CN104693036A - Process for separating and utilizing mixing components of o-, m-, and p-nitrochlorobenzene - Google Patents
Process for separating and utilizing mixing components of o-, m-, and p-nitrochlorobenzene Download PDFInfo
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- CN104693036A CN104693036A CN201310647781.9A CN201310647781A CN104693036A CN 104693036 A CN104693036 A CN 104693036A CN 201310647781 A CN201310647781 A CN 201310647781A CN 104693036 A CN104693036 A CN 104693036A
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Abstract
The invention discloses a separation and utilization method for mixed component of O-Nitrochlorobenzene, meta-nitrochlorobenzene, paranitrochlorobenzene. The separation and utilization method takes the industrial production residues of the paranitrochlorobenzene, O-Nitrochlorobenzene as starting material, and the starting material is chloridized to obtain 2, 3-dichloronitrobenzene products and the mixture of 2, 4-dichloronitrobenzene, 2, 5-dichloronitrobenzene and 3, 4-dichloronitrobenzene with catalytic function of metal halides; wherein, the mixture of dichloronitrobenzene is carried out fluoro-reaction. with anhydrous potassium fluoride in DMF with the existence of phase-transfer catalyst, 2, 4-difluoronitrobenzene product and the mixture of 2-fluorine-5-chlorine nitrobenzene and 3- fluorine -4-fluoride nitrobenzene are obtained; wherein, the obtained mixture acted by the catalytic agent carries out chlorination reaction to replace nitro group; 2,4-dichlorofluorobenzene is obtained by distillation to the generated product. The technique of the invention adopts the synthetic routes which change waste into valuables, the goal of zero emission is achieved, and the method has the advantages of sustainable development, saving energy, lowering consumption and small environmental pollution.
Description
Technical field
The present invention relates to a kind of neighbour, the Green Sustainable extraction and application engineering technology of p-Nitrophenyl chloride blending ingredients, be specifically related to a kind of new technology being separated and producing highly purified nitro-chlorobenzene and derived product.
Background technology
Due to the sharp increase of world population, the quickening of various countries' process of industrialization, resource and the energy day by day reduce, and are on the verge of exhaustion, and industrial or agricultural pollutent and the domestic refuse of a large amount of discharge make the ecotope of human survival worsen rapidly.Be mainly manifested in topsoil, acid rain cause disaster, global warming, depletion of the ozone layer, the anxiety of Freshwater resources and pollution, pollution of the sea, land resource degradation,
Sharp reduction of the forests, species diversity reduce and environmental hazard noxious chemical and Hazardous wastes increase.The mankind are faced with ecocrisis the most serious since the dawn of human civilization.Ecocrisis Calling for Green chemistry, the lesson of western countries' industrialization development is worth us to note and draws.The extensive management pattern of that " first pollute, rear improvement ", not only accelerates the exhaustion of natural resources, and investment is large, flower amine is many, cure the symptoms, not the disease, and even may cause the danger of secondary pollution.Therefore, how from preventing pollution source, fundamentally reduce or eliminate pollution, realize zero-emission and enter, this is the primary goal of Green Chemistry research and the strategy of sustainable development to improve " Atom economy ".
Green Chemistry is a kind of novel method, the new approaches of the solution environmental problem of rising in recent years, its starting point is the deficiency for traditional end-of-pipe control technology, proposes to reduce (eliminating when possible) chemical industry from source to the pollution of environment.The novel method that Green Chemistry proposes as solving environmental problem, has its distinctive feature, and obtains many achievements.But its starting point is mainly chemical reaction process, be no matter the change of reaction scheme, or the change of reaction conditions, what provide is all conclusion qualitatively, in the sense that, Green Chemistry can be interpreted as green reaction.Green Chemistry is applied to actual industrial production, needs to develop the green chemical technology adapted with it.Green chemical technology is the Chemical Engineering Technology stoping environmental pollution from source developed on Green Chemistry basis.Green chemical technology is the technology of the greenization simultaneously comprising each Chemical Manufacture subsystems such as chemical reaction, sepn process and general facilities.The research of green chemical technology makes the impact of concrete chemical process on environment minimum.Green chemical industry considers the engineering factor in chemical process more, finds out the relation between various engineering specifications in chemical process and " green ", using to environmental impact minimization as optimization aim, utilize various optimization method to find out optimum various engineering specifications.Separation engineering, as an important branch of chemical engineering, covers the many unit operations in chemical process.Sepn process accounts for very large proportion on the capital cost and operational cost of whole chemical process, and single from energy consumption soil, traditional sepn process (as distillation, drying, evaporation etc.) accounts for 30% in chemical industry.The ratio escheat that the cost in the production of biological technology products, being separated, purifying and purifying accounts for its total cost is large.Therefore, the research of greenization is carried out to separation engineering significant.The present invention is directed to Green Chemistry and emphasis is concentrated on reaction process, and the impact that each subsystems such as reaction, separation and general facilities cause environment in the middle of actual chemical process, should be considered simultaneously, the thought of " green " is incorporated in the research of sepn process, design and optimization, proposes the concept of " Green Sustainable extraction and application engineering ": and representative with most in separation engineering, to the most significant rectifying of environmental influence for main contents carry out the technical study of green separation utilizing works.Two paths realizing green separation engineering are proposed: (1) carries out the analysis of green intensity to traditional sepn process, is reached the target of green separation utilizing works by various engineering specifications such as optimizing equipment investment, operating parameterss; (2) green separation engineering novel method, the novel process with green characteristic is researched and developed out.Nitro-chlorobenzene compound is the important intermediate of producing dyestuff, pigment, medicine, agricultural chemicals, rubber ingredients and industrial plastic etc., is also the important source material of fine chemical product, has very wide purposes.
