CN109569675B - Attapulgite-based supported catalyst and preparation method and application thereof - Google Patents

Attapulgite-based supported catalyst and preparation method and application thereof Download PDF

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CN109569675B
CN109569675B CN201811422327.2A CN201811422327A CN109569675B CN 109569675 B CN109569675 B CN 109569675B CN 201811422327 A CN201811422327 A CN 201811422327A CN 109569675 B CN109569675 B CN 109569675B
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attapulgite
catalyst
phthalic anhydride
preparation
anhydride
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CN109569675A (en
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杨勇
施晓琪
王绒
崔超
田韦琴
范超群
杜卫刚
钱运华
蒋金龙
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Huaiyin Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention discloses an attapulgite-based supported catalyst, a preparation method and application thereof, wherein the mass ratio of active components of the catalyst to attapulgite is 1: 5-1: 10. the preparation method comprises the steps of mixing the active components of the catalyst and the attapulgite according to the mass ratio, extruding, forming, drying, roasting at the temperature of 200-280 ℃, grinding and sieving. The application is that the attapulgite-based supported catalyst is put into molten phthalic anhydride, the mass of the attapulgite-based supported catalyst is 1.5-2.0% of the mass of the phthalic anhydride, chlorine with the flow rate of 15-20 mL/min is introduced at normal pressure, and direct chlorination catalytic reaction is carried out for 14-20 hours at the reaction temperature of 150-180 ℃. The invention has high conversion rate of raw materials and high selectivity of monochlorophthalic anhydride; the catalyst has stable performance, is easy to recover and can be repeatedly used; the catalyst preparation and reaction operation are simple, the reaction condition is mild, the energy consumption is saved, and the production cost is reduced.

Description

Attapulgite-based supported catalyst and preparation method and application thereof
Technical Field
The invention relates to a catalyst, a preparation method and application thereof, in particular to a concave soil-based supported catalyst, and a preparation method and application thereof.
Background
The monochlorobenzene anhydride can be used for preparing compounds such as biphenyl tetracarboxylic dianhydride, dimethyl ether tetracarboxylic dianhydride, diphenyl sulfide tetracarboxylic dianhydride and the like, and the polyamide and polyimide engineering plastics prepared by taking the compounds as monomers are widely applied to the high-tech fields such as aviation, aerospace, microelectronics and the like.
The preparation method of monochlorobenzene anhydride comprises a heterocyclic synthesis method, a nitrobenzene dry chlorination method, a phthalic anhydride photochlorination method, a phthalic anhydride gas phase chlorination method and the like, but the preparation method has the problems of low yield, low product purity, high production cost and the like. The existing molten phthalic anhydride chlorination method has the advantages of mild reaction conditions and simple and convenient production operation, but still has the defects of more byproducts and poor monochlorophthalic anhydride selectivity, not only is the product difficult to separate, but also the raw material waste is caused, so that the process adopts a high-efficiency catalyst to overcome the defects. At present, the most used catalyst is mainly FeCl3、AlCl3And ZnCl2Free Lewis acid catalysts, in which FeCl is additionally present3The catalytic effect is optimal. But free FeCl3The catalyst has low recovery rate, and the conversion rate and the selectivity do not meet the requirements of industrial production.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention aims to provide the attapulgite-based supported catalyst with good adsorption activity, the invention also aims to provide a preparation method of the attapulgite-based supported catalyst with energy saving and consumption reduction, and the invention also aims to provide application of the attapulgite-based supported catalyst with high conversion rate and high selectivity in preparation of monochlorophthalic anhydride.
The technical scheme is as follows: the attapulgite-based supported catalyst has the mass ratio of the active components of the catalyst to the attapulgite of 1: 5-1: 10. the active component of the catalyst is metal chloride Lewis acid FeCl3、AlCl3Or ZnCl2。
The preparation method comprises the following steps of mixing the active components of the catalyst and attapulgite according to the ratio of 1: 5-1: 10, roasting at the temperature of 200-280 ℃ for 2-3 hours, grinding and sieving with a sieve of 80-100 meshes to obtain the catalyst.
