CN112452354B - Preparation method of multiple modified beta zeolite molecular sieve and application of multiple modified beta zeolite molecular sieve in aromatic hydrocarbon nitration - Google Patents
Preparation method of multiple modified beta zeolite molecular sieve and application of multiple modified beta zeolite molecular sieve in aromatic hydrocarbon nitration Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
Abstract
The invention discloses a preparation method of a multiple modified beta zeolite molecular sieve and application thereof in aromatic hydrocarbon nitration. The invention adopts a classical dealuminization method combined with an ion exchange method to prepare the multiple modified beta zeolite molecular sieve, and then the multiple modified beta zeolite molecular sieve is applied to the nitration reaction of aromatic hydrocarbon. The invention uses oxynitride as nitrating agent and uses the prepared modified molecular sieve as catalyst to replace the traditional mixed acid system. The method belongs to green nitration, reduces the generation of waste acid and waste water, avoids the aggregation of mixed acid, and can be widely applied to nitration reactions of various aromatic hydrocarbons.
Description
Technical Field
The invention relates to a preparation method of an efficient, green and environment-friendly multiple modified beta zeolite molecular sieve and application of the multiple modified beta zeolite molecular sieve in aromatic nitration.
Background
The nitration reaction of aromatic hydrocarbon is an important organic substitution reaction, and the generated nitro aromatic hydrocarbon compound plays an important role in synthesizing organic compounds. The aromatic nitro compound can be used as a raw material or an intermediate product and widely applied to the synthesis fields of synthetic drugs, dyes, spices, fertilizers, plastics, explosives and the like. Therefore, in the basic theory research of the aromatic hydrocarbon nitration reaction and the industrial production of the aromatic hydrocarbon nitration reaction, the nitration reaction researchers at home and abroad carry out intensive research on the basic theory research.
In the traditional industry, the aromatic hydrocarbon nitration is mainly performed by the nitration of mixed nitric acid and sulfuric acid, and is the most commonly applied method for producing nitro aromatic compounds at home and abroad at present, and the technology is applied to industrial production for more than 160 years and is the most mature production process. However, the method has the disadvantages of poor atom economy, poor regioselectivity (occurrence of oxidation side reaction and excessive nitrification), generation of a large amount of waste acid, environmental harm and the like. Therefore, in recent years, in order to solve the above-mentioned disadvantages, many researchers have been working on the nitration of novel green aromatic hydrocarbons. Research work has focused on improvements in both nitrating agents and catalysts, and has led to a search for greener nitrating agents and novel solid acid catalysts for use in aromatics nitration in place of sulfuric acid.
The nitrating agent commonly used at present is traditional nitric acid (HNO)3) Sulfuric acid (H)2SO4) Mixed acid, nitric acid (HNO)3) Sulfuric acid (H)2SO4) -phosphoric acid (H)3PO4) Nitric acid and acetic anhydride, nitrate esters or nitrates, and oxynitrides, among others. When the nitrogen oxide is used as a nitrating agent, the defect of poor selectivity of a target product in the traditional nitric-sulfuric mixed acid method can be changed, and the nitrating agent has good regional selectivity for nitration reaction, so that the selectivity of the target product in a nitrated product isomer can be controlled by changing reaction conditions.
For the nitration catalyst, zeolite molecular sieve catalysts, clay catalysts, heteropolyacid catalysts, metal oxides, rare earth metal salts, ionic liquids and the like are mainly used. Among them, the research on acidic zeolite molecular sieves is active.
