CN109721463A - The method for preparing halogenated aromatic compound - Google Patents
The method for preparing halogenated aromatic compound Download PDFInfo
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- CN109721463A CN109721463A CN201711023809.6A CN201711023809A CN109721463A CN 109721463 A CN109721463 A CN 109721463A CN 201711023809 A CN201711023809 A CN 201711023809A CN 109721463 A CN109721463 A CN 109721463A
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Abstract
This disclosure relates to a kind of method for preparing halogenated aromatic compound, it is characterized in that, it is reacted this method comprises: contacting the liquid material containing aromatic compound, oxidant and halogen acids with catalyst, wherein the catalyst is titanium-silicon molecular sieve catalyst and/or zirconium-silicon molecular sieve catalyst.This method operating process is simple, and reaction condition is mild, and feed stock conversion is high.
Description
Technical field
This disclosure relates to a kind of method for preparing halogenated aromatic compound.
Background technique
Starting material or intermediate of the halogenated organic compounds as organic synthesis are a kind of important compounds, extensively
The fields such as the general preparation for materials synthesis, industrial chemical and bioactive compound.
It is the main method of industrial production chlorinated compound using chlorine as chlorinating agent.When preparing chlorinated aromatic compound,
Since the activity of aromatic compound is lower, it usually needs catalyst is added, such as lewis acid catalyst ferric trichloride, four chlorinations
Tin, alchlor etc..In order to solve the problems, such as homogeneous chlorination reaction catalyst difficulty separation, Si-Al molecular sieve, which is incorporated by, is urged
Agent, such as Y type molecular sieve, X-type molecular sieve, L-type molecular sieve (patent US 4794201), modenite all have it is good
Catalytic activity.However, by-product hydrogen chloride is understood after having reacted by chlorinating agent of chlorine, and Si-Al molecular sieve is in high concentration chlorination
Hydrogen system flowering structure will receive badly damaged, influence its recycling.In addition, chlorine is as toxic gas, transport, storage
Special installation is required to using.Chlorine as chlorinating agent in use, reaction generates hydrogen chloride, only have by chlorine atom utilization rate
50%, the by-product hydrogen chloride of generation absorbs to obtain hydrochloric acid because influencing its further benefit containing organic impurity treatment difficulty by water
With.
The chlorination in situ that can be used for aromatic hydrocarbons using hydrogen chloride or hydrogen bromide and hydrogen peroxide system, does not need not only to make
With toxic halogen simple substance, and strong acidic by-products are not generated, the Atom economy of halogen atom is improved significantly, therefore benefit
It is one with the oxygen chlorination of the system to have a high potential and environmental-friendly halogenated compound preparation route.
Document (Angew.Chem.Int.Ed.2009,48,8424-8450) is with hydrogen chloride and hydrogen peroxide system chlorination
Active aromatic ring, methyl phenyl ethers anisole prepare 2,4- Banair, and paranitroanilinum chlorination prepares 2,6- dichloro paranitroanilinum, naphthalene chlorine
Change one chloronaphthalene of preparation, all obtains preferable result.Relative to this kind of higher aromatic substrate of activity, the not high alkyl of activity
Aromatic hydrocarbons needs excessive hydrogen chloride just to improve conversion ratio (Tetrahedron, the 1999,55,11127- of alkylaromatic hydrocarbon
11142;Tetrahedron Lett.2003,44, 4085-4088).These in the prior art, due to be not used catalyst,
It to reach preferable reaction effect, needs largely to use hydrogen peroxide, therefore the effect for being catalyzed reaction is limited still needs further
It improves;Or the homogeneous catalyst containing molybdenum, vanadium isoreactivity center is used, but bring the problem of the recycling difficulty of catalyst.
Document (J.Am.Chem.Soc.2003,125,12116-12117) report makees solvent catalysis mistake using more fluorinated alcohols
Hydrogen oxide simultaneously promotes ring chlorination reaction, is remarkably improved the rate of reaction, such as uses trifluoroethanol as solvent catalysis chlorination toluene
When, monochlorotoluene yield reaches 99%.But it is expensive to make solvent using more fluorinated alcohols etc., is unsuitable for heavy industrialization
Production.
Document (J.Am.Chem.Soc.1997,119,6921-6922) by by titanium grafting in mesoporous MCM-48 or
After on MCM-41 molecular sieve, bromo is carried out to reactant with hydrogen peroxide and bromide ion in neutral conditions, is achieved preferably
Effect, solve the problems, such as catalyst separation, but this material is not suitable for being used for a long time under strongly acidic conditions.
Summary of the invention
Purpose of this disclosure is to provide a kind of methods for preparing halogenated aromatic compound, and this method operating process is simple, instead
Mild condition is answered, feed stock conversion is high.
To achieve the goals above, the disclosure provides a kind of method for preparing halogenated aromatic compound, this method comprises:
It contacts the liquid material containing aromatic compound, oxidant and halogen acids with catalyst to be reacted, wherein the catalysis
Agent is titanium-silicon molecular sieve catalyst and/or zirconium-silicon molecular sieve catalyst.
Optionally, the Titanium Sieve Molecular Sieve is selected from MFI type Titanium Sieve Molecular Sieve, MEL type Titanium Sieve Molecular Sieve, BEA type titanium silicon
At least one of molecular sieve and MWW type Titanium Sieve Molecular Sieve;
The zirconium-silicon molecular sieve is selected from MFI type zirconium-silicon molecular sieve, MEL type zirconium-silicon molecular sieve, BEA type zirconium-silicon molecular sieve
At least one of with MWW type zirconium-silicon molecular sieve.