To, o-Nitrochlorobenzene annual production, oneself reaches more than 300,000 tons in current China, in the industrial production, a large amount of resistatess is had to produce, its main component is the mixture of m-nitrochlorobenzene, p-Nitrophenyl chloride and o-Nitrochlorobenzene, how Appropriate application these to the industrial production resistates of, o-Nitrochlorobenzene, to be separated and the derived product of production high added value is a technical problem being worth research.
Summary of the invention
The technical problem to be solved in the present invention is all to utilize the industrial resistates to, o-Nitrochlorobenzene, and provide a kind of simple to operate, can mass-producing, be continuously separated and produce the new technology of high value-added product.
For reaching the object of the invention, the present invention adopts following technical scheme:
Neighbour, the extraction and application method of p-Nitrophenyl chloride blending ingredients, comprise the steps:
(1) chlorine is passed into in the industrial production resistates of, o-Nitrochlorobenzene; chlorination is carried out in 50 ~ 150 DEG C under the catalysis of metal halide; 2 are separated according to boiling point difference rectifying tower after abundant reaction; 3-dichloronitrobenzene; obtain 2 simultaneously; the mixture of 4-dichloronitrobenzene, 2,5-dichloronitrobenzenes and 3,4-dichloronitrobenzene; The described industrial production excess main component to, o-Nitrochlorobenzene is m-nitrochlorobenzene, p-Nitrophenyl chloride and o-Nitrochlorobenzene; The mass ratio of described metal halide and resistates is 1 ~ 10:100; Described resistates total mass is 1:0.1 ~ 3 with the mass ratio passing into chlorine;
(2) in solvent DMF; add that step (1) obtains 2; 4-dichloronitrobenzene, 2; 5-dichloronitrobenzene and 3; the mixture of 4-dichloronitrobenzene and anhydrous potassium fluoride, phase-transfer catalyst; fluoro-reaction is carried out under 150 ~ 250 DEG C of temperature condition; the rear mistake of abundant reaction filters Repone K; filtrate is through steaming DMF; rectifying separates 2 again; 4-difluoro nitrobenzene, obtains staying the mixture of 2-fluoro-5-chloronitrobenzene in rectifying tower and 3-chloro-4-fluoronitrobenzene: described phase-transfer catalyst is quaternary ammonium salt compound or cup cyclic cpds simultaneously; The mass ratio of described DMF, anhydrous potassium fluoride, phase-transfer catalyst and dichloronitrobenzene mixture is 1 ~ 5:0.1 ~ 1:0.01 ~ 0.25:1;
(3) mixture of the 2-fluoro-5-chloronitrobenzene that obtains of step (2) and the chloro-4-fluoronitrobenzene of 3-is under catalyst action; pass into chlorine and carry out chlorination reaction displacement nitro in 150 ~ 250 DEG C; the product generated obtains 2 through distillation; 4-dichlor fluorbenzene; described catalyzer is organo-peroxide, inorganic peroxide or azo compound, and described catalyst levels is l% ~ 15% of the mixture quality of 2-fluoro-5-chloronitrobenzene and the chloro-4-fluoronitrobenzene of 3-; Mixture and the mass ratio passing into chlorine are 1:0.1 ~ 2.
The main component of the industrial production resistates to, o-Nitrochlorobenzene used in the present invention is (quality composition): ask nitro-chlorobenzene about 40%, p-Nitrophenyl chloride about 50%, o-Nitrochlorobenzene about 10%.
The present invention, in three-step reaction process, adopts gas-chromatography (GC) to monitor reaction end.