In the nitration reaction process, the zeolite molecular sieve can change the isomer ratio of the nitration product in the catalytic reaction process by virtue of a unique structure, so that the selectivity of the reaction is improved. Therefore, the catalyst of the type is widely applied to the aromatic nitration reaction. Zealand and Luchun uses ZSM-5 molecular sieve to catalyze toluene and increase the generation ratio of p-nitrotoluene. The Penxinhua and Luchun threads are modified by a ZSM-5 catalyst, so that the obtained catalyst has better catalytic selectivity, the better catalyst is a LaZSM-5 molecular sieve, the yield of the mononitrotoluene generated by catalyzing toluene is 21%, and the ratio of the o-nitrotoluene to the p-nitrotoluene is 1.16. Keith Smith and other researches find that the beta molecular sieve is used as a catalyst to catalyze and nitrify fluorobenzene in a nitric acid system, and the selectivity of the p-nitrofluorobenzene reaches 94%. Ganjala et al conducted nitration studies on benzene, toluene, chlorobenzene, etc. using a beta-SBA-15 composite molecular sieve (ZBS-15) as a catalyst, and the nitrating agent was nitric acid, and the following results were obtained: the benzene conversion rate is 89%, and the nitrobenzene selectivity is 100%; the conversion rate of toluene is 100 percent, and the selectivity of p-nitrotoluene is 55 percent; the chlorobenzene conversion was 63% and the p-nitrochlorobenzene selectivity was 70%. US4418230 and US5324872 report the use of molecular sieve catalysts, primarily mordenite, under nitration conditions at a reaction temperature of about 200 ℃ and a benzene to nitric acid molar ratio of above 1.4. The Cu Chemical Uetikon company respectively discloses a nitration technology using H-mordenite as a catalyst in US5324872 and US5334781, the selectivity of nitrobenzene can reach 92-99% and the yield reaches 70-80% under the conditions of the temperature of 150-170 ℃ and the molar ratio of benzene to nitric acid being 1:0.4, but experimental data of the stability of the catalyst are not reported. US4107220 and US5324872 both disclose the use of H-type mordenite for catalyzing NO2The technology for nitrifying benzene and benzene aromatics is 100-350oC range (preferably 150 to 250)oC) The best results of gas phase nitration are nitrobenzene yields of not more than 80%. US4347389 and US4415744 use P-V-O composite oxides and SO, respectively3Treated alumino-silicate-metal oxide as catalyst, benzene and NO2At a temperature range of 170-225oC and molar ratio range 1: 1.5-1: 4, carrying out nitration reaction, wherein the yield of the obtained mononitrobenzene is 70-90%.
Disclosure of Invention
The invention aims to provide a preparation method of a nitration catalyst and a green method for preparing an aromatic nitro compound by nitrating aromatic hydrocarbon with an oxynitride.
The purpose of the invention is realized by the following modes:
the application of the multiple modified beta zeolite molecular sieve in aromatic hydrocarbon nitration adopts the multiple modified beta zeolite molecular sieve as a catalyst, introduces oxygen as a nitration activator, directly performs nitration reaction on aromatic hydrocarbon and nitrogen oxide, wherein the molar ratio of the aromatic hydrocarbon to the nitrogen oxide is 1: 0.5-5, and the reaction temperature is 15-75oC, the reaction time is 1-12 h, the reaction oxygen pressure is 0.1-3 MPa, and the nitroaromatic compound is efficiently prepared; the catalyst is easy to separate, stable and reusable.
Further, the nitration reaction is carried out in a closed tank reactor.
Further, the oxynitride is NO2And N2O5One or two of them.
Furthermore, the molar ratio of the aromatic hydrocarbon to the nitrogen oxide is preferably 1: 1-4.
Further, the reaction temperature is preferably 30 to 55 ℃.
Further, the reaction time is preferably 1-6 h.
Further, the reaction oxygen pressure is preferably 0.5 to 2.5 MPa. Further, the aromatic hydrocarbon can be benzene, toluene, halogenated benzene, nitrobenzene, naphthalene, 1-nitronaphthalene, o-xylene, m-xylene, p-xylene, etc.
The invention also provides a preparation method of the multiple modified beta zeolite molecular sieve, which comprises the following steps: the beta zeolite molecular sieve with the silicon-aluminum ratio of 25 or 40 is firstly subjected to acid treatment or hydrothermal treatment (preferably acid treatment) to remove partial aluminum, one or two metal ions are introduced into a product after dealumination through ion exchange, and the obtained product is roasted and activated to obtain the multiple modified beta zeolite molecular sieve. Further, the acid used for the acid treatment is one of oxalic acid, acetic acid, nitric acid, sulfuric acid, or phosphoric acid, and preferably one of oxalic acid, nitric acid, and sulfuric acid.
Further, the concentration of the acid used for acid treatment is 0.2-5 mol/L, preferably 1-4 mol/L; the acid treatment time is 2-24 h, preferably 4-12 h.
Further, the metal salt used for ion exchange is one or two of ferric nitrate, cupric nitrate, cobalt nitrate, cerous nitrate, manganese nitrate, bismuth nitrate, ferric chloride, cupric chloride, cobalt chloride, cerium chloride, manganese chloride or bismuth chloride, preferably one or two of nitrate or chloride of copper, cobalt, cerium or manganese.
