CN103623867A - Composite catalyst for selective chlorination of aromatic compounds and application thereof - Google Patents
Composite catalyst for selective chlorination of aromatic compounds and application thereof Download PDFInfo
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Abstract
The invention provides a composite catalyst for the selective chlorination of aromatic compounds, which comprises a metal complex and an organic sulfide. The invention also provides application of the composite catalyst as a reaction catalyst for the selective chlorination of aromatic compounds, which is specifically implemented by carrying out selective chlorination on aromatic compounds by taking chlorine gas as a chlorine source under the catalytic action of the composite catalyst. According to the composite catalyst, para-selectivity is good, meta-position products are few, the composite catalyst is suitable for being practically used, and wide in application range, can be applied to the chlorination of all aromatic compounds and derivatives thereof, including di-chlorination and poly-chlorination, as well as the chlorination of monocyclic or polycyclic hydrocarbons and derivatives thereof.
Description
Technical field
The invention belongs to organic synthesis field, particularly a kind of composite catalyst for aromatic selective chlorination, also relates to the application that this meets catalyst.
Background technology
Paracide is a kind of important Organic chemical products, as far back as external just large-scale production paracide of 19 beginnings of the century; Research and the production of Er China paracide are started late, until the beginning of the eighties in 19th century just synthetic the and purification techniques of the Directional Method of paracide in China, just obtain large development.
The dichloro product of benzene or chlorobenzene comprises paracide (PDCB), o-dichlorohenzene (ODCB) and m-dichlorobenzene (MDCB).Because the using value of paracide is far away higher than o-dichlorohenzene and m-dichlorobenzene, so require to improve the high selectivity of paracide in industrial production.The amplification of China dichloro-benzenes production capacity is very fast, but the paracide synthesis technique of high selectivity also do not grasped completely, and this factor has determined that its production still has good development space and potentiality.
The process that benzene or chlorobenzene prepare dichloro-benzenes as raw material of take is to belong to nucleophilic substitution, and conventional catalyst is mainly lewis acid catalyst, comprises ferric trichloride, trichloride antimony, Antimony pentachloride, zinc chloride and aluminium chloride etc.Take single lewis acid if ferric trichloride is catalyst, carry out benzene chlorination under liquid-phase condition, in product, the content of paracide accounts for 55% left and right, and m-dichlorobenzene is about 5%, and o-dichlorohenzene accounts for 40% left and right; The single lewis acid of take is prepared the requirement that paracide can not meet industrial high selectivity as catalyst under liquid-phase condition.US3029296 (1962) discloses take iron chloride as chlorination reagent, between 155-199 ℃, make chlorobenzene under gaseous state with solid-state ferric chloride reaction, the paracide purity obtaining reaches 96%; Yet this reaction is carried out under gas phase condition, is difficult for operation and controlling, in can not being widely used in producing.
Revital Ben-Daniel, Samuel P.de Visser etc. are at J.AM.CHEM.SOC.2003, and 125,12116-12117 discloses at HCl and H
2o
2sour environment under existing is lower, take trifluoroethanol as solvent, without with catalyst, benzene/chlorobenzene being carried out to original position chlorination.In this process, HCl elder generation and H
2o
2effect forms HOCl, then generates chlorobenzene with benzene effect, and the conversion ratio of benzene is 73%.When substrate is chlorobenzene, HCl elder generation and H
2o
2effect forms HOCl, then reacts generation dichloro-benzenes and polystream with chlorobenzene.Chlorobenzene conversion ratio is that 23%, P/O is 2.03(because the content of metacompaund is conventionally minimum, investigate contraposition product selective available be that the ratio (P/O) of paracide and o-dichlorohenzene represents), conversion ratio and P/O are all too low.The method is only applicable to very active aromatic chlorination in addition, and need to consume a large amount of HCl.