In step (1), the mass ratio of described metal halide catalyst and resistates is preferably 1 ~ 5:100.Described resistates is preferably 1:0.1 ~ 1 with the mass ratio passing into chlorine.Described metal halide is preferably iron trichloride or aluminum chloride, more preferably iron trichloride.Described temperature of reaction is preferably 80 ~ 105 DEG C, and time of described chlorination reaction is generally recommended as 2 ~ 20 little
Time, preferably 8 ~ 10 hours.Step (1) is obtained by reacting in product mixtures a chloronitrobenzene compound that may also have non-chlorination, now needs the chloronitrobenzene compound first isolating non-chlorination according to boiling point difference, then enters rectifying tower and separate 2,3-dichloronitrobenzene.One chloronitrobenzene of non-chlorination returns chlorination again.
In step (2), the mass ratio of described DMF, anhydrous potassium fluoride, phase-transfer catalyst and dichloronitrobenzene mixture is preferably 1 ~ 3:0.1 ~ 0.5:0.03 ~ 0.15:1.Described fluorination reaction temperature is preferably 150 ~ 200 DEG C; The described fluoridation time is generally 5 ~ 30h, is preferably 15 ~ 25h.Described phase-transfer catalyst is quaternary ammonium salt compound or cup cyclic cpds, and preferred compound season continues salt compound.Described quaternary ammonium salt compound and cup cyclic cpds can be made by oneself according to existing method, also can buy from the market.
In step (3), described catalyst levels is preferably 1% ~ 10% of the mixture quality of 2-fluoro-5-chloronitrobenzene and the chloro-4-fluoronitrobenzene of 3-, and described mixture is preferably 1:0.1 ~ 1 with the mass ratio passing into chlorine.Described catalyzer can be organo-peroxide, inorganic peroxide or azo compound, preferably one of following: benzoyl peroxide first is cruel, peroxidation carbonic acid vinegar, persulphate, azo two isobutyl are cured, azo two eyeball in different heptan.Described temperature of reaction is preferably 170 ~ 220 DEG C.The described reaction times is 5 ~ 25h, is preferably 5 ~ 15h.
Embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto.
Embodiment 1:
Add 157.5 kilograms in a kettle. to the industrial production resistates of, o-Nitrochlorobenzene, add 1.58 kilograms of al dichlorides, be heated to 80 DEG C, pass into 15.8 kilograms of chlorine with 8 hours and carry out chlorination, according to boiling point difference, one chloronitrobenzene compound of non-chlorination is returned chlorination again, the product that chlorination produces is mixing dichloronitrobenzene 3,4-dichloronitrobenzene simultaneously, 2,5-dichloronitrobenzene, 2,4-dichloronitrobenzene, 2,3-dichloronitrobenzene.Then according to boiling point difference, 2,3-dichloronitrobenzene 2.4 kilograms is separated with rectifying tower, through its purity of gas chromatographic detection two three 99.5%, fusing point 62 DEG C, productive rate about 1.3%; Obtain 45.6 kilograms, the mixture of 2,4-dichloronitrobenzene, 2,5-dichloronitrobenzenes and 394 dichloronitrobenzenes, productive rate about 23.80/0 simultaneously.
Embodiment 2:
Add 157.5 kilograms in a kettle. to the industrial production resistates of, o-Nitrochlorobenzene, add 3.95 kilograms of aluminum chlorides, be heated to 95 DEG C, pass into 60 kilograms of chlorine with 9 hours and carry out chlorination, according to boiling point difference, one chloronitrobenzene compound of non-chlorination is returned chlorination again, the product that chlorination produces is mixing dichloronitrobenzene 3,4-dichloronitrobenzene simultaneously, 2,5-dichloronitrobenzene, 2,4-dichloronitrobenzene, 2,3-dichloronitrobenzene.Then according to boiling point difference, 2.3-dichloronitrobenzene 7.2 kilograms is separated with rectifying tower, through its purity of gas chromatographic detection two three 99.5%, fusing point 62 DEG C, productive rate about 3.8%; Obtain 129.6 kilograms, the mixture of the high and steep base benzene of 2,4-dichloronitrobenzene, 2,5-dichloronitrobenzenes and 3,4-dichloro, productive rate about 67.5% simultaneously.
Embodiment 3:
Add 157.5 kilograms in a kettle. to the industrial production resistates of, o-Nitrochlorobenzene, add 7.87 kilograms of aluminum chlorides, be heated to 105 DEG C, pass into 157.5 kilograms of chlorine with 9 hours and carry out chlorination, according to boiling point difference, one chloronitrobenzene compound of non-chlorination is returned chlorination again, the product that chlorination produces is mixing dichloronitrobenzene: 3,4-dichloronitrobenzenes simultaneously, 2,5-dichloronitrobenzene, 2,4-dichloronitrobenzene, 2,3-dichloronitrobenzene.Then according to boiling point difference, 2,3 are separated with rectifying tower, dichloronitrobenzene 15.4 kilograms, through its purity of gas chromatographic detection two three 99.5%, fusing point 62 DEG C, productive rate about 8%; Obtain 176.6 kilograms, the mixture of 2,4-dichloronitrobenzene, anti-3, the 4-dichloronitrobenzenes of 2,5-dichloronitrobenzenes, productive rate about 92% simultaneously.