Furthermore, the concentration of the metal salt used for ion exchange is 0.1-5 mol/L, preferably 0.5-2 mol/L, the time of ion exchange is 1-12 h, preferably 4-8 h, and the frequency of ion exchange is 1-5 times, preferably 2-3 times.
Further, the roasting temperature is 200-700 DEG CoC, preferably 400-600oAnd C, roasting for 2-10 hours, preferably 4-8 hours.
The reaction effect analysis method comprises the following steps: according to the method provided by the invention, after the nitration reaction in the kettle type reactor is finished, the catalyst and the reaction mixture are cooled, filtered and separated, the mixture is sampled and subjected to gas chromatography analysis, and the data are analyzed and the conversion rate of the aromatic hydrocarbon and the selectivity of the nitration product are calculated.
The invention has the beneficial effects that:
(1) the method does not adopt sulfuric acid in the reaction, obviously reduces the generation of waste acid and waste water, and the catalyst is easy to separate and stable and can be recycled.
(2) The invention can efficiently catalyze and nitrify aromatic hydrocarbon to obtain the aromatic nitro compound with high selectivity, wherein the conversion rate of toluene can reach more than 90 percent and the selectivity of p-nitrotoluene can reach more than 70 percent in the process of preparing p-nitrotoluene by nitrifying toluene.
Detailed Description
The following examples are intended to illustrate the invention, but not to limit it.
The following multiple modified beta zeolite molecular sieves are treated by nitric acid and then introduced with one or two of copper, cobalt or manganese by ion exchange, and the specific method comprises the following steps: mixing a beta zeolite molecular sieve with 0.2-5 mol/L nitric acid according to the proportion of 1g to 20ml, refluxing the obtained suspension at 60 ℃ for 12h, filtering and washing to be neutral, drying to obtain dealuminized productThe sample is subjected to ion exchange with one or two solutions of 0.5-2 mol/L of copper nitrate, cobalt nitrate or manganese nitrate according to the proportion of 1g:15ml, the exchange frequency is 3 times, and the obtained sample is 500 timesoActivation for 6H at C, different samples were labeled H β D4 (treated with only 4mol/L nitric acid, without introducing metal ions), Cu0.5H.beta.D 4 (treated with 4mol/L nitric acid and then ion exchanged with 0.5mol/L copper nitrate solution), Ce0.5H.beta.D 4 (treated with 4mol/L nitric acid and then ion exchanged with 0.5mol/L cerium nitrate solution), Ce0.5-Mn0.5H.beta.D 4 (treated first with 4mol/L nitric acid and then ion exchanged with a solution of cerium nitrate and manganese nitrate in a volume ratio of 1:1 and each at a concentration of 0.5 mol/L).
Example 1: 5.0g of toluene, 5.0g of acetic anhydride and 5.0g of NO are weighed out2Placing in a 100ml kettle reactor with reaction oxygen pressure of 0.5MPa at 35%oAfter 4h of reaction at C, the mixture was cooled and filtered to obtain a liquid mixture, which was sampled for gas phase analysis to obtain a toluene conversion of 69.9% and a p-nitrotoluene selectivity of 37.7%.
Example 2: except that 5.0gNO2The operation was carried out in the same manner as in example 1 except that 2.5 g was used, whereby the conversion of toluene was 35.1% and the selectivity for p-nitrotoluene was 36.9%.
Example 3: except that the reaction temperature was changed to 25oIn addition, the same procedure as in example 1 was repeated except that the conversion of toluene was 58.7% and the selectivity to nitrotoluene was 37.0%.
Example 4: the same procedure as in example 1 was repeated except that the reaction oxygen pressure was changed to 0.2MPa, whereby the conversion of toluene was 50.1% and the selectivity to p-nitrotoluene was 36.3%.
Example 5: the same procedure as in example 1 was repeated except that 0.5g of H.beta.D 4 catalyst was charged into the autoclave to obtain a toluene conversion of 76.1% and a p-nitrotoluene selectivity of 53.5%.
Example 6: except that the catalyst is changed into Cu0.5The same procedure as in example 5, except for the catalyst-H.beta.D 4, gave a toluene conversion of 80.5% and a p-nitrotoluene selectivity of 59.4%.
Example 7: except that the catalyst is changed into Ce0.5The same procedure as in example 5, except for the catalyst-H.beta.D 4, gave a toluene conversion of 83.4% and a p-nitrotoluene selectivity of 61.2%.