Optionally, the aromatic compound is selected from substituted or unsubstituted mononuclear aromatics, substituted or unsubstituted condensed ring
At least one of aromatic hydrocarbons and substituted or unsubstituted heterocyclic compound, the substituted mononuclear aromatics, substituted condensed-nuclei aromatics
In substituted heterocyclic compound, substituent group be selected from alkyl, hydroxyl, ketone group, carboxyl, ether, ester group, phenyl, sulfonic group,
At least one of nitro, amido and halogen.
Optionally, the aromatic compound is selected from benzene, toluene, ethylbenzene, isopropylbenzene, dimethylbenzene, trimethylbenzene, phenol, chlorine
Benzene, bromobenzene, iodobenzene, nitrobenzene, benzoic acid, benzene sulfonic acid, methyl phenyl ethers anisole, benzyl chloride, acetophenone, biphenyl, naphthalene, anthracene, furans, pyrroles,
Thiophene, pyridine, 2- picoline, 3- pyridine-sulfonic acid, 1,3,5- trimethylpyridine, 2 hydroxy pyrimidine, N- pyridine oxide, indoles,
At least one of quinoline, isoquinolin and imidazoles.
Optionally, the oxidant be selected from least one of inorganic peroxide, organic peroxide and ozone,
The inorganic peroxide is selected from hydrogen peroxide, potassium hydrogen peroxymonosulfate, potassium peroxydisulfate, SODIUM PERCARBONATE, percarbamide and to cross boron
At least one of sour sodium, the organic peroxide are selected from tert-butyl hydroperoxide, cyclohexyl hydroperoxide, peroxidating
Isopropylbenzene, hydrogen peroxide ethylbenzene, perbenzoic acid, methyl ethyl ketone peroxide, tert-Butyl peroxypivalate, hydrogen peroxide are different
At least one of propyl, tert-pentyl hydroperoxide and di-t-butyl peroxide.
Optionally, the halogen acids is selected from least one of hydrochloric acid, hydrobromic acid and hydroiodic acid.
Optionally, relative to the aromatic compound of 1 parts by weight, the dosage of the catalyst is 0.01-1.5 weight
Part;
With H+The halogen acids of meter and the molar ratio of the aromatic compound are (0.2-8): 1;
The oxidant with H+The molar ratio of the halogen acids of meter is (0.1-3): 1.
Optionally, relative to the aromatic compound of 1 parts by weight, the dosage of the catalyst is 0.2-1.2 weight
Part;
With H+The halogen acids of meter and the molar ratio of the aromatic compound are (1-5): 1;
The oxidant with H+The molar ratio of the halogen acids of meter is (1-2.5): 1.
Optionally, the liquid material also contains the compound that can ionize out acid ion, the acid ion be selected from
At least one in sulfate ion, hydrogen sulfate ion, phosphate anion, one hydrogen radical ion of phosphoric acid and dihydrogen phosphate ions
Kind, with the molar ratio of the acid ion of the ionometer of complete ionized state and aromatic compound for (0.01-0.2): 1.
Optionally, this method further include: described to react in the presence of a solvent, the solvent and the aromatization
The molar ratio for closing object is (5-100): 1.
Optionally, the solvent be water and/or organic solvent, the organic solvent be selected from ether, C1-C6 alcohol,
The ketone of C3-C8, the nitrile of C2-C6, tetrahydrofuran, methylene chloride, chloroform, tetrachloromethane, dichloroethanes, acetic anhydride and 1,
At least one of 4- dioxane.
Optionally, the condition of the reaction are as follows: the temperature of reaction is 0-80 DEG C, and the time of reaction is 0.1-48h.
Through the above technical solutions, the disclosure is using titanium-silicon molecular sieve catalyst and/or zirconium-silicon molecular sieve catalyst in acid
Property under the conditions of be catalyzed halide ion and oxidant reaction and generate reactive halogen, and halogenating reaction preparation is carried out to aromatic compound
Halogenated aromatic compound.Compared with prior art, the method reaction process that the disclosure provides does not need toxic using chlorine etc.
Halogen simple substance, operating process is simple, and reaction condition is mild, and feed stock conversion is high, catalyst performance stabilised and easily separated, product
Later separation energy consumption is lower, and technique is safer efficiently, is suitble to large-scale industrial production application.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Specific embodiment
The specific embodiment of the disclosure is described in detail below.It should be understood that described herein specific
Embodiment is only used for describing and explaining the disclosure, is not limited to the disclosure.
The disclosure provides a kind of method for preparing halogenated aromatic compound, this method comprises: make containing aromatic compound,
The liquid material of oxidant and halogen acids is contacted with catalyst to be reacted, wherein the catalyst is titanium molecular sieve catalysis
Agent and/or zirconium-silicon molecular sieve catalyst.
The method that the disclosure provides can make halide ion and oxidant anti-under the effect of catalyst and acid condition
Reactive halogen should be generated, and halogenating reaction is carried out to aromatic compound and prepares halogenated aromatic compound.Have compared with prior art
Have without using toxic halogen simple substance, operating process is simple, and reaction condition is mild, and feed stock conversion is high, catalyst stability it is good and
It is easily separated, the features such as reaction process is safe and efficient.
According to the disclosure, the Titanium Sieve Molecular Sieve and/or zirconium-silicon molecular sieve are the Titanium Sieve Molecular Sieve of common various structures
And/or zirconium-silicon molecular sieve.Particularly, the stable in catalytic performance in order to ensure molecular sieve in strong acidic environment, the disclosure use
Molecular sieve in hetero atom (i.e. titanium or zirconium) need it is at least a part of exist in the form of cage heteroatom, molecular sieve is female
The crystal structure that body needs to have stable.Support type hetero-atom molecular-sieve, as the silica zeolite or parent of supported titanium are
Unbodied mesoporous hetero-atom molecular-sieve, such as Ti-MCM-22, Ti-SBA-15, Ti-MCM-41, because activated centre is former
The bonding of son and molecular sieve parent is stablized not as good as hetero-atom molecular-sieve bonding of the activated centre on skeleton, it is difficult to bear harsh
Under the conditions of use.