The application of the invention comprises the steps of putting the attapulgite-based supported catalyst into molten phthalic anhydride, wherein the mass of the attapulgite-based supported catalyst is 1.5-2.0% of the mass of the phthalic anhydride, introducing chlorine gas with the flow rate of 15-20 mL/min at normal pressure, and carrying out direct chlorination catalytic reaction for 14-20 hours at the reaction temperature of 150-180 ℃.
The reaction principle is as follows: the attapulgite is a special adsorption material and has a unique pore channel structure, so that FeCl can be loaded3The selectivity of the reaction and the conversion rate of the raw materials are improved.
Has the advantages that: compared with the prior art, the invention has the following remarkable characteristics: the conversion rate of the raw materials and the selectivity of the monochlorophthalic anhydride are high, the conversion rate of the phthalic anhydride is 85.3-96.8%, and the selectivity of the monochlorophthalic anhydride is 83.7-93.6%; the catalyst has stable performance, is easy to recover and can be repeatedly used; the preparation and reaction of the catalyst are simple, the reaction condition is mild, and the energy consumption is saved; the attapulgite is a cheap natural aluminum magnesium silicate mineral, has large specific surface area and good adsorption activity, is a good adsorbent and carrier, and reduces the production cost.
Drawings
Figure 1 is an XRD pattern of the present invention.
Detailed Description
FeCl used in the following examples3The content is more than or equal to 99.0 percent, and the AR is analytically pure and is produced by the Yawegian chemical Co., Ltd in the tin-free market; AlCl3Produced by Shentai chemical reagent limited company of Tianjin, the content of the analytically pure AR is more than or equal to 97.0 percent; ZnCl2Pure AR is analyzed by the production of Dalochi chemical reagent factory in Tianjin, the content is 98.0 percent; the attapulgite clay is produced by Jiangsu Huai Yuan mining company Limited, and the content of the attapulgite clay is more than or equal to 80 percent; the phthalic anhydride is produced by Shanghai Linfeng chemical reagent limited company, and the content of the analytically pure AR is more than or equal to 99.7 percent; the chlorine gas is produced by Anbang electrochemical Co., Ltd, and the volume fraction of the chlorine is more than or equal to 99.6%.
Example 1
Uniformly mixing white powdery attapulgite with deionized water, stirring into a proper paste, adding FeCl with the mass ratio of the white powdery attapulgite to the attapulgite being 1:103Mixing, extruding, drying at 80 deg.C for 4 hr in oven, calcining at 280 deg.C in muffle furnace for 3 hr, grinding, and sieving with 80 mesh sieveAttapulgite-loaded FeCl3A catalyst.
200g of phthalic anhydride is heated and melted to 150 ℃, and after the temperature is constant, the attapulgite loaded FeCl is added3The catalyst is added into the molten phthalic anhydride according to 1.5 percent of the mass of the fed phthalic anhydride, chlorine is introduced under mechanical stirring, the flow rate of the chlorine is 15mL/min, and the reaction lasts for 16 hours.
Wherein, the conversion rate of the phthalic anhydride is 96.1 percent, and the selectivity of the monochlorophthalic anhydride is 93.6 percent.
The attapulgite catalyst is processed by FeCl3After being loaded, XRD (X-ray diffraction) spectrum analysis is carried out, and the result shows that the attapulgite catalyst is subjected to FeCl3After loading, the characteristic diffraction peak (2 θ ═ 8.3 °) of the attapulgite disappeared, the intensity of the characteristic diffraction peak (2 θ ═ 26.55 °) of the quartz increased, and FeCl increased3The catalyst loading causes the attapulgite to change its properties.
Example 2
The reaction solution in example 1 was distilled under reduced pressure, and the reaction product and unreacted raw material were collected and recovered to obtain used attapulgite-supported FeCl3A catalyst. Adding 200g of fresh phthalic anhydride again, heating and melting to 150 ℃, introducing chlorine gas under mechanical stirring, wherein the chlorine flow is 15mL/min, and reacting for 18 hours.
Wherein the conversion rate of the phthalic anhydride is 95.4 percent, and the selectivity of the monochlorophthalic anhydride is 91.6 percent.
