104557639A CN 104557639 A CN104557639 A CN 104557639A CN 201410808190 A CN201410808190 A CN 201410808190A CN 104557639 A CN104557639 A CN 104557639A
Authority
CN
China
Prior art keywords
nitryl
benzoic acid
nitro
reaction
methylsulfonyltoluene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410808190.XA
Other languages
Chinese (zh)
Other versions
CN104557639B (en
Inventor
单体育
刘红翼
郑玉安
祁巍
王雪梅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenyang Research Institute of Chemical Industry
Original Assignee
Shenyang Research Institute of Chemical Industry
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenyang Research Institute of Chemical Industry filed Critical Shenyang Research Institute of Chemical Industry
Priority to CN201410808190.XA priority Critical patent/CN104557639B/en
Publication of CN104557639A publication Critical patent/CN104557639A/en
Application granted granted Critical
Publication of CN104557639B publication Critical patent/CN104557639B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a novel method of preparing 2-nitro-4-methylsulfonyl benzoic acid. The target product which is 2-nitro-4-methylsulfonyl benzoic acid is prepared by carrying out reaction by adopting an oxidation reaction device with a self-priming stirrer, wherein 2-nitro-4-methylsulfonyltoluene is used as the raw material, sulfuric acid is used as a reaction medium, a transition metal oxide is used as the catalyst, and oxygen is introduced in the course of reaction. The method provided by the invention has the advantage that the reaction condition is easy to control, the production cost is low, and the amount of the generated three wastes is reduced.