Article Tetrahedron Letters, 21,3809 (1980) disclose solid acid zeolites, and as ZSM-5, ZSM-11, Mordenite, L and Y type can be used as the catalyst of benzene chlorination, wherein the chlorination effect of zeolite L is best.US4835327 (1989) also discloses usings L-type or Y zeolite and prepares polystream as catalyst, because have tradable cation in this molecular sieve of two types, comprises metal cation, hydrogen or ammonium.The cation of hydrogen and ammonium can be replaced by other ions and can not cause that substantial variation occurs basic crystal structure as metal ion.WO9718893(1997) disclose with the chloride of transition metal salt, rare alkaline metal salt or its mixture, alkali metal or alkaline-earth metal and comprised LiCl, NaCl, KCl, MgCl
2, CaCl
2, by infusion process, solid acid zeolite modified is become to alkali metal crossover zeolite, as the catalyst of chlorobenzene chlorination.When using while being catalyst by the solid acid zeolites of modified, conversion ratio can reach 92.5%, P/O can reach 12.2.Take zeolite during as catalyst as seen, the conversion ratio of chlorobenzene and P/O are all higher, but the HCl producing in course of reaction can make the aperture of catalyst cave in, catalysqt deactivation.Zeolite is during as catalyst, and consumption is very large, if can not solve the problem of reusing of catalyst, during this kind of method can not be widely used in producing.
B.Jayachandran etc. are at Indian Journal of Chemistry Vol.45B, April2006, in pp.972-975, disclose take containing transition metal as the kaolin of iron and titanium be catalyst, with Cl
2/ SO
2cl
2for chlorination group, to aromatic hydrocarbons or arylamine chlorination, obtain the contraposition product of high-load.When take benzene as raw material, Cl
2during for chlorine source, benzene conversion ratio is 70%, product consist of 41% chlorobenzene, 56% paracide and 3% o-dichlorohenzene; With SO
2cl
2during for chlorine source, benzene conversion ratio is for being only 2%.Take chlorobenzene during as raw material, respectively with Cl
2, SO
2cl
2during for chlorination group, chlorobenzene conversion ratio be respectively 100% and 25%, P/O be respectively 2.76 and 3.
Single catalyst can not meet the requirement that meets the high selectivity of paracide under liquid-phase condition, and people start composite catalyst to study.
US1946040 (1934), EP0829461A1 (1997), US5210343 (1993) and US3226447 (1965) disclose usings the catalyst of composite catalyst as benzene or chlorobenzene chlorination.
US1946040 (1934) discloses the composite catalyst using lithium metal, sulphur and trichloride antimony as benzene chlorination, and the chlorine of take reacts under liquid-phase condition as chlorine source, and its effect is better than one-component or two combination of components as the effect of catalyst.
EP0829461A1 (1997) is used lewis acid catalyst iron chloride, aluminium chloride etc. and sulphur, sulfur-containing compound together with dimethyl dichloro thianthrene etc.With take chlorobenzene and compare as raw material, take benzene during as raw material, when elemental sulfur is used together with lewis acid catalyst, P/O is higher, when having trichloro-benzenes to occur, P/O is 1.17.
US5210343 (1993) discloses take benzene as raw material, iron or ferric trichloride, alchlor, trichloride antimony etc. are catalyst, when being co-catalyst containing the organic compound of sulfydryl as the product of thioacetic acid, thiophene and they and halogen reaction, P/O can reach 3.3, and in product, the content of m-dichlorobenzene obviously reduces.
US3226447(1965) disclose that benzene is made catalyst at iron chloride and TGA, chlorine is chlorine source, under reflux state, through 5.5h, transforms completely, the chlorizate obtaining is chlorobenzene 52.2%, P/O=1.5, m-dichlorobenzene 0.75%.Benzene is made catalyst at iron filings and thioacetic acid, chlorine is chlorine source, reacts 3h and transform completely at 35-38 ℃, and chlorizate consists of chlorobenzene 43%, P/O=3.3.Take chlorobenzene as raw material, and iron filings and thioacetic acid are made catalyst, and chlorine is chlorine source, and at 35-39 ℃, reacting 1.5h conversion ratio is 57.9%, and chlorizate consists of P/O=3.1.