Example 3
Uniformly mixing white powdery attapulgite with deionized water, stirring into a proper paste, adding FeCl with the mass ratio of the white powdery attapulgite to the attapulgite being 1:73Uniformly mixing, extruding to form strips, drying in an oven at 80 ℃ for 4 hours, roasting in a muffle furnace at 240 ℃ for 2 hours, grinding, and sieving with a 100-mesh sieve to prepare the attapulgite-loaded FeCl3A catalyst.
200g of phthalic anhydride is heated and melted to 150 ℃, and after the temperature is constant, the attapulgite loaded FeCl is added3The catalyst is added into the molten phthalic anhydride according to 2.0 percent of the mass of the fed phthalic anhydride, chlorine is introduced under mechanical stirring, the flow rate of the chlorine is 16mL/min, and the reaction lasts for 14 hours.
Wherein, the conversion rate of the phthalic anhydride is 85.3 percent, and the selectivity of the monochlorophthalic anhydride is 90.5 percent.
Example 4
Uniformly mixing white powdery attapulgite with deionized water, stirring into a proper paste, adding FeCl with the mass ratio of the white powdery attapulgite to the attapulgite being 1:63Uniformly mixing, extruding to form strips, drying in an oven at 80 ℃ for 4 hours, roasting in a muffle furnace at 220 ℃ for 2.5 hours, grinding, sieving with a 90-mesh sieve to prepare the attapulgite-loaded FeCl3A catalyst.
200g of phthalic anhydride is heated and melted to 150 ℃, and after the temperature is constant, the attapulgite loaded FeCl is added3The catalyst is added into the molten phthalic anhydride according to 1.6 percent of the mass of the fed phthalic anhydride, chlorine is introduced under mechanical stirring, the flow rate of the chlorine is 17mL/min, and the reaction is carried out for 20 hours.
Wherein, the conversion rate of the phthalic anhydride is 96.8 percent, and the selectivity of the monochlorophthalic anhydride is 83.7 percent.
Example 5
Uniformly mixing white powdery attapulgite with deionized water, stirring into a proper paste, and adding AlCl with the mass ratio of 1:10 to the attapulgite3Uniformly mixing, extruding to form strips, drying in an oven at 80 ℃ for 4 hours, roasting in a muffle furnace at 280 ℃ for 3 hours, grinding, sieving with a 80-mesh sieve to prepare the attapulgite loaded AlCl3A catalyst.
200g of phthalic anhydride is heated and melted to 150 ℃, and the attapulgite loaded AlCl is heated and melted after the temperature is constant3The catalyst is added into the molten phthalic anhydride according to 1.5 percent of the mass of the fed phthalic anhydride, chlorine is introduced under mechanical stirring, the flow rate of the chlorine is 15mL/min, and the reaction is carried out for 18 hours.
Wherein, the conversion rate of the phthalic anhydride is 70.6 percent, and the selectivity of the monochlorophthalic anhydride is 82.9 percent.
Example 6
Uniformly mixing white powdery attapulgite with deionized water, stirring into a proper paste, and adding ZnCl with the mass ratio of the attapulgite to the white powdery attapulgite being 1:102Uniformly mixing, extruding and forming, drying in an oven at 80 ℃ for 4 hours, roasting in a muffle furnace at 280 ℃ for 3 hours, grinding, and sieving with a 100-mesh sieve to prepare the attapulgite supported ZnCl2A catalyst.
200g of phthalic anhydride is heated and melted to 150 ℃, and the attapulgite loaded ZnCl is added after the temperature is constant2The catalyst is added into the molten phthalic anhydride according to 1.5 percent of the mass of the fed phthalic anhydride and is mechanically stirredChlorine gas was introduced at a flow rate of 15mL/min, and the reaction was carried out for 18 hours.
Wherein, the conversion rate of the phthalic anhydride is 65.8 percent, and the selectivity of the monochlorophthalic anhydride is 78.4 percent.
Example 7
Uniformly mixing white powdery attapulgite with deionized water, stirring into a proper paste, adding FeCl with the mass ratio of the white powdery attapulgite to the attapulgite being 1:93Uniformly mixing, extruding to form strips, drying in an oven at 80 ℃ for 4 hours, roasting in a muffle furnace at 200 ℃ for 3 hours, grinding, and sieving with a 90-mesh sieve to prepare the attapulgite-loaded FeCl3A catalyst.