Therefore, the Titanium Sieve Molecular Sieve is preferably selected from MFI type Titanium Sieve Molecular Sieve (such as TS-1 molecular sieve), MEL type titanium silicon
Molecular sieve (such as TS-2 molecular sieve), BEA type Titanium Sieve Molecular Sieve (such as Ti-beta molecular sieve) and MWW type Titanium Sieve Molecular Sieve (such as Ti-
At least one of MCM-22 molecular sieve);Further preferably MFI type Titanium Sieve Molecular Sieve;Still more preferably for hollow
The MFI type Titanium Sieve Molecular Sieve of structure, the radical length of the chamber portion of hollow structure are 5-300 nanometers, the titanium silicon point
Son sieve is in 25 DEG C, P/P0=0.10, the benzene adsorbance that adsorption time measures under conditions of 1 hour is at least 70 milligrams per grams molecules
Sieve, there are hysteresis loops between the adsorption isotherm and desorption isotherm of low temperature nitrogen absorption.
According to the disclosure, the catalyst is preferably zirconium-silicon molecular sieve catalyst.The zirconium-silicon molecular sieve can for selected from
MFI type zirconium-silicon molecular sieve (such as Zr-MFI molecular sieve), MEL type zirconium-silicon molecular sieve (such as Zr-MEL molecular sieve), BEA type zirconium silicon point
Son sieve at least one of (such as Zr-beta molecular sieve) and MWW type zirconium-silicon molecular sieve (such as Zr-MCM-22 molecular sieve), further
Preferably MFI type zirconium-silicon molecular sieve.
Disclosed method is suitable for arbitrarily meeting the aromatic compound of your 4n+2 rule of shock, for example, the aromatization
Closing object can be for selected from substituted or unsubstituted mononuclear aromatics, substituted or unsubstituted condensed-nuclei aromatics and substituted or unsubstituted
At least one of heterocyclic compound, the substituted mononuclear aromatics, substituted condensed-nuclei aromatics and substituted heterocyclic compound
In, substituent group can be for selected from alkyl, hydroxyl, ketone group, carboxyl, ether, ester group, phenyl, sulfonic group, nitro, amido and halogen
At least one of.Specifically, the aromatic compound can include but is not limited to benzene, toluene, ethylbenzene, isopropylbenzene, diformazan
Benzene, trimethylbenzene, phenol, chlorobenzene, bromobenzene, iodobenzene, nitrobenzene, benzoic acid, benzene sulfonic acid, methyl phenyl ethers anisole, benzyl chloride, acetophenone, connection
Benzene, naphthalene, anthracene, furans, pyrroles, thiophene, pyridine, 2- picoline, 3- pyridine-sulfonic acid, 1,3,5- trimethylpyridine, 2- hydroxyl pyrrole
Pyridine, N- pyridine oxide, indoles, quinoline, isoquinolin and imidazoles etc..
According to the disclosure, the oxidant can in inorganic peroxide, organic peroxide and ozone extremely
Few one kind.The inorganic peroxide can be for selected from hydrogen peroxide, potassium hydrogen peroxymonosulfate, potassium peroxydisulfate, SODIUM PERCARBONATE, mistake
At least one of carbamide and sodium perborate;The organic peroxide can be for selected from tert-butyl hydroperoxide, cyclohexyl
Hydrogen peroxide, dicumyl peroxide, hydrogen peroxide ethylbenzene, perbenzoic acid, methyl ethyl ketone peroxide, peroxidating neopentanoic acid uncle
At least one of butyl ester, hydrogen peroxide isopropyl, tert-pentyl hydroperoxide and di-t-butyl peroxide.The oxidant is most
Preferably hydrogen peroxide.
According to the disclosure, the halogen acids can be for selected from least one of hydrochloric acid, hydrobromic acid and hydroiodic acid.It is described
Halogen acids can be the aqueous solution of hydrogeneous hydracid, and when the halogen acids is when containing aqueous acid, the disclosure is to water in reaction system
Dosage be not particularly limited.
It is described relative to the aromatic compound of 1 parts by weight in order to reach ideal reaction effect according to the disclosure
The dosage of catalyst can be 0.01-1.5 parts by weight, preferably 0.2-1.2 parts by weight.With H+The halogen acids of meter and institute
The molar ratio for stating aromatic compound can be (0.2-8): 1, preferably (1-5): 1.The oxidant with H+The hydrogen of meter
The molar ratio of hydracid can be (0.1-3): 1, preferably (1-2.5): 1.
According to the disclosure, in order to further increase the conversion ratio of raw material, can also contain in the liquid material can be ionized
The compound of acid ion out, the acid ion can be for selected from sulfate ion (SO4 2-), hydrogen sulfate ion
(HSO4 -), phosphate anion (PO4 3-), one hydrogen radical ion (HPO of phosphoric acid4 2-) and dihydrogen phosphate ions (H2PO4 -) at least
It is a kind of.With the ionometer of complete ionized state, the molar ratio of the acid ion and aromatic compound can be (0.01-
0.2): 1, preferably (0.05-0.15): 1.
It may include salt or acid containing above-mentioned ion according to the disclosure, in the liquid material.Also, the liquid
The metal cation or ammonium ion that appropriate first main group and/or the second main group are introduced in body material will not cause reaction
Apparent side effect, therefore, can ionize out the cation in the salt of above-mentioned acid ion is preferably cation for selected from the first main group
At least one of cation, the second main group metal cation and ammonium ion.