The electric medium of super parent when Applied Catalysis A:General401 (2011) 176 – 181 disclose in the sulfuric acid that trifluoro isocyanuric acid is dissolved in to 98% as aromatic chlorination such as Gabriela Fonseca Mendonca, when substrate is chlorobenzene, after reaction 24h, obtaining dichloro-benzenes content is 68%, wherein P/O is 2.0, and many chlorine accounts for 32%.
US6825383B1 (2004) discloses take alkali-metal chloride as chlorine source, at high price iodine, is, under catalyst condition, alkanes, olefinic hydro carbons and aromatic hydrocarbon substance are carried out to chlorination.Take sodium metaperiodate as catalyst, sodium chloride are chlorination group, add 20% sulfuric acid to make pH=2-3, acetonitrile: during water=2:1, at 80 ℃, benzene is carried out to chlorination, the chlorizate obtaining is chlorobenzene 33%, and the content of paracide is few.Take chlorobenzene as raw material, under same condition, react, the conversion ratio of chlorobenzene is only 10%.
Above method all can not meet the requirement of actual production well, therefore must invent new method, should improve the high selectivity of paracide and also want to be applied to actual production.Meanwhile, in the reaction of preparing dichloro-benzenes, good catalyst also will guarantee that in dichloro-benzenes, the content of m-dichlorobenzene is less than 0.1%, because the fusing point of m-dichlorobenzene and paracide is very close, the method by simple economy is difficult to separation.
Summary of the invention
Goal of the invention: the first object of the present invention is to provide the composite catalyst for aromatic selective chlorination that a kind of para-selectivity is good, be suitable for practicality.
The second object of the present invention is to provide above-mentioned composite catalyst as the application of aromatic selective chlorination catalysts.
Technical scheme: a kind of composite catalyst for aromatic selective chlorination provided by the invention, comprises metal complex and organic sulfur compound.
As preferably, the central atom of described metal complex is selected from a kind of in the metal of the 3rd and the 5th main group in 3-6 cycle and transition elements; The part of described metal complex is organic monoacid or inorganic acid, preferably
pka is the organic ligand of 3-9.
Preferred as another kind, the central atom of described metal complex is iron, cobalt, nickel, copper, zinc, aluminium, manganese, molybdenum, antimony, vanadium, niobium, palladium or platinum, preferably iron, cobalt, nickel, copper, zinc, aluminium or manganese, more preferably aluminium or iron; The organic ligand of described metal complex is carboxylic acid, acetylacetone,2,4-pentanedione, stearic acid, carboxylic acid derivates, acetylacetone,2,4-pentanedione derivative or stearic acic derivative, preferably acetylacetone,2,4-pentanedione.Preferred part acetylacetone,2,4-pentanedione is to have 1 methylene (CH
2-) structure that is connected with 2 carbonyls, it has the tautomerism of enol and ketone, proton on wherein 1 hydroxyl of its dynamic isomer more easily removes, and the negative electrical charge of the carbanion of generation is dispersed on two adjacent with it oxygen atoms by conjugation, and therefore this conjugated structure can be very steady; Meanwhile, acetylacetone,2,4-pentanedione is the simplest beta-diketone compound, is therefore a kind of double-tooth chelate ligand of excellence; Doing the used time with central atom, generally, acetylacetone,2,4-pentanedione is with oxygen key chelating bidentate form and metallic ion coordination, forms hexa-atomic chelate ring.
Preferred as another kind, described metal complex is selected from one or more in manganese chloride, iron chloride, aluminium chloride, niobium chloride, copper sulphate, nickel acetylacetonate, ferric acetyl acetonade, acetylacetone copper, aluminium acetylacetonate, manganese acetylacetonate, acetylacetone cobalt, copper stearate and ferric stearate etc., preferably one or more in nickel acetylacetonate, ferric acetyl acetonade, acetylacetone copper, aluminium acetylacetonate, manganese acetylacetonate and acetylacetone cobalt.