200g of phthalic anhydride is heated and melted to 180 ℃, and after the temperature is constant, the attapulgite loaded FeCl is added3The catalyst is added into the molten phthalic anhydride according to 1.7 percent of the mass of the fed phthalic anhydride, chlorine is introduced under mechanical stirring, the flow rate of the chlorine is 18mL/min, and the reaction is carried out for 19 hours.
Wherein the conversion rate of the phthalic anhydride is 90.3 percent, and the selectivity of the monochlorophthalic anhydride is 84.1 percent.
Example 8
Uniformly mixing white powdery attapulgite with deionized water, stirring into a proper paste, adding FeCl with the mass ratio of the white powdery attapulgite to the attapulgite being 1:83Uniformly mixing, extruding and forming, drying for 4 hours at 80 ℃ in an oven, roasting for 3 hours at 280 ℃ in a muffle furnace, grinding, and sieving with a 80-mesh sieve to prepare the attapulgite-loaded FeCl3A catalyst.
200g of phthalic anhydride is heated and melted to 150 ℃, and after the temperature is constant, the attapulgite loaded FeCl is added3The catalyst is added into the molten phthalic anhydride according to 1.8 percent of the mass of the fed phthalic anhydride, chlorine is introduced under mechanical stirring, the flow rate of the chlorine is 19mL/min, and the reaction lasts 18 hours.
Wherein, the conversion rate of the phthalic anhydride is 85.4 percent, and the selectivity of the monochlorophthalic anhydride is 87.2 percent.
Example 9
Uniformly mixing white powdery attapulgite with deionized water, stirring into a proper paste, adding FeCl with the mass ratio of the white powdery attapulgite to the attapulgite being 1:103Uniformly mixing, extruding to form strips, drying in an oven at 80 ℃ for 4 hours, roasting in a muffle furnace at 260 ℃ for 3 hours, grinding, and sieving with a 100-mesh sieve to prepare the attapulgite-loaded FeCl3Catalyst and process for preparing same。
200g of phthalic anhydride is heated and melted to 180 ℃, and after the temperature is constant, the attapulgite loaded FeCl is added3The catalyst is added into the molten phthalic anhydride according to 1.9 percent of the mass of the fed phthalic anhydride, chlorine is introduced under mechanical stirring, the flow rate of the chlorine is 20mL/min, and the reaction is carried out for 15 hours.
Wherein the conversion rate of the phthalic anhydride is 95.4 percent, and the selectivity of the monochlorophthalic anhydride is 80.9 percent.
Comparative example 1
Heating and melting 200g of phthalic anhydride to 150 ℃, and heating pure FeCl after the temperature is constant3The catalyst is added into the molten phthalic anhydride according to 0.5 percent of the mass of the fed phthalic anhydride, chlorine is introduced into the magnetic stirrer under the continuous stirring state, the flow rate of the introduced chlorine is 15mL/min, and the reaction is carried out for 18 hours.
Wherein, the conversion rate of the phthalic anhydride is 75.9 percent, and the selectivity of the monochlorophthalic anhydride is 77.4 percent.
In contrast to example 1, the active component is FeCl3The reaction conditions in comparative example 1 were significantly lower in conversion and monochlorophthalic anhydride selectivity of the starting material phthalic anhydride in comparative example 1 than in example 1 due to the difference in catalysts, although the amount of the catalyst active component charged and the reaction time were significantly higher than in example 1 under the same reaction temperature and chlorine flow rate.
Comparative example 2
Uniformly mixing white powdery attapulgite with deionized water, stirring into a proper paste, extruding into strips, drying in an oven at 80 ℃ for 4 hours, roasting in a muffle furnace at 280 ℃ for 3 hours, grinding, and sieving by a sieve of 80-100 meshes to prepare the attapulgite carrier.
FeCl is added3Heating to 600 deg.C in roaster for gasification, and vapor-phase deposition of FeCl3Loading on the attapulgite carrier to prepare the attapulgite-based supported catalyst. 200g of phthalic anhydride is heated and melted to 180 ℃, and after the temperature is constant, the attapulgite loaded FeCl is added3The catalyst is added into the molten phthalic anhydride according to 1.5 percent of the feeding amount of the phthalic anhydride, chlorine is introduced into the magnetic stirrer under the continuous stirring state, the flow rate of the introduced chlorine is 15mL/min, and the reaction is carried out for 18 hours.