Description

A kind of method preparing 2-nitryl-4-thiamphenicol benzoic acid
Technical field
The invention belongs to organic synthesis field, relate to a kind of method preparing 2-nitryl-4-thiamphenicol benzoic acid particularly.
Background technology
2-nitryl-4-thiamphenicol benzoic acid (2-Nitro-4-methylsulfonylbenzoic acid; Be called for short NMSBA) be important organic synthesis intermediate, there is larger using value at producer masks such as dyestuff, medicine and agricultural chemicals.Especially, in agricultural chemicals, be the important intermediate of synthesis mesotrione.Mesotrione belongs to three ketones weedicide, is a kind of herbicide specially for corn field efficiently, is used widely in developed country.The domestic synthesis technique due to 2-nitryl-4-thiamphenicol benzoic acid is immature, limits mesotrione application at home.Therefore the improvement of the synthesis technique of 2-nitryl-4-thiamphenicol benzoic acid is seemed very urgent.
The method for oxidation that 2-nitro-4-methylsulfonyltoluene directly prepares 2-nitryl-4-thiamphenicol benzoic acid can be divided into: chemical oxidization method and liquid-phase air oxidation.Chemical oxidization method mainly contains: sodium dichromate 99 method, potassium permanganate process, sodium hypochlorite oxidization and nitric acid oxidation method etc.
CN201010258725 provides a kind of production method of 2-nitryl-4-thiamphenicol benzoic acid, molten as reaction medium with the vitriol oil, with nitration mixture (concentrated nitric acid and the vitriol oil composition) by nitrated for methylsulfonyltoluene become 2-nitro-4-methylsulfonyltoluene; Finally adopt potassium permanganate oxidation 2-nitro-4-methylsulfonyltoluene to become 2-nitryl-4-thiamphenicol benzoic acid, single step yield is more than 90%, and average yield reaches 85%.This method oxygenant used is expensive, generates thinner MnO 2aftertreatment difficulty, waste residue amount is large.For avoiding using expensive oxygenant, people's research nitric acid such as Helmut Hagen are as oxygenant, and using 70% sulfuric acid as reaction medium, Vanadium Pentoxide in FLAKES is catalyzer, and pass into dry oxygen, and the yield of 2-nitryl-4-thiamphenicol benzoic acid reaches 83%.The oxygenant of this method is cheap, and operation is easy, and has higher yield, but produces the toxic gases such as NO.Liquid-phase air oxidation is because having environmental friendliness, and the feature such as with low cost and be subject to extensive concern, this method reaction yield is low, and apparatus and process requires high, is difficult to large-scale application.
In sum, current chemical oxidization method reaction conditions gentleness is easy to control, but in actual production, face many problems; Liquid phase air oxidationization is difficult to be applied in industrial production at present.
Summary of the invention
The object of this invention is to provide one can reduce three wastes generation, improve reaction yield, reduce the 2-nitryl-4-thiamphenicol benzoic acid preparation method of production cost.
For realizing object of the present invention, the present invention adopts technical scheme to be:
Prepare a method for 2-nitryl-4-thiamphenicol benzoic acid,
Reaction formula is as follows,
With 2-nitro-4-methylsulfonyltoluene be raw material, transition metal oxide is catalyzer, sulfuric acid for solvent, under airtight agitation condition, pass into oxygen, and slowly drip nitric acid, at 130-170 DEG C, react 5-10h, obtain 2-nitryl-4-thiamphenicol benzoic acid.
Preferably, 2-nitro-4-methylsulfonyltoluene, transition metal oxide, sulfuric acid are joined in the closed reactor with self-absorbing type stirrer, stirring and dissolving; In reactor, pass into oxygen makes system pressure reach 0-1.6MPa, regulate stirring velocity, make the gas holdup (volume) >=10% in reaction solution, and slowly drip nitric acid, simultaneously to supplemental oxygen in system, make gas holdup in reaction solution remain on (volume) >=10%, system pressure remains at low malleation or slight positive pressure state (0-1.6MPa).Speed of response is controlled by the rate of addition and vapour-liquid ratio that adjust nitric acid.Adopt liquid chromatography to follow the tracks of the content of 2-nitro-4-methylsulfonyltoluene, as content < 0.1%, reaction reaches terminal.Reaction solution is cooled to room temperature and filters, filter cake washes with water to neutrality, the 2-nitryl-4-thiamphenicol benzoic acid of high-quality can be obtained after oven dry, content > 98%, filtrated stock recovery, 2-nitryl-4-thiamphenicol benzoic acid yield is (in 2-nitro-4-methylsulfonyltoluene) more than 90%.
Described system pressure is 0 ~ 0.5MPa, gas holdup 10 ~ 30% in reaction solution.