Claims (7)
1. neighbour, the extraction and application method of p-Nitrophenyl chloride blending ingredients, it is characterized in that described extraction and application method comprises the steps:
(1) chlorine is passed into in the industrial production resistates of, o-Nitrochlorobenzene; chlorination is carried out in 50 ~ 150 DEG C under the catalysis of metal halide; 2 are separated according to boiling point difference rectifying training after abundant reaction; the high and steep base benzene of 3-dichloro; obtain 2 simultaneously; the mixture of 4-dichloronitrobenzene, 2,5-dichloronitrobenzenes and 3,4-dichloronitrobenzene; The described industrial production resistates main component to, o-Nitrochlorobenzene is for asking nitro-chlorobenzene, p-Nitrophenyl chloride and o-Nitrochlorobenzene: the mass ratio of described metal halide catalyst and resistates is 1 ~ 10:100; Described resistates total mass is 1:0.1 ~ 3 with the mass ratio passing into chlorine;
(2) in solvent DMF; add that step (1) obtains 2; 4-dichloronitrobenzene, 2; 5-dichloronitrobenzene and 3; the mixture of 4-dichloronitrobenzene and anhydrous potassium fluoride, phase-transfer catalyst; fluoro-reaction is carried out under 150 ~ 250 DEG C of temperature condition; the rear mistake of abundant reaction filters Repone K; filtrate is after steaming DMF; rectifying separates 2.4-difluoro nitrobenzene again; obtain staying the mixture of 2-fluoro-5-chloronitrobenzene in rectifying tower and the chloro-4-fluoronitrobenzene of 3-, described phase-transfer catalyst is quaternary ammonium salt compound or cup cyclic cpds simultaneously; The mass ratio of described DMF, anhydrous potassium fluoride, phase-transfer catalyst and dichloronitrobenzene mixture is 1 ~ 5:0.1 ~ 1:0.01 ~ 0.25:1;
(3) mixture of the 2-fluoro-5-chloronitrobenzene that obtains of step (2) and the chloro-4-fluoronitrobenzene of 3-is under catalyst action, pass into chlorine and carry out chlorination reaction displacement nitro in 150 ~ 250 DEG C, the product generated obtains 2 through distillation, 4-dichlor fluorbenzene, described catalyzer is organo-peroxide, inorganic peroxide or azo compound, described catalyst levels is the mixture of 1% ~ 15%, 2-fluoro-5-chloronitrobenzene of the mixture quality of 2-fluoro-5-chloronitrobenzene and 3-chloro-4-fluoronitrobenzene and the chloro-4-fluoronitrobenzene of 3-and the mass ratio that passes into chlorine is 1:0.1 ~ 2.
2. extraction and application method as claimed in claim 1, is characterized in that step (1) described metal halide is iron trichloride or aluminum chloride.
3. the extraction and application method as described in claim l, it is characterized in that step (1) described chlorination reaction temperature is 80 ~ 105 DEG C, the reaction times is 8 ~ 10 hours.
4. the extraction and application method as described in claim l, is characterized in that the mass ratio of step (1) described metal halide catalyst and resistates is 1 ~ 5:100, and described resistates is 1:0.1 ~ 1 with the mass ratio passing into chlorine.
5. extraction and application method as claimed in claim 1, is characterized in that the phase-transfer catalyst described in step (2) is compound quaternary ammonium salt compound.
6. extraction and application method as claimed in claim 1, is characterized in that the mass ratio of the DMF described in step (2), anhydrous potassium fluoride, phase-transfer catalyst and dichloronitrobenzene mixture is 1 ~ 3:0.1 ~ 0.5:0.03 ~ 0.15:1.
7. extraction and application method as claimed in claim 1, is characterized in that step.Described fluorination reaction temperature is 150 ~ 200 DEG C, and the reaction times is 15 ~ 25h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110437073A (en) * | 2018-05-03 | 2019-11-12 | 浙江解氏新材料股份有限公司 | A kind of comprehensive exploitation separation method of chloronitrobenzene meta position oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110437073A (en) * | 2018-05-03 | 2019-11-12 | 浙江解氏新材料股份有限公司 | A kind of comprehensive exploitation separation method of chloronitrobenzene meta position oil |
| CN110437073B (en) * | 2018-05-03 | 2022-04-29 | 浙江解氏新材料股份有限公司 | Comprehensive development and separation method of chloronitrobenzene meta-oil |
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Application publication date: 20150610 |