According to the disclosure, in order to keep each reaction raw materials mass transfer in the reactant containing catalyst good, the reaction can
With in the presence of a solvent, the molar ratio of the solvent and the aromatic compound can be (5-100): 1, preferably
(15-70): 1.The solvent can be water and/or organic solvent, and the organic solvent can be selected from ether, C1-C10
Alcohol, the ketone of C3-C8, the nitrile of C2-C6, tetrahydrofuran, methylene chloride, chloroform, tetrachloromethane, dichloroethanes, acetic anhydride and
At least one of 1,4- dioxane.
According to the disclosure, the condition of the reaction can be with are as follows: and the temperature of reaction is 0-80 DEG C, preferably 20-50 DEG C, instead
The time answered is 0.1-48h.
Reaction described in the disclosure can carry out in Conventional catalytic reactor, and the disclosure does not do special limitation, example
Such as, the reaction of the disclosure can carry out in batch tank reactor or three-necked flask, or in suitable other reactor examples
Such as fixed bed, moving bed carry out in suspension bed.
It will be appreciated by persons skilled in the art that according to the difference of used reactor, titanium silicon described in the disclosure
Molecular sieve and/or zirconium-silicon molecular sieve catalyst can be molecular screen primary powder, after being also possible to molecular sieve and carrier mixed-forming
Preformed catalyst.The separation of product and catalyst can be accomplished in several ways, for example, being catalysis with former mealy molecular sieve
When agent, the separation of product and the recycling of catalyst can be realized by modes such as sedimentation, filtering, centrifugation, evaporation, UF membranes
It recycles, alternatively, fixed bed reactors can also will be loaded on after shaping of catalyst, to recycle catalyst after reaction, respectively
It is in the separation and recovery method existing literature of kind catalyst to relate to more, it is no longer numerous herein to state.
The disclosure is described further below by embodiment, but does not therefore limit content of this disclosure.
TS-1 molecular sieve employed in embodiment the preparation method comprises the following steps: by the tetrapropylammonium hydroxide of about 3/4 amount
(TPAOH, 20%, be purchased from U.S.'s aldrich company) solution is added into ethyl orthosilicate (TEOS) solution, and obtaining pH is about
Then the desired amount of metatitanic acid is being added dropwise just into obtained liquid mixture under conditions of being vigorously stirred in 13 liquid mixture
Butyl ester [Ti (OBu)4] anhydrous isopropanol solution, stirring 15 minutes after obtain clear liquid, finally, by remaining TPAOH
It is slowly added in supernatant liquid, stir about 3 hours at 348-353K, obtaining chemical composition is 0.03TiO2: SiO2:
0.36TPA:35H2Then the colloidal sol of O is carried out crystallization 3 days at a temperature of 443K, is later filtered obtained solid, with distillation
After water washing, is dried at a temperature of 373K 5 hours, then roast 10h under the conditions of 823K and obtain sieve sample.Wherein,
The dosage of TEOS is 42g, and the dosage of TPAOH is 73g, Ti (OBu)4Dosage be 2g, the dosage of anhydrous isopropyl alcohol is 10g, water
Dosage be 68g.
Hollow Titanium Sieve Molecular Sieve HTS is to be prepared by Chinese patent CN1301599A specification method described in embodiment 1
It arrives, it is 5-100 nanometers of hollow structure which, which has radical length, using static adsorptive method in 25 DEG C, P/P0=
0.10, the benzene adsorbance that adsorption time measures under conditions of 1 hour is 85 milligrams per grams molecular sieves;According to ASTM D4222-98
There are hysteresis loops between the adsorption isotherm and desorption isotherm of the low temperature nitrogen absorption of standard method measurement.
TS-2 molecular sieve used in embodiment the preparation method comprises the following steps: a certain amount of tetrabutylammonium hydroxide solution
(TBAOH, 20%) is mixed with ethyl orthosilicate (TEOS), then mixed to obtained transparency liquid under conditions of being vigorously stirred
It closes in object and the desired amount of tetrabutyl titanate [Ti (OBu) is added dropwise4] anhydrous isopropanol solution, stir 30 minutes hydrolysis after the completion of
Obtain clear liquid.Finally, 2 times of the desired amount of distilled water are added, gained colloidal sol stirs 2h at 348-353K and removes alcohol.
Resulting colloidal sol chemical composition is 0.20TBAOH:SiO2:0.03TiO2:20H2O.Colloidal sol is placed in 443K crystallization 3 days,
Resulting crystallization product is by filtering, washing, and dry 6h under the conditions of 373K, then roasts 16h under the conditions of 823K and obtains
Sieve sample.Wherein, the dosage of TEOS is 42g, and the dosage of TBAOH is 52g, Ti (OBu)4Dosage be 2g, anhydrous isopropyl
The dosage of alcohol is 10g, and the dosage of water is 30g.
Ti-beta molecular sieve used in embodiment the preparation method comprises the following steps: a certain amount of ethyl orthosilicate (TEOS) is added
To in the tetraethyl ammonium hydroxide solution of metering (TEAOH, 20%) and the solution of hydrogen peroxide, hydrolyze while stirring
2h.Then by the tetrabutyl titanate of weighing [Ti (OBu)4] anhydrous isopropanol solution be added to the hydrolyzate of ethyl orthosilicate
In, continue to stir 3h so that except alcohol, last available chemical composition is TiO2:60SiO2:33TEAOH:400H2O:20H2O2's
Colloidal sol.P-zeolite crystal seed after being eventually adding dealuminzation and be vigorously stirred (Seed charge is colloidal sol in terms of silica,
4g crystal seed is added in 100g silica).Gained mixture under the conditions of 413K after crystallization 14 days, resulting slurries by filtering,
Washing, and dry 6h under the conditions of 373K, then roast 12h under the conditions of 823K and obtain sieve sample.Wherein, TEOS
Dosage is 42g, and the dosage of TEAOH is 81g, Ti (OBu)4Dosage be 1.16g, the dosage of anhydrous isopropyl alcohol is 10g, dioxygen
The dosage of water is 7.5g.