Described system pressure is 0 ~ 0.1MPa, the gas holdup 15% ~ 20% in reaction solution.
System pressure in described reaction process in reactor keeps constant or fluctuates; When system pressure floats, domain of walker is 0 ~ 0.1MPa.System internal pressure is in barotropic state all the time.
Described transition metal oxide is the oxide compound of vanadium or cobalt; Weight ratio 1:10 ~ 100 of transition metal oxide and 2-nitro-4-methylsulfonyltoluene.The preferred V of transition metal oxide 2o 5; V 2o 5with weight ratio 1:10 ~ 100 of 2-nitro-4-methylsulfonyltoluene, preferred 1:40 ~ 60, most preferably 1:50.
Weight ratio 1 ~ the 10:1 of described sulfuric acid and 2-nitro-4-methylsulfonyltoluene, preferably 6 ~ 8:1, most preferably 7:1; Sulfuric acid concentration is 70% ~ 98%.
Described concentration of nitric acid is 30 ~ 75wt%, and preferred concentration is 45% ~ 55%, and the consumption of nitric acid is 1-5 times of raw material 2-nitro-4-methylsulfonyltoluene weight, and the consumption of preferred nitric acid is 3 times of raw material 2-nitro-4-methylsulfonyltoluene weight.
Described catalytic oxidation temperature is 138 ~ 140 DEG C, and the reaction times is 6 ~ 9h.
Gas on liquid level in reactor can be sucked again and be scattered in liquid phase during the self-absorbing type stirrer work that the present invention adopts, thus realization response gas internal recycle, increase substantially Gas-liquid interfacial area, reach the object improving speed of reaction.The size of self-absorbing type stirrer gettering ability, depends on the many factors such as structural shape, mounting means, mixing speed and feed liquid character.Agitator paddle is with reactor diameter ratio is larger, mixing speed is higher, liquid-column height is lower, feed liquid proportion proportion that is larger, gas is less, then inspiratory capacity is larger; Under device structure and the certain condition of material system, inspiratory capacity depends on stirring velocity.The self-absorbing type stirrer of any one structural shape can be adopted, by regulating stirring velocity to reach suitable inspiratory capacity, obtain desirable reaction effect in the present invention.Self-priming hollow vortex wheel-type or hollow windmill-shaped agitator are selected in recommendation.
The inventive method tool has the following advantages:
The present invention adopts the closed reactor with self-suction stirrer to carry out 2-nitro-4-methylsulfonyltoluene oxidizing reaction.Through a large amount of condition tests, determine suitable reaction parameter and reaction conditions, improve reaction yield, reduce oxygenant usage quantity, and three wastes generation is few.Specifically:
1, carrying out oxidizing reaction with in the closed reactor of self-absorbing type stirrer, oxygen is internal recycle in reaction unit, and the NO that reaction generates etc. directly oxidized being recycled in solution use as oxygenant, improve reaction yield;
2, easily-controlled reaction conditions, aftertreatment is simple, three wastes generation is few, has larger industrial utility value.
Embodiment
The following examples for further describing the present invention, but do not form limitation of the invention.
Embodiment 1
Be equipped with in the reactor of self-absorbing type stirrer in 500mL, add 140g 75% sulfuric acid, 20g 2-nitro-4-methylsulfonyltoluene, 0.4g V 2o 5stirring and dissolving, closed system, connect oxygen storage tank, stirring velocity is regulated to make the gas holdup in reaction solution (volume) reach 15%, be warming up to 138 ~ 140 DEG C gradually, in system, add 60g 50% nitric acid in 5 ~ 6h, simultaneously to supplemental oxygen in system, make system pressure remain at 5 × 10 -3mPa, reaction 3h, when liquid chromatography follows the tracks of the content < 0.1% of 2-nitro-4-methylsulfonyltoluene, reaction terminates.Reaction solution naturally cools to room temperature, filter, filter cake 100g clear water is washed till neutrality, 2-nitryl-4-thiamphenicol benzoic acid is obtained after drying, content > 98%, filtrate recovery, 2-nitryl-4-thiamphenicol benzoic acid yield reaches 96.7% (in 2-nitro-4-methylsulfonyltoluene).1g product produces 6g waste water, does not produce waste gas and waste residue
Embodiment 2
By 210g 75% sulfuric acid, 30g 2-nitro-4-methylsulfonyltoluene, 0.3g V 2o 5being added in the closed reactor with self-absorbing type stirrer, stirring and pass into oxygen, adjustment temperature to 155 DEG C, making the gas holdup in reaction solution (volume) reach 15% by regulating stir speed (S.S.); Dripping 90g concentration is the nitric acid of 50%, drips 6h, along with the carrying out of reaction is to supplemental oxygen in system, makes system pressure remain at 5 × 10 -3mPa.Control speed of response by the rate of addition and vapour-liquid ratio that adjust nitric acid, drip reaction 2h, when liquid chromatography follows the tracks of the content < 0.1% of 2-nitro-4-methylsulfonyltoluene, reaction terminates.Reaction solution is cooled to room temperature and filters, filter cake 150g is washed to neutrality, can obtain the 2-nitryl-4-thiamphenicol benzoic acid of high-quality after oven dry, content > 98% filtrated stock recovery, the yield of 2-nitryl-4-thiamphenicol benzoic acid is 88.7%.