Preferred as another kind, described organic sulfur compound is compound and halo derivatives thereof containing sulfydryl, preferably one or more in mercaptan, sulfydryl aliphatic carboxylic acid, dipropyl sulfide, benzenethiol, alkylthio carboxylic acid, alkyl sulfur compounds, alkyl disulfide, aromatic yl sulfide, fragrant disulphide, perchloro-methyl mercaptan, phenthazine, thiophene, thiophane and thiocarbamide.
Preferred as another kind, the mass ratio of metal complex and organic sulfur compound is (1-2000): (1-2000).
The present invention also provides the application of above-mentioned composite catalyst as aromatic selective chlorination catalysts, is specially: take chlorine as chlorine source, aromatic is selective chlorination under the catalytic action of composite catalyst.
As preferably, in aromatic and composite catalyst, the mass ratio of metal complex, organic sulfur compound is 100:(0.005-10): (0.005-10), preferred 100:(0.01-2): (0.01-2).
Preferred as another kind, chlorination reaction temperature is 5-90 ℃, preferred 30-80 ℃, most preferably 65 ℃.
Preferred as another kind, chlorine passes in reaction system with constant flow rate, chlorine flow velocity 40-60mL/min, preferably 50mL/min; In the process of whole reaction, chlorine is to pass into continuously in reaction system with constant speed, because at a certain temperature with catalyst content under, if amount of chlorine is too little, the conversion ratio of raw material is lower, experiment carry out slower, and if the amount of chlorine is too large, what experiment was carried out will more acutely should not control, and has more many chlorine product and occurs.
Beneficial effect: composite catalyst para-selectivity provided by the invention is good and metacompaund is few, be suitable for practicality, applied range, can be used for the chlorination of all aromatics and derivative thereof, comprise dichloride and many chlorinations, also comprise the chlorination of the hydrocarbon and their derivative of monocycle or many rings.
The central atom of the metal complex in this composite catalyst and part exist to form the form of complex, it is not simple mechanical mixture, metal complex is dissolved in aromatic and derivative thereof, thereby make reaction that homogeneous reaction occur in liquid phase environment, make reaction condition comparatively gentle, make it be more suitable for industrial selective catalysis chlorination.
This meets catalyst and dissolves in aromatic liquid compound, and this composite catalyst is applied to the reaction of aromatic selective chlorination, and aromatic, if chlorobenzene itself is raw material and solvent, does not need to add other organic solvent; Aromatic directly reacts with chlorine under composite catalyst exists, and obtains chloro-product; This composite catalyst can be accelerated reaction process, improve the selective of target product paracide.
Take lewis acid and compare as catalyst with existing, composite catalyst consumption of the present invention, particularly wherein metal complex consumption is less, greatly reduces cost and reaction efficiency.
The specific embodiment
According to following embodiment, the present invention may be better understood.Yet, those skilled in the art will readily understand, the described concrete material proportion of embodiment, process conditions and result thereof be only for the present invention is described, and should also can not limit the present invention described in detail in claims.
The preparation method of metal complex of the present invention is a lot, comprises solid phase method and liquid phase method etc., for known in this field, adopts solid phase method to prepare metal complex used in the present invention.(Li Guangmei etc. the preparation and application of acetylacetonate. < < chemical intermediate > > .2009.8.01-04)
Take ferric acetyl acetonade as example: gets 36mmol (1.44g) solid base NaOH and put into mortar; the acetylacetone,2,4-pentanedione that adds 80mmol (16g); grind 2～3min; add again 20mmol (3.25g) iron chloride; after adding molysite, be ground to scattered paste shape; continue to be ground to pressed powder, grind 15min; After reacting completely, use distilled water immersion, suction filtration, then with 60mL distilled water washing 3 times, dry under room temperature, be reddish orange crystal, under room temperature normal pressure, surveying its fusing point is 179-182 ℃.Profit uses the same method can synthesis of acetyl acetone aluminium, is white powder, and under room temperature normal temperature, surveying its fusing point is 190-194 ℃.
Other metal complexs preparation method is to above-mentioned similar.