Zr-MFI molecular sieve employed in embodiment the preparation method comprises the following steps: by the tetrapropylammonium hydroxide of about 3/4 amount
(TPAOH, 20%, be purchased from U.S.'s aldrich company) solution is added into ethyl orthosilicate (TEOS) solution, and obtaining pH is about
Then the desired amount of normal propyl alcohol is added dropwise in 13 liquid mixture under conditions of being vigorously stirred into obtained liquid mixture
The normal propyl alcohol solution (70%) of zirconium, stirring obtained clear liquid after 30 minutes, finally, remaining TPAOH is slowly added to
In supernatant liquid, stir about 3 hours at 348-353K, obtaining chemical composition is 0.01ZrO2: SiO2: 0.3TPA:30H2O
Colloidal sol, then carry out crystallization 3 days at a temperature of 443K, later filter obtained solid, after being washed with distilled water,
It is dried at a temperature of 373K 5 hours, then roasts 10h under the conditions of 823K and obtain sieve sample.Wherein, the dosage of TEOS is
The dosage of 42g, TPAOH are 61g, and the dosage of zirconium-n-propylate solution is 1g, and the dosage of water is 60g.
Ti-SBA-15 molecular sieve employed in embodiment the preparation method comprises the following steps: with tetraethyl orthosilicate (TEOS) be silicon
Source, tetra-n-butyl titanate (TBOT) are titanium source, and P123 is surfactant, and under 40 DEG C of constant temperatures, 2g P123 is dissolved in
In the solution of HCl (60g, 2mol/L) and 15g water, tetraethyl orthosilicate 2.08g is then added, while being added by a certain percentage
The reaction solution (tetra-n-butyl titanate: acetylacetone,2,4-pentanedione (mol)=1: 0.6) of tetra-n-butyl titanate and acetylacetone,2,4-pentanedione.React 30min
After precipitate, continue stirring for 24 hours, then mixed liquor be transferred in polytetrafluoroethylene (PTFE) bottle, aging is for 24 hours at 100 DEG C.Always
Product is taken out and filtered after the completion of change, then dry 6h under the conditions of 120 DEG C, finally by dry products therefrom at 550 DEG C
6h is roasted to get Ti-SBA-15 is arrived.
It is raw materials used in addition to special instruction in embodiment, it is analytical reagents.
Reaction product is quantified using its composition of gas chromatographic analysis, analysis result using external standard method.Wherein, chromatography
Analysis condition are as follows: Agilent-6890 type chromatograph, HP-5 capillary chromatographic column, 0.5 μ L of sample volume, injector temperature 280
℃.Column temperature then rises to 260 DEG C in 100 DEG C of holding 3min with the rate of 10 DEG C/min, and keep 20min.Fid detector,
300 DEG C of detector temperature.
Using the content of activated centre titanium in XRF measurement molecular sieve, instrument is the production of Rigaku Electric Co., Ltd
3013 type Xray fluorescence spectrometers.
In each embodiment and comparative example:
Aromatic compound conversion ratio (%)=(aromatic compound rubs in molal quantity-product of aromatic compound in raw material
Your number) molal quantity × 100% of aromatic compound in/raw material
Embodiment 1
The water of toluene, the aqueous hydrogen peroxide solution of 30 weight %, the aqueous hydrochloric acid solution of 37 weight % and requirement is thrown
Enter into reaction kettle, obtains containing toluene, H2O2, HCl and water liquid material, wherein H2O2, HCl, water and toluene molar ratio
For 3:6:10:1.Using TS-1 molecular sieve as in catalyst investment reaction kettle, the weight ratio of TS-1 molecular sieve and toluene is 0.1:
1.Then make reaction mixture in reaction kettle 20 DEG C at a temperature of react 6h, sampling analysis, analyzes result after the reaction was completed
It is shown in Table 1.
Embodiment 2
It is reacted according to the method for embodiment 1, difference is, will repeat 3 after TS-1 molecule sieve separation after reaction
The secondary reaction under the same terms.After sampling analysis, and take its Ti content of TS-1 molecule mesh analysis, analysis result is shown in
Tables 1 and 2.
Embodiment 3
It is reacted according to the method for embodiment 1, difference is, using Ti-SBA-15 molecular sieve as catalyst, Ti-SBA-
The weight ratio of 15 molecular sieves and toluene is 0.1: 1.Sampling analysis after the reaction was completed, analysis the results are shown in Table 1.
Embodiment 4
It is reacted according to the method for embodiment 3, difference is, after reaction will be after Ti-SBA-15 molecule sieve separation
It is repeated 3 times for the reaction under the same terms.After sampling analysis, and take its Ti content of Ti-SBA-15 molecule mesh analysis,
Analysis the results are shown in Table 1 and table 2.
Embodiment 5
Benzene, the aqueous hydrogen peroxide solution of 30 weight %, the aqueous hydrochloric acid solution of 37 weight % and acetone are put into reaction
In kettle, obtain containing benzene, H2O2, HCl and acetone liquid material, wherein H2O2, HCl, acetone and benzene molar ratio be 2.4:
0.8:80:1.Using TS-1 molecular sieve as in catalyst investment reaction kettle, the weight ratio of TS-1 molecular sieve and benzene is 1.5:1.So
Make afterwards reaction mixture in reaction kettle 50 DEG C at a temperature of react 12h, sampling analysis, analysis result are shown in after the reaction was completed
Table 1.