Embodiment 3
By 70g 75% sulfuric acid, 10g 2-nitro-4-methylsulfonyltoluene, 1g V 2o 5being added in the closed reactor with self-absorbing type stirrer, stirring and pass into oxygen, adjustment temperature to 140 DEG C, making the gas holdup in reaction solution (volume) reach 15% by regulating stir speed (S.S.); Dripping 30g concentration is the nitric acid of 70%, drips 7h.Carry out supplemental oxygen in system along with what react, make system pressure remain at 5 × 10 -3mPa.Speed of response is controlled by the rate of addition and vapour-liquid ratio that adjust nitric acid.Drip reaction 3h, when liquid chromatography follows the tracks of the content < 0.1% of 2-nitro-4-methylsulfonyltoluene, reaction terminates.Reaction solution is cooled to room temperature and filters, filter cake 60g is washed to neutrality, can obtain the 2-nitryl-4-thiamphenicol benzoic acid of high-quality after oven dry, content > 98% filtrated stock recovery, the yield of 2-nitryl-4-thiamphenicol benzoic acid is 90.6%.
Embodiment 4
By the mother liquor reclaimed in embodiment 1,20g 2-nitro-4-methylsulfonyltoluene, 0.4g V 2o 5being added in the closed reactor with self-absorbing type stirrer, stirring and pass into oxygen, adjustment temperature to 140 DEG C, making the gas holdup in reaction solution (volume) reach 15% by regulating stir speed (S.S.); Dripping 60g concentration is the nitric acid of 50%, drips 6h, along with the carrying out of reaction is to supplemental oxygen in system, makes system pressure remain at 5 × 10 -3mPa.Control speed of response, dropwise reaction 3h by the rate of addition and vapour-liquid ratio that adjust nitric acid, liquid chromatography follows the tracks of the content < 0.1% of 2-nitro-4-methylsulfonyltoluene, and reaction terminates.Reaction solution is cooled to room temperature and filters, and filter cake 100g is washed to neutrality, can obtain the 2-nitryl-4-thiamphenicol benzoic acid of high-quality, content > 98% after oven dry.Filtrated stock recovery, the yield of 2-nitryl-4-thiamphenicol benzoic acid is 95.6%.
Embodiment 5
Adopt the method for CN201010258725, adopt potassium permanganate as oxygenant, by 100g 90% vitriol oil, 30g, to methylsulfonyltoluene, cools to 0 ~ 4 DEG C, adds 60g by 90% vitriol oil and 60% nitric acid (ratio is 1:0.5), maintain the temperature at 0 ~ 4 DEG C, after adding, be warming up to 20 ~ 30 DEG C, add 100g water, 2g potassium permanganate, be warming up to 50 ~ 60 DEG C, add 70g bis-hydration potassium bichromate, 120g potassium bichromate solution, be warming up to 70 ~ 80 DEG C, reaction 5 ~ 6h.Reaction end is cooled to 20 DEG C once, adds 200g water and stirs 1 ~ 2h, filter.Filter cake 250g aqueous sodium hydroxide solution, agitation and filtration, it is 1 that filtrate concentrated hydrochloric acid is adjusted to pH, and cold filtration is dry, obtains product, yield 85.7%.This method is produced 1g product and is produced 25g waste water, and has MnO 2waste residue produces, and quantity of three wastes is larger.
Embodiment 6
By 3500kg75% sulfuric acid, 50kg 2-nitro-4-methylsulfonyltoluene, 1kg V 2o 5being added in the closed reactor with self-absorbing type stirrer, stirring and pass into oxygen, adjustment temperature to 138 ~ 140 DEG C, making the gas holdup in reaction solution (volume) reach 15% by regulating stir speed (S.S.); Dripping 150kg concentration is the nitric acid of 50%, drips 6h, along with the carrying out of reaction is to supplemental oxygen in system, makes system pressure remain at 5 × 10 -3mPa.Control speed of response by the rate of addition and vapour-liquid ratio that adjust nitric acid, drip reaction 2h, when liquid chromatography follows the tracks of the content < 0.1% of 2-nitro-4-methylsulfonyltoluene, reaction terminates.Reaction solution is cooled to room temperature and filters, filter cake 150kg is washed to neutrality, the 2-nitryl-4-thiamphenicol benzoic acid of high-quality can be obtained after oven dry, content > 98% filtrated stock recovery, the yield of 2-nitryl-4-thiamphenicol benzoic acid is 95.3% (with 2-nitro-4-methylsulfonyltoluene).Produce 158kg waste water, do not produce waste gas and waste residue.Adopt potassium permanganate oxidation method, estimate to produce 900kg waste water, and produce the waste residue of about 5kg.