Embodiment 1
The chlorobenzene that adds 1500g in 5mL reaction bulb, starts to stir, and is heated to 50 ℃ of steady temperatures, adds the ferric acetyl acetonade of 18g, blasts quantitative chlorine simultaneously.Whole device reacts under normal pressure.Every 0.5h sampling, the content of each material in the carrying out of monitor reaction by gas chromatograph and detection reaction system, stops reacting when having trichlorine product to occur.
Embodiment 2
The chlorobenzene that adds 1500g in 5L reaction bulb, starts to stir, and is heated to 50 ℃ of steady temperatures, adds ferric acetyl acetonade and the 0.4g mercaptan of 18g, blasts quantitative chlorine simultaneously.Whole device reacts under normal pressure.Every 0.5h sampling, the content of each material in the carrying out of monitor reaction by gas chromatograph and detection reaction system, stops reacting when having trichlorine product to occur.
Embodiment 3
The chlorobenzene that adds 1500g in 5L reaction bulb, starts to stir, and is heated to 50 ℃ of steady temperatures, adds aluminium acetylacetonate and the 0.4g mercaptan of 18g, blasts quantitative chlorine simultaneously.Whole device reacts under normal pressure.Every 0.5h sampling, the content of each material in the carrying out of monitor reaction by gas chromatograph and detection reaction system, stops reacting when having trichlorine product to occur.
Embodiment 4
The chlorobenzene that adds 1000g in 5L reaction bulb, starts to stir, and is heated to 65 ℃ of steady temperatures, adds iron chloride and the 0.005g dipropyl sulfide of 10g, blasts quantitative chlorine simultaneously.Whole device reacts under normal pressure.Every 0.5h sampling, the content of each material in the carrying out of monitor reaction by gas chromatograph and detection reaction system, stops reacting when having trichlorine product to occur.
Embodiment 5
The chlorobenzene that adds 1000g in 5L reaction bulb, starts to stir, and holding temperature is constant at 30 ℃, adds aluminium chloride and the 5g sulfydryl aliphatic carboxylic acid of 0.005g, blasts quantitative chlorine simultaneously.Whole device reacts under normal pressure.Every 0.5h sampling, the content of each material in the carrying out of monitor reaction by gas chromatograph and detection reaction system, stops reacting when having trichlorine product to occur.
Embodiment 6
The chlorobenzene that adds 1000g in 5L reaction bulb, starts to stir, and is heated to 80 ℃ of steady temperatures, adds niobium chloride and the 1g benzenethiol of 1g, blasts quantitative chlorine simultaneously.Whole device reacts under normal pressure.Every 0.5h sampling, the content of each material in the carrying out of monitor reaction by gas chromatograph and detection reaction system, stops reacting when having trichlorine product to occur.
Embodiment 7
The chlorobenzene that adds 1000g in 5L reaction bulb, starts to stir, and is heated to 90 ℃ of steady temperatures, adds copper sulphate and 5g (ethylenebis dithiocarbamate) acetic acid of 0.05g, blasts quantitative chlorine simultaneously.Whole device reacts under normal pressure.Every 0.5h sampling, the content of each material in the carrying out of monitor reaction by gas chromatograph and detection reaction system, stops reacting when having trichlorine product to occur.
Embodiment 8
The chlorobenzene that adds 1000g in 5L reaction bulb, starts to stir, and is heated to 50 ℃ of steady temperatures, adds nickel acetylacetonate and the positive decyl sulfuration of the 0.05g methyl of 5g, blasts quantitative chlorine simultaneously.Whole device reacts under normal pressure.Every 0.5h sampling, the content of each material in the carrying out of monitor reaction by gas chromatograph and detection reaction system, stops reacting when having trichlorine product to occur.
Embodiment 9
The chlorobenzene that adds 1000g in 5L reaction bulb, starts to stir, and is refrigerated to 5 ℃ of steady temperatures, adds acetylacetone copper and the 0.5g dicyclohexyl bisulfide of 7g, blasts quantitative chlorine simultaneously.Whole device reacts under normal pressure.Every 0.5h sampling, the content of each material in the carrying out of monitor reaction by gas chromatograph and detection reaction system, stops reacting when having trichlorine product to occur.