Embodiment 6
The water of toluene, the aqueous hydrogen peroxide solution of 30 weight %, the aqueous hydrochloric acid solution of 37 weight % and requirement is thrown
Enter into reaction kettle, obtains containing toluene, H2O2, HCl and water liquid material, wherein H2O2, HCl, water and toluene molar ratio
For 1.6:1:50:1.Using TS-1 molecular sieve as in catalyst investment reaction kettle, the weight ratio of TS-1 molecular sieve and toluene is
0.8:1.Then make reaction mixture in reaction kettle 30 DEG C at a temperature of react 6h, sampling analysis after the reaction was completed, analysis
It the results are shown in Table 1.
Embodiment 7
By aqueous hydrochloric acid solution, phosphoric acid and the requirement of toluene, the aqueous hydrogen peroxide solution of 30 weight %, 37 weight %
Water put into reaction kettle, obtain containing toluene, H2O2、HCl、PO4 3-With the liquid material of water, wherein H2O2、HCl、PO4 3-、
The molar ratio of water and toluene is 1.6:1:0.05: 50:1.Using TS-1 molecular sieve as in catalyst investment reaction kettle, TS-1 divides
The weight ratio of son sieve and toluene is 0.8:1.Then make reaction mixture in reaction kettle 30 DEG C at a temperature of react 6h, instead
Sampling analysis after the completion of answering, analysis the results are shown in Table 1.
Embodiment 8
It is reacted according to the method for embodiment 7, difference is, using hollow Titanium Sieve Molecular Sieve HTS as catalyst.Reaction
Sampling analysis after the completion, analysis the results are shown in Table 1.
Embodiment 9
By ethylbenzene, the aqueous hydrogen peroxide solution of 30 weight %, the aqueous hydrochloric acid solution of 37 weight %, sodium dihydrogen phosphate and
The water of requirement is put into reaction kettle, is obtained containing ethylbenzene, H2O2、HCl、H2PO4 -With the liquid material of water, wherein H2O2、
HCl、H2PO4 -, water and ethylbenzene molar ratio be 11:5:0.18: 20:1.It is put into hollow Titanium Sieve Molecular Sieve HTS as catalyst
In reaction kettle, the weight ratio of HTS and ethylbenzene is 0.3:1.Then make reaction mixture in reaction kettle 30 DEG C at a temperature of
12h is reacted, after the reaction was completed sampling analysis, analysis the results are shown in Table 1.
Embodiment 10
By nitrobenzene, the aqueous hydrogen peroxide solution of 30 weight %, 48 weight % hydrobromic acid aqueous solution, sodium dihydrogen phosphate
And the water of requirement is put into reaction kettle, and nitrobenzene-containing, H are obtained2O2、HCl、 H2PO4 -With the liquid material of water, wherein
H2O2、HCl、H2PO4 -, water and nitrobenzene molar ratio be 3.6:3:0.05: 60:1.Using hollow Titanium Sieve Molecular Sieve HTS as urging
Agent is put into reaction kettle, and the weight ratio of HTS and nitrobenzene is 0.6:1.Then make the reaction mixture in reaction kettle 50
It is reacted at a temperature of DEG C for 24 hours, after the reaction was completed sampling analysis, analysis the results are shown in Table 1.
Embodiment 11
By anthracene, the aqueous hydrogen peroxide solution of 30 weight %, the aqueous hydrochloric acid solution of 37 weight %, sodium phosphate and three chloromethanes
Alkane is put into reaction kettle, is obtained containing anthracene, H2O2、HCl、PO4 3-, water and chloroform liquid material, wherein H2O2、HCl、
PO4 3-, water, chloroform and anthracene molar ratio be 2.25:1.5:0.1:16:50:1.Using hollow Titanium Sieve Molecular Sieve HTS as urging
Agent is put into reaction kettle, and the weight ratio of HTS and anthracene is 1:1.Then make temperature of the reaction mixture at 20 DEG C in reaction kettle
Degree is lower to react 36h, and sampling analysis, analysis the results are shown in Table 1 after the reaction was completed.
Embodiment 12
It is reacted according to the method for embodiment 7, difference is, using Zr-MFI molecular sieve as catalyst.After the reaction was completed
Sampling analysis, analysis the results are shown in Table 1.
Embodiment 13
By naphthalene, the aqueous hydrogen peroxide solution of 30 weight %, the hydrobromic acid aqueous solution of 48 weight %, disodium hydrogen phosphate and
The water of requirement is put into reaction kettle, is obtained containing naphthalene, H2O2、HBr、HPO4 2-With the liquid material of water, wherein H2O2、HBr、
HPO4 2-, water and naphthalene molar ratio be 5.4:3:0.09: 50:1.It is put into Zr-MFI molecular sieve as catalyst in reaction kettle,
The weight ratio of Zr-MFI molecular sieve and naphthalene is 0.8:1.Then make reaction mixture in reaction kettle 25 DEG C at a temperature of react
8h, sampling analysis, analysis the results are shown in Table 1 after the reaction was completed.
Embodiment 14
Anthracene, the aqueous hydrogen peroxide solution of 30 weight %, the aqueous hydrochloric acid solution of 37 weight %, sulfuric acid and acetonitrile are put into
Into reaction kettle, obtain containing anthracene, H2O2、HCl、SO4 2-With the liquid material of acetonitrile, wherein H2O2、HCl、SO4 2-, acetonitrile and anthracene
Molar ratio be 3.25:1.3:0.15:15:1.It is put into Zr-MFI molecular sieve as catalyst in reaction kettle, Zr-MFI molecule
The weight ratio of sieve and anthracene is 1:1.Then make reaction mixture in reaction kettle 30 DEG C at a temperature of react for 24 hours, reacted
At rear sampling analysis, analysis the results are shown in Table 1.