Claims (10)

1. prepare a method for 2-nitryl-4-thiamphenicol benzoic acid, it is characterized in that:
Reaction formula is as follows,
With 2-nitro-4-methylsulfonyltoluene be raw material, transition metal oxide is catalyzer, with sulfuric acid for solvent, airtight and pass into oxygen under agitation condition, and slowly drip nitric acid, at 130 ~ 170 DEG C, react 5 ~ 10h, obtain 2-nitryl-4-thiamphenicol benzoic acid.
2. preparation 2-nitryl-4-thiamphenicol benzoic acid method according to claim 1, is characterized in that: join in the closed reactor with self-absorbing type stirrer by 2-nitro-4-methylsulfonyltoluene, transition metal oxide, sulfuric acid, stirring and dissolving; Closed reactor, passes into oxygen and makes system pressure reach 0 ~ 1.6MPa, regulates stirring velocity, make the gas holdup (volume) >=10% in reaction solution, and slowly drip nitric acid, supplemental oxygen in system, make gas holdup in reaction solution keep (volume) >=10%.
3. the method preparing 2-nitryl-4-thiamphenicol benzoic acid according to claim 2, is characterized in that: described system pressure is 0 ~ 0.5MPa, gas holdup 10 ~ 30% in reaction solution.
4. the method preparing 2-nitryl-4-thiamphenicol benzoic acid according to claim 3, is characterized in that: described system pressure is 0 ~ 0.1MPa, the gas holdup 15% ~ 20% in reaction solution.
5. the method preparing 2-nitryl-4-thiamphenicol benzoic acid according to claim 2, is characterized in that: the system pressure in described reaction process in reactor keeps constant or fluctuates; When system pressure floats, domain of walker is 0 ~ 0.1MPa.
6. the method preparing 2-nitryl-4-thiamphenicol benzoic acid according to claim 1, is characterized in that: described transition metal oxide is the oxide compound of vanadium or cobalt; Weight ratio 1:10 ~ 100 of transition metal oxide and 2-nitro-4-methylsulfonyltoluene.
7. the method preparing 2-nitryl-4-thiamphenicol benzoic acid according to claim 1, is characterized in that: described transition metal oxide is V 2o 5; V 2o 5with weight ratio 1:10 ~ 100 of 2-nitro-4-methylsulfonyltoluene.
8. the method preparing 2-nitryl-4-thiamphenicol benzoic acid according to claim 1, is characterized in that: weight ratio 1:1 ~ 10 of described sulfuric acid and 2-nitro-4-methylsulfonyltoluene; Sulfuric acid concentration is 70% ~ 98%.
9. the method preparing 2-nitryl-4-thiamphenicol benzoic acid according to claim 1, is characterized in that: described concentration of nitric acid is 30 ~ 75wt%, and the consumption of nitric acid is 1 ~ 5 times of raw material 2-nitro-4-methylsulfonyltoluene weight.
10. the method preparing 2-nitryl-4-thiamphenicol benzoic acid according to claim 1, is characterized in that: described catalytic oxidation temperature is 138 ~ 140 DEG C, and the reaction times is 6 ~ 9h.
CN201410808190.XA 2014-12-22 2014-12-22 Method of preparing 2-nitro-4-methylsulfonyl benzoic acid Active CN104557639B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410808190.XA CN104557639B (en) 2014-12-22 2014-12-22 Method of preparing 2-nitro-4-methylsulfonyl benzoic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410808190.XA CN104557639B (en) 2014-12-22 2014-12-22 Method of preparing 2-nitro-4-methylsulfonyl benzoic acid

Publications (2)

Publication Number Publication Date
CN104557639A true CN104557639A (en) 2015-04-29
CN104557639B CN104557639B (en) 2017-05-10

Family

ID=53074818

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410808190.XA Active CN104557639B (en) 2014-12-22 2014-12-22 Method of preparing 2-nitro-4-methylsulfonyl benzoic acid

Country Status (1)

Country Link
CN (1) CN104557639B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105017101A (en) * 2015-08-08 2015-11-04 浙江大学 Synthesizing method of 2-chloro-4-(methylsulfonyl)benzoic acid
CN105669504A (en) * 2016-03-07 2016-06-15 山东润博生物科技有限公司 Preparation method of 2-nitro-4-methyl sulphonyl benzoic acid
CN106496079A (en) * 2016-09-12 2017-03-15 华东理工大学 The technique that a kind of Oxygen Catalytic Oxidation produces 2 nitro, 4 thiamphenicol benzoic acid