Embodiment 10
The chlorobenzene that adds 1000g in 5L reaction bulb, starts to stir, and is heated to 50 ℃ of steady temperatures, adds manganese acetylacetonate and the 1g triphenyl phosphine sulfide of 2g, blasts quantitative chlorine simultaneously.Whole device reacts under normal pressure.Every 0.5h sampling, the content of each material in the carrying out of monitor reaction by gas chromatograph and detection reaction system, stops reacting when having trichlorine product to occur.
Embodiment 11
Substantially the same manner as Example 2, difference is only: adopt acetylacetone cobalt to replace ferric acetyl acetonade, adopt two (4-amino-2-chlorphenyl) disulfides to replace mercaptan.
Embodiment 12
Substantially the same manner as Example 2, difference is only: adopt copper stearate to replace ferric acetyl acetonade, adopt perchloro-methyl mercaptan to replace mercaptan.
Embodiment 13
Substantially the same manner as Example 2, difference is only: adopt ferric stearate to replace ferric acetyl acetonade, adopt phenthazine to replace mercaptan.
Embodiment 14
Substantially the same manner as Example 2, difference is only: adopt thioacetic acid zinc to replace ferric acetyl acetonade, adopt thiophene to replace mercaptan.
Embodiment 15
Substantially the same manner as Example 2, difference is only: adopt stearic acid molybdenum to replace ferric acetyl acetonade, adopt thiophane to replace mercaptan.
Embodiment 16
Substantially the same manner as Example 2, difference is only: adopt hexafluoroacetylacetone palladium to replace ferric acetyl acetonade, adopt thiocarbamide to replace mercaptan.
Embodiment 17
Substantially the same manner as Example 2, difference is only: adopt (stearic acid mercapto ethyl ester) antimony to replace ferric acetyl acetonade.Embodiment 18
Substantially the same manner as Example 2, difference is only: adopt vanadium acetylacetonate to replace ferric acetyl acetonade.
Embodiment 19
Substantially the same manner as Example 2, difference is only: adopt platinum tetrachloride to replace ferric acetyl acetonade.
Embodiment 20
Substantially the same manner as Example 2, difference is only: adopt yttrium chloride to replace ferric acetyl acetonade.
Embodiment 21
Substantially the same manner as Example 2, difference is only: adopt titanium acetylacetone to replace ferric acetyl acetonade.
Conversion ratio and P/O value are in Table 1:
Table 1 conversion ratio and P/O value
| Embodiment | Conversion ratio/% | P/O | Embodiment | Conversion ratio/% | P/O |
| 1 | 76 | 1.78 | 12 | 67 | 4.68 |
| 2 | 72 | 4.65 | 13 | 68 | 4.44 |
| 3 | 73 | 4.78 | 14 | 75 | 4.29 |
| 4 | 77 | 4.76 | 15 | 71 | 4.38 |
| 5 | 69 | 4.58 | 16 | 76 | 4.67 |
| 6 | 65 | 4.61 | 17 | 75 | 4.16 |
| 7 | 73 | 4.73 | 18 | 70 | 4.34 |
| 8 | 75 | 4.91 | 19 | 69 | 4.29 |
| 9 | 76 | 4.61 | 20 | 64 | 4.57 |
| 10 | 71 | 4.28 | 21 | 65 | 4.38 |
| 11 | 71 | 4.38 | ? | ? | ? |
The data of table 1 show: composite catalyst is for being dichloro-benzenes by monochloro-benzene chlorination, can meet high selective of higher conversion and target product paracide.Take single organometallic complex as catalyst, also can realize the high conversion of chlorobenzene, the high selectivity of paracide.
Claims (9)
1. for a composite catalyst for aromatic selective chlorination, it is characterized in that: comprise metal complex and organic sulfur compound.
2. a kind of composite catalyst for aromatic selective chlorination according to claim 1, is characterized in that: the central atom of described metal complex is selected from metal and the transition elements of the 3rd and the 5th main group that are positioned at the 3-6 cycle; The part of described metal complex is organic monoacid or inorganic acid.