Embodiment 15
By methyl phenyl ethers anisole, the aqueous hydrogen peroxide solution of 30 weight %, the aqueous hydrochloric acid solution of 37 weight %, disodium hydrogen phosphate with
And the water of requirement is put into reaction kettle, is obtained containing methyl phenyl ethers anisole, H2O2、HCl、HPO4 2-And the liquid material of water, wherein
H2O2、HCl、HPO4 2-, water and methyl phenyl ethers anisole molar ratio be 5.6:4:0.08:40:1.It is thrown Zr-MFI molecular sieve as catalyst
Enter in reaction kettle, the weight ratio of Zr-MFI molecular sieve and methyl phenyl ethers anisole is 1.2:1.Then the reaction mixture in reaction kettle is made to exist
18h is reacted at a temperature of 45 DEG C, after the reaction was completed sampling analysis, analysis the results are shown in Table 1.
Embodiment 16
By pyridine, the cumene solution of the cumyl hydroperoxide of 80 weight %, 37 weight % aqueous hydrochloric acid solution and
Acetone is put into reaction kettle, obtains the liquid material containing pyridine, cumyl hydroperoxide, HCl and acetone, wherein peroxidating
Hydrogen isopropylbenzene, HCl, acetone and pyridine molar ratio be 1.2:8:5:1.Reaction kettle is put into using TS-2 molecular sieve as catalyst
In, the weight ratio of TS-2 molecular sieve and pyridine is 0.05:1.Then make reaction mixture in reaction kettle 5 DEG C at a temperature of
36h is reacted, after the reaction was completed sampling analysis, analysis the results are shown in Table 1.
Embodiment 17
By the aqueous solution of the tert-butyl hydroperoxide of naphthalene, 70 weight %, the aqueous hydrochloric acid solution and the tert-butyl alcohol of 37 weight %
It puts into reaction kettle, obtains the liquid material containing naphthalene, tert-butyl hydroperoxide, HCl and the tert-butyl alcohol, wherein t-butyl peroxy
The molar ratio for changing hydrogen, HCl, the tert-butyl alcohol and naphthalene is 2.4:0.8:90:1.Ti-beta molecular sieve is put into as catalyst and is reacted
In kettle, the weight ratio of Ti-beta molecular sieve and naphthalene is 1.3:1.Then make temperature of the reaction mixture at 70 DEG C in reaction kettle
Lower reaction 48h, sampling analysis, analysis the results are shown in Table 1 after the reaction was completed.
Comparative example 1
It is reacted according to the method for embodiment 1, difference is, this comparative example is without using TS-1 molecular sieve as catalysis
Agent.Sampling analysis after the reaction was completed, analysis the results are shown in Table 1.
Comparative example 2
It is reacted according to the method for embodiment 1, difference is, this comparative example is with ferric chloride (FeCl36H2O) (FeCl3·6H2O)
For catalyst, the weight ratio of ferric chloride (FeCl36H2O) and toluene is 0.1:1.Sampling analysis after the reaction was completed, analysis the results are shown in Table 1.
Table 1
Table 2
Fresh dose of TiO2Content/% weight | TiO after reuse2Content/% weight | |
Embodiment 2 | 4.2 | 4.2 |
Embodiment 4 | 4.5 | 1.3 |
By the result of Tables 1 and 2 as it can be seen that the method operating process of disclosure offer is simple, reaction condition is mild, raw material
High conversion rate, catalyst performance stabilised.Specifically, by the comparison of embodiment 1-17 and comparative example 1-2 as it can be seen that using titanium silicon point
Son sieve and/or zirconium-silicon molecular sieve can increase substantially the conversion ratio of raw material as catalyst.By embodiment 1-2 and embodiment 3-4
Comparison as it can be seen that be unbodied mesoporous hetero-atom molecular-sieve compared to support type hetero-atom molecular-sieve or parent, use
Hetero atom it is at least a part of in the form of cage heteroatom existing for molecular sieve catalytic performance it is more stable, reuse
Shi Yiran can keep higher activated centre Ti content, and can further increase the conversion ratio of raw material.By embodiment
1,5 and embodiment 6 comparison as it can be seen that the aromatic compound relative to 1 parts by weight, the dosage of the catalyst are 0.2-
The molar ratio of 1.2 parts by weight, the halogen acids and the aromatic compound is (1-5): 1, the molar ratio of oxidant and halogen acids
For (1-2.5): when 1, the conversion ratio of raw material can be further increased.By the comparison of embodiment 6 and embodiment 7 as it can be seen that when described
When containing acid ion in liquid material, the conversion ratio of raw material can be further increased.The comparison of embodiment 7 and embodiment 12
As it can be seen that the conversion ratio of raw material can be further increased when using zirconium-silicon molecular sieve as catalyst.
The preferred embodiment of the disclosure is described in detail above, still, during the disclosure is not limited to the above embodiment
Detail a variety of simple variants can be carried out to the technical solution of the disclosure in the range of the technology design of the disclosure,
These simple variants belong to the protection scope of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance
It in the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the disclosure is to various
No further explanation will be given for possible combination.
In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought equally should be considered as disclosure disclosure of that.
Claims (12)
1. a kind of method for preparing halogenated aromatic compound, which is characterized in that this method comprises: making containing aromatic compound, oxygen
The liquid material of agent and halogen acids is contacted with catalyst to be reacted, wherein the catalyst is titanium-silicon molecular sieve catalyst
And/or zirconium-silicon molecular sieve catalyst.