Wherein the conversion rate of the phthalic anhydride is 80.4 percent, and the selectivity of the monochlorophthalic anhydride is 88.3 percent.
In contrast to example 1, the conversion and monochlorophthalic anhydride selectivity of the starting material phthalic anhydride of comparative example 2 is significantly lower than that of example 1 due to the difference in the catalyst preparation method, although the reaction temperature and reaction time are significantly higher than those of example 1 in comparative example 2 under the same catalyst charge and chlorine flow rate.

Claims (6)

1. The application of the attapulgite-based supported catalyst in the preparation of monochlorophthalic anhydride is characterized in that: putting the attapulgite-based supported catalyst into molten phthalic anhydride, introducing chlorine gas at normal pressure, and performing direct chlorination catalytic reaction, wherein the mass of the attapulgite-based supported catalyst is 1.5-2.0% of that of the phthalic anhydride; the mass ratio of the active components of the catalyst to the attapulgite is 1: 5-1: 10; the active component of the catalyst is FeCl3。
2. The use of an attapulgite-based supported catalyst according to claim 1 for the preparation of monochlorophthalic anhydride, wherein: mixing the active components of the catalyst and attapulgite according to the proportion of 1: 5-1: 10, molding by extrusion, drying, roasting at 200-280 ℃ for 2-3 h, grinding and sieving to obtain the catalyst.
3. The use of an attapulgite-based supported catalyst according to claim 2 for the preparation of monochlorophthalic anhydride, wherein: and sieving with a 80-100 mesh sieve.
4. The use of an attapulgite-based supported catalyst according to claim 1 for the preparation of monochlorophthalic anhydride, wherein: the reaction temperature of the chlorination catalytic reaction is 150-180 ℃.
5. The use of an attapulgite-based supported catalyst according to claim 1 for the preparation of monochlorophthalic anhydride, wherein: the flow rate of the chlorine gas is 15-20 mL/min.
6. The use of an attapulgite-based supported catalyst according to claim 1 for the preparation of monochlorophthalic anhydride, wherein: the reaction time of the chlorine and the molten phthalic anhydride is 14-20 hours.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1460677A (en) * 2003-06-11 2003-12-10 黑龙江省石油化学研究院 Method for preparing monochlorophthalic anhydride by means of chloration of phthalic anhydride
CN101947444A (en) * 2010-08-06 2011-01-19 淮阴工学院 Attapulgite load nano Pd catalyst and method for preparing chloroaniline by catalyzing and deoxidating attapulgite load nano Pd catalyst
CN103769177A (en) * 2014-02-11 2014-05-07 常州大学 Preparation method for attapulgite clay-based cycloaddition reaction catalyst
CN106378140A (en) * 2016-08-28 2017-02-08 安徽金邦医药化工有限公司 Solid catalyst and catalytic preparation method of propylene carbonate by using solid catalyst
CN108380204A (en) * 2018-03-06 2018-08-10 常州大学 A kind of preparation of Mn bases attapulgite catalyst and characterization

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1460677A (en) * 2003-06-11 2003-12-10 黑龙江省石油化学研究院 Method for preparing monochlorophthalic anhydride by means of chloration of phthalic anhydride
CN101947444A (en) * 2010-08-06 2011-01-19 淮阴工学院 Attapulgite load nano Pd catalyst and method for preparing chloroaniline by catalyzing and deoxidating attapulgite load nano Pd catalyst
CN103769177A (en) * 2014-02-11 2014-05-07 常州大学 Preparation method for attapulgite clay-based cycloaddition reaction catalyst
CN106378140A (en) * 2016-08-28 2017-02-08 安徽金邦医药化工有限公司 Solid catalyst and catalytic preparation method of propylene carbonate by using solid catalyst
CN108380204A (en) * 2018-03-06 2018-08-10 常州大学 A kind of preparation of Mn bases attapulgite catalyst and characterization

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