3. a kind of composite catalyst for aromatic selective chlorination according to claim 1, it is characterized in that: the central atom of described metal complex is iron, cobalt, nickel, copper, zinc, aluminium, manganese, molybdenum, antimony, vanadium, niobium, palladium or platinum, preferably aluminium or iron; The part of described metal complex is carboxylic acid, acetylacetone,2,4-pentanedione, stearic acid, carboxylic acid derivates, acetylacetone,2,4-pentanedione derivative or stearic acic derivative, preferably acetylacetone,2,4-pentanedione.
4. a kind of composite catalyst for aromatic selective chlorination according to claim 1, is characterized in that: described metal complex is manganese chloride, iron chloride, aluminium chloride, niobium chloride, copper sulphate, nickel acetylacetonate, ferric acetyl acetonade, acetylacetone copper, aluminium acetylacetonate, manganese acetylacetonate, acetylacetone cobalt, copper stearate or ferric stearate.
5. a kind of composite catalyst for aromatic selective chlorination according to claim 1, is characterized in that: described organic sulfur compound is selected from one or more in mercaptan, sulfydryl aliphatic carboxylic acid, dipropyl sulfide, benzenethiol, alkylthio carboxylic acid, alkyl sulfur compounds, alkyl disulfide, aromatic yl sulfide, fragrant disulphide, perchloro-methyl mercaptan, phenthazine, thiophene, thiophane and thiocarbamide.
6. a kind of composite catalyst for aromatic selective chlorination according to claim 1, is characterized in that: the mass ratio of metal complex and organic sulfur compound is (1-2000): (1-2000).
7. composite catalyst claimed in claim 1, as the application of aromatic selective chlorination catalysts, is characterized in that: take chlorine as chlorine source, aromatic is selective chlorination under the catalytic action of composite catalyst.
8. application as claimed in claim 6, is characterized in that: in aromatic and composite catalyst, the mass ratio of metal complex, organic sulfur compound is 100:(0.005-10): (0.005-10), preferred 100:(0.01-2): (0.01-2).
9. application as claimed in claim 6, is characterized in that: chlorination reaction temperature is 5-90 ℃, preferred 30-80 ℃, most preferably 65 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588113A (en) * | 2015-02-05 | 2015-05-06 | 东南大学 | Polymer supported catalyst and application thereof in aromatic selective chlorination reaction |
| CN106944125A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN108295899A (en) * | 2018-02-02 | 2018-07-20 | 国家纳米科学中心 | A kind of two dimension copper-based nano piece catalyst and its preparation method and application |
| CN115850195A (en) * | 2022-11-29 | 2023-03-28 | 宁夏格瑞精细化工有限公司 | Synthetic method of sulfentrazone intermediate |
| CN115894162A (en) * | 2022-11-28 | 2023-04-04 | 南京工业大学 | Method for preparing p-bromotoluene by catalyzing toluene with niobium |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588113A (en) * | 2015-02-05 | 2015-05-06 | 东南大学 | Polymer supported catalyst and application thereof in aromatic selective chlorination reaction |
| CN106944125A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of preparation method of hydrocracking catalyst |
| CN108295899A (en) * | 2018-02-02 | 2018-07-20 | 国家纳米科学中心 | A kind of two dimension copper-based nano piece catalyst and its preparation method and application |
| CN108295899B (en) * | 2018-02-02 | 2020-12-11 | 国家纳米科学中心 | Two-dimensional copper-based nanosheet catalyst, and preparation method and application thereof |
| CN115894162A (en) * | 2022-11-28 | 2023-04-04 | 南京工业大学 | Method for preparing p-bromotoluene by catalyzing toluene with niobium |
| CN115850195A (en) * | 2022-11-29 | 2023-03-28 | 宁夏格瑞精细化工有限公司 | Synthetic method of sulfentrazone intermediate |
| WO2024114106A1 (en) * | 2022-11-29 | 2024-06-06 | 宁夏格瑞精细化工有限公司 | Sulfentrazone intermediate synthesis method |
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