2. according to the method described in claim 1, wherein, the Titanium Sieve Molecular Sieve is selected from MFI type Titanium Sieve Molecular Sieve, MEL type
At least one of Titanium Sieve Molecular Sieve, BEA type Titanium Sieve Molecular Sieve and MWW type Titanium Sieve Molecular Sieve;
The zirconium-silicon molecular sieve is selected from MFI type zirconium-silicon molecular sieve, MEL type zirconium-silicon molecular sieve, BEA type zirconium-silicon molecular sieve and MWW
At least one of type zirconium-silicon molecular sieve.
3. the method according to claim 1, wherein the aromatic compound is selected from substituted or unsubstituted mononuclear aromatics, takes
Generation or at least one of unsubstituted condensed-nuclei aromatics and substituted or unsubstituted heterocyclic compound, the substituted monocycle virtue
In hydrocarbon, substituted condensed-nuclei aromatics and substituted heterocyclic compound, substituent group is selected from alkyl, hydroxyl, ketone group, carboxyl, ether, ester
At least one of base, phenyl, sulfonic group, nitro, amido and halogen.
4. according to the method in claim 3, wherein the aromatic compound is selected from benzene, toluene, ethylbenzene, isopropylbenzene, diformazan
Benzene, trimethylbenzene, phenol, chlorobenzene, bromobenzene, iodobenzene, nitrobenzene, benzoic acid, benzene sulfonic acid, methyl phenyl ethers anisole, benzyl chloride, acetophenone, biphenyl,
Naphthalene, anthracene, furans, pyrroles, thiophene, pyridine, 2- picoline, 3- pyridine-sulfonic acid, 1,3,5- trimethylpyridine, 2 hydroxy pyrimidine,
At least one of N- pyridine oxide, indoles, quinoline, isoquinolin and imidazoles.
5. the method according to claim 1, wherein the oxidant is selected from inorganic peroxide, organic peroxide and smelly
At least one of oxygen, the inorganic peroxide be selected from hydrogen peroxide, potassium hydrogen peroxymonosulfate, potassium peroxydisulfate, SODIUM PERCARBONATE,
At least one of percarbamide and sodium perborate, the organic peroxide are selected from tert-butyl hydroperoxide, cyclohexyl mistake
Hydrogen oxide, dicumyl peroxide, hydrogen peroxide ethylbenzene, perbenzoic acid, methyl ethyl ketone peroxide, the tertiary fourth of peroxidating neopentanoic acid
At least one of ester, hydrogen peroxide isopropyl, tert-pentyl hydroperoxide and di-t-butyl peroxide.
6. the method according to claim 1, wherein the halogen acids is at least one in hydrochloric acid, hydrobromic acid and hydroiodic acid
Kind.
7. the method according to claim 1, wherein relative to the aromatic compound of 1 parts by weight, the dosage of the catalyst
For 0.01-1.5 parts by weight;
With H+The halogen acids of meter and the molar ratio of the aromatic compound are (0.2-8): 1;
The oxidant with H+The molar ratio of the halogen acids of meter is (0.1-3): 1.
8. method according to claim 7, wherein relative to the aromatic compound of 1 parts by weight, the dosage of the catalyst
For 0.2-1.2 parts by weight;
With H+The halogen acids of meter and the molar ratio of the aromatic compound are (1-5): 1;
The oxidant with H+The molar ratio of the halogen acids of meter is (1-2.5): 1.
9. the method according to claim 1, wherein the liquid material also contains the compound that can ionize out acid ion, institute
Stating acid ion is selected from sulfate ion, hydrogen sulfate ion, phosphate anion, one hydrogen radical ion of phosphoric acid and dihydrogen phosphate
At least one of ion, the molar ratio with the acid ion of the ionometer of complete ionized state and aromatic compound are
(0.01-0.2): 1.
10. the method according to claim 1, wherein this method further include: the reaction is in the presence of a solvent, described
The molar ratio of solvent and the aromatic compound is (5-100): 1.
11. method according to claim 10, wherein the solvent be water and/or organic solvent, the organic solvent be selected from
Ether, the alcohol of C1-C6, the ketone of C3-C8, the nitrile of C2-C6, tetrahydrofuran, methylene chloride, chloroform, tetrachloromethane, two chloroethenes
At least one of alkane, acetic anhydride and 1,4- dioxane.
12. the method according to claim 1, wherein the condition of the reaction are as follows: the temperature of reaction be 0-80 DEG C, reaction when
Between be 0.1-48h.
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CN113264880A (en) * | 2021-05-25 | 2021-08-17 | 湖北工业大学 | Preparation method of 4-halogenated isoquinoline compound |
CN115403461A (en) * | 2022-09-16 | 2022-11-29 | 吕梁学院 | Method for synthesizing benzoic acid by oxidizing ethylbenzene |
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CN112409136A (en) * | 2020-12-12 | 2021-02-26 | 中唯炼焦技术国家工程研究中心有限责任公司 | Method for preparing 6,6 ' -dibromo-1, 1 ' -binaphthyl-2, 2 ' -diphenol by efficient clean bromination |
CN113264880A (en) * | 2021-05-25 | 2021-08-17 | 湖北工业大学 | Preparation method of 4-halogenated isoquinoline compound |
CN115403461A (en) * | 2022-09-16 | 2022-11-29 | 吕梁学院 | Method for synthesizing benzoic acid by oxidizing ethylbenzene |
CN115403461B (en) * | 2022-09-16 | 2023-09-22 | 吕梁学院 | Method for synthesizing benzoic acid by oxidizing ethylbenzene |
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