Example 8: except that the catalyst is changed into Ce0.5-Mn0.5The same procedure as in example 5, except for the catalyst-H.beta.D 4, gave a toluene conversion of 86.3% and a p-nitrotoluene selectivity of 68.4%.
Example 9: the same procedure as in example 8 was repeated except that the amount of the catalyst used was changed to 1.5g, to obtain a toluene conversion of 91.2% and a p-nitrotoluene selectivity of 75.8%.
Example 10: the same procedure as in example 9 was repeated except that the reaction substrate was changed from toluene to benzene, whereby the conversion of benzene was 99% and the selectivity of nitrobenzene was 99%.
Example 11: the same procedure as in example 9 was repeated except that the reaction substrate was changed from toluene to chlorobenzene, whereby the conversion of chlorobenzene was 82.0% and the selectivity to nitrochlorobenzene was 91.2%.
Example 12: the same procedure as in example 9 was repeated except that the reaction substrate was changed from toluene to naphthalene, whereby the conversion of naphthalene was 100% and the selectivity for 1, 5-dinitronaphthalene was 52.0%.
Example 13: the same procedure as in example 9 was repeated except that the reaction substrate was changed from toluene to o-xylene, whereby the conversion of o-xylene was 54% and the selectivity for 3, 4-dimethylnitrobenzene was 61.8%.
Claims (8)
1. The application of the multiple modified beta zeolite molecular sieve in aromatic hydrocarbon nitration is characterized in that the multiple modified beta zeolite molecular sieve is used as a catalyst, oxygen is introduced as a nitration activator, aromatic hydrocarbon and nitrogen oxide are subjected to a nitration reaction directly, the molar ratio of the aromatic hydrocarbon to the nitrogen oxide is 1: 0.5-5, and the reaction temperature is 15-75oC, the reaction time is 1-12 h, and the reaction oxygen pressure is 0.1-3 MPa;
the preparation method of the multiple modified beta zeolite molecular sieve comprises the following steps: removing partial aluminum of the beta zeolite molecular sieve with the silicon-aluminum ratio of 25 or 40 by acid treatment or hydrothermal treatment, introducing two metal ions into a product after dealumination by ion exchange, and roasting and activating the obtained product to obtain the multiple modified beta zeolite molecular sieve; the metal salt used for ion exchange is one of cerium nitrate and cerium chloride and one of manganese nitrate and manganese chloride.
2. The application of the multiple modified beta zeolite molecular sieve in arene nitration according to claim 1, wherein the nitration reaction is carried out in a closed tank reactor.
3. The use of the multiple modified zeolite beta molecular sieve of claim 1, wherein the nitrogen oxide is NO2And N2O5One or two of them; the molar ratio of the aromatic hydrocarbon to the nitrogen oxide is 1: 1-4.
4. The application of the multiple modified beta zeolite molecular sieve in arene nitration according to claim 1, wherein the reaction temperature is 30-55 ℃, and the reaction time is 1-6 h.
5. The application of the multiple modified beta zeolite molecular sieve in arene nitration, according to claim 1, wherein the reaction oxygen pressure is 0.5-2.5 MPa.
6. The application of the multiple modified beta zeolite molecular sieve in aromatic hydrocarbon nitration according to claim 1, wherein the aromatic hydrocarbon is one or more than two of benzene, toluene, halogenated benzene, nitrobenzene, naphthalene, 1-nitronaphthalene, o-xylene, m-xylene and p-xylene.
7. The application of the multiple modified beta zeolite molecular sieve in arene nitration according to claim 1, wherein the acid used in the acid treatment is one of oxalic acid, acetic acid, nitric acid, sulfuric acid or phosphoric acid; the concentration of acid adopted for acid treatment is 0.2-5 mol/L; the acid treatment time is 2-24 h.
8. The application of the multiple modified beta zeolite molecular sieve in arene nitration according to claim 1, wherein the concentration of metal salt adopted by ion exchange is 0.1-5 mol/L, the time of ion exchange is 1-12 h, and the frequency of ion exchange is 1-5 times; the roasting temperature is 200-700 ℃, and the roasting time is 2-10 h.
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| "锰基氧化物低温脱硝催化剂的研究";黄增斌;《中国优秀学位硕士论文全文数据库》;20070315;第12-59页 * |
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