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0213892A2 (en) * 1985-08-27 1987-03-11 Rohm And Haas Company Herbicidally active enols
CN1038584A (en) * 1988-06-24 1990-01-10 中国人民解放军第八一医院 The extraction process of anticancer health-protecting tea extract
CN1038584C (en) * 1992-10-19 1998-06-03 Basf公司 Preparation of methylsulfonylbenzoic acids
CN2649170Y (en) * 2003-10-28 2004-10-20 杭州原正化学工程技术装备有限公司 Efficient self-absorption gas-liquid stirring device
CN101177369A (en) * 2007-12-14 2008-05-14 嘉兴学院 Method for oxidation of benzene ring side chain containing electron-attracting groups by combination of ozone and nitric acid
CN101503383A (en) * 2009-03-16 2009-08-12 嘉兴学院 Preparation of o-nitro p-methylsulfonylbenzoic acid
CN103626681A (en) * 2012-08-20 2014-03-12 中国中化股份有限公司 Method for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0213892A2 (en) * 1985-08-27 1987-03-11 Rohm And Haas Company Herbicidally active enols
CN1038584A (en) * 1988-06-24 1990-01-10 中国人民解放军第八一医院 The extraction process of anticancer health-protecting tea extract
CN1038584C (en) * 1992-10-19 1998-06-03 Basf公司 Preparation of methylsulfonylbenzoic acids
CN2649170Y (en) * 2003-10-28 2004-10-20 杭州原正化学工程技术装备有限公司 Efficient self-absorption gas-liquid stirring device
CN101177369A (en) * 2007-12-14 2008-05-14 嘉兴学院 Method for oxidation of benzene ring side chain containing electron-attracting groups by combination of ozone and nitric acid
CN101503383A (en) * 2009-03-16 2009-08-12 嘉兴学院 Preparation of o-nitro p-methylsulfonylbenzoic acid
CN103626681A (en) * 2012-08-20 2014-03-12 中国中化股份有限公司 Method for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105017101A (en) * 2015-08-08 2015-11-04 浙江大学 Synthesizing method of 2-chloro-4-(methylsulfonyl)benzoic acid
CN105669504A (en) * 2016-03-07 2016-06-15 山东润博生物科技有限公司 Preparation method of 2-nitro-4-methyl sulphonyl benzoic acid
CN106496079A (en) * 2016-09-12 2017-03-15 华东理工大学 The technique that a kind of Oxygen Catalytic Oxidation produces 2 nitro, 4 thiamphenicol benzoic acid
CN106496079B (en) * 2016-09-12 2018-07-27 华东理工大学 A kind of technique for producing 2- nitryl-4-thiamphenicol benzoic acids with Oxygen Catalytic Oxidation

Also Published As

Publication number Publication date
CN104557639B (en) 2017-05-10

Similar Documents

Publication Publication Date Title
CN104557639A (en) Method of preparing 2-nitro-4-methylsulfonyl benzoic acid
CN101503383B (en) Preparation of o-nitro p-methylsulfonylbenzoic acid
CN103566949A (en) Copper-based catalyst for preparing ethylene glycol and ethylene glycol monomethyl ether through hydrogenation of dimethyl oxalate and preparation method thereof
CN106179502A (en) The preparation method and application of graphene oxide immobilized four (4 carboxyl phenyl) manganoporphyrin catalysis material
CN105837391A (en) Application of metal-free hydrogenation catalyst to catalysis of benzene hydrogenation
CN103626681B (en) One prepares 4, the method for 4 &#39;-dinitrostilbene-2,2 &#39;-disulfonic acid
CN102516054A (en) Method for synthesizing 2-methyl-1, 4-naphthoquinone
CN104909993B (en) A kind of industrial preparative method of the chlorophenesic acid of Mediben key intermediate 2,5
CN104368340B (en) A kind of preparation of sponge silver catalyst and the application in cinnamic acid oxidation synthesizing cinnamic acid thereof
CN103977819B (en) A kind of activation method of adipic dinitrile hydrogenation catalyst
CN104262215A (en) Preparation method of 2-nitro-4-methyl sulfone benzoic acid
CN206244540U (en) A kind of tungsten mineral material baking flue gas spent shower water processing system
CN102602977B (en) Method for preparing copper oxide by dissolving copper
CN106831643B (en) The method for preparing rubber accelerator MBTS using micro-reaction device
CN205216527U (en) Processing apparatus of manganese acetate production tail gas
CN102060336B (en) Method for preparing high-purity anhydrous nickel chloride
CN103920507A (en) Catalyst for oxidation of hydrogen chloride to prepare chlorine and application thereof
CN104860901B (en) Preparation method of benzothiazole-2-carboxylic acid
CN102964230A (en) Method for preparing benzaldehyde from methylbenzene through liquid-phase catalytic oxidation
CN102627591B (en) Preparation method of 2-chloro-4-methylsulfonylbenzoic acid
CN104892522A (en) Preparation method of 4-nitroimidazole and 4,5-dimetridazloe
CN105820054A (en) Preparation method of 3-methoxy-2-nitrobenzoate
CN101643399B (en) Method for preparing cobalt acetate solution
CN106565440B (en) Application of the salt-free nitrosyl sulfuric acid in catalytic oxidation of benzyl alcohol reaction
CN204447950U (en) A kind of Special reverse for 9-Fluorenone production answers flow container

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
GR01 Patent grant