CN106179493B

CN106179493B - A kind of hydrophobic solid acid catalyst and preparation and the application in aromatic acid esterification

Info

Publication number: CN106179493B
Application number: CN201510226637.7A
Authority: CN
Inventors: 徐杰; 杜文强; 陈晨; 高进; 石松; 马红
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2015-05-06
Filing date: 2015-05-06
Publication date: 2018-11-13
Anticipated expiration: 2035-05-06
Also published as: CN106179493A

Abstract

The present invention discloses a kind of hydrophobic solid acid catalyst and preparation method thereof and the application in aromatic acid and low-carbon alcohols esterification.The catalyst is with SiO₂Particle is substrate, in its bulk phase-doped acid site lewis, links hydrophobic group on the surface thereof；The hydrophobic catalyst can be esterified with efficient catalytic aromatic acid and low-carbon alcohols, and for the high conversion rate of aromatic acid up to 99%, aromatic esters are selectively 95% or more.Compared with traditional solid acid catalyst, the catalyst usage amount is low, and thermal stability is good, reusable.

Description

A kind of hydrophobic solid acid catalyst and preparation and the application in aromatic acid esterification

Technical field

The present invention relates to chemical field, specifically a kind of hydrophobic solid acid catalyst and preparation method thereof and Application in aromatic acid esterification.

Background technology

Ester type compound is important Organic chemical products, there is the wide market demand.Methyl benzoate is a kind of heavy The fragrance wanted, and phthalate is then important plasticizer.Traditional catalyst for esterification reaction mainly has inorganic acid (such as The concentrated sulfuric acid, phosphoric acid), heteropoly acid, oxide, sulfonate resin etc..Conventional method uses the homogeneous inorganic acid such as concentrated sulfuric acid as ester Change catalysts, active high, advantage of low cost, but sulfuric acid severe corrosion equipment in production process, subsequent Product treatment during generate largely containing acid waste water be difficult to handle.Solid acid catalyst is because its corrosivity is small, recyclable profit With the features such as, become the emphasis developed in recent years.Such as：103990449 A of patent CN disclose a kind of mesoporous Ti-Mo solids Acid catalyst achieves good effect in the esterification reaction.Document (ACS Catal.2012,2,565-572) reports A kind of solid acid based on polymer achieves catalytic effect more better than Amberlyst-15 in the esterification reaction.But this Dosage is big under normal conditions for a little solid acids, and effect is not so good as homogeneous acid, and it is anti-to improve usually to still need water removal in reaction process The selectivity answered.Therefore the efficiency that the solid acid of Development of Novel improves esterification is highly important.The ester of aromatic acid and alcohol A feature for changing reaction is that reaction will produce water, and traditional solid acid catalyst surface is hydrophilic, is unfavorable for the desorption of water It will be improved with the absorption of reactant if making surface hydrophobic enhancing that water be made to be not easy to adsorb by the modification on surface The catalytic activity of catalyst increases the rate of reaction.

Invention content

Acid-bearing wastewater and solid acid catalyst, which are generated, for above-mentioned inorganic acid etching apparatus is unfavorable for the desorption of water and anti- The problems such as answering the absorption of object, a kind of Hydrophobic Catalyst of present invention offer and preparation method thereof, and use this hydrophobic catalyst The application that aromatic acid is efficiently esterified is realized in agent, and under the catalyst action, up to 99%, aromatic esters select the high conversion rate of aromatic acid Selecting property is 95% or more.

Specifically technical solution is：

The present invention discloses a kind of catalyst, with SiO₂Particle is substrate, in SiO₂The bulk phase-doped acid sites lewis, and In SiO₂Hydrophobic group is linked on surface.

Hydrophobic Catalyst formula M Og-SiO₂(X, Y) is indicated, wherein M is the acid sites lewis, and Og is hydrophobicity Group, one kind or two or more in M Zr, Cr, Fe, Ti, Sn or Al, Og are methyl (Me), ethyl (Et), propyl (Pr), second Alkenyl (Vi), Chloroallyl (Pc), naphthalene (Na), phenyl (Ph), trifluoro propyl (Fp), phenyl-monofluoride base (Fb) and pentafluorophenyl group One or more of (Pf), X is the mass content in the acid sites lewis, and Y is the mass content of hydrophobic group.

Catalyst can be prepared as follows：

1) surfactant, ammonium hydroxide, organic phase and cosurfactant are mixed into composition reverse micro emulsion A；

2) B is referred to as with the ammonia spirit of metal soluble-salt；

3) ethyl orthosilicate and organosilan are silicon source, are mixed and made into solution C, and the organosilan is three ethoxy of monomethyl One kind in base silane, a vinyltriethoxysilane, a propyl-triethoxysilicane, Chloroallyl triethoxysilane；

4) solution A and B are mixed to get solution D；Under conditions of being vigorously stirred, solution C is added in solution D, aging 2-48h；

5) acetone demulsification is added, solid is collected by centrifugation, the surfactant in removal solid is washed with ethyl alcohol, in 80-150 DEG C drying, finally obtain a kind of granular nano material of uniform size.

In step 1), surfactant：Ammonium hydroxide：Organic phase：The mass ratio of cosurfactant is 0.1~8：0~4:1~ 4:0.5~6, the mass concentration of the ammonium hydroxide is 25-28%；

In step 2), the mass ratio of metal ion and ethyl orthosilicate is 0.5~6 in source metal：1；

In step 3), the mass ratio of ethyl orthosilicate and organosilan is 1：0.05~1.5；

In step 5), the acetone quality is 5-10 times of ethyl orthosilicate quality.

Surfactant described in step 1) be C8-20 sodium n-alkylbenzenesulfonates in anion surfactant or α-sodium olefin sulfonate, alternatively, for the organic primary amine, Np series or TWEEN Series of the C8-20 long-chains in nonionic surfactant Surfactant, alternatively, for the cetyltrimethylammonium bromide in cationic surfactant；The organic phase is hexamethylene Alkane, n-hexane or toluene；Cosurfactant is n-butanol, n-amyl alcohol, n-hexyl alcohol or n-octyl alcohol.

The ammonia complexing solution of metal described in step 2) is the clear solution that metal salt is formed with ammonium hydroxide and water, metal Salt：Water：The mass ratio of ammonium hydroxide is 0.01~1：1~4:0~4；Wherein, metal is lewis acid as claimed in claim 1 or 2 Center.

The invention discloses the Hydrophobic Catalysts in catalysis aromatic acid and the application in low-carbon alcohols esterification.

In the application, aromatic acid includes benzoic acid, methyl benzoic acid, phthalic acid, one kind in benzenetricarboxylic acid or It is two or more, wherein the methyl benzoic acid is p-methylbenzoic acid, one in o-toluic acid or m-methyl benzoic acid Kind is two or more, and the phthalic acid is terephthalic acid (TPA), one or both of phthalic acid or M-phthalic acid More than, the benzenetricarboxylic acid is 1,3,5- tri- benzoic acid, 1,2,3- tri- benzoic acid or 1, one kind in 2,4- tri- benzoic acid or It is two or more；

The low-carbon alcohols are C1-C8 alcohol, specially methanol, ethyl alcohol, propyl alcohol, butanol, amylalcohol, hexanol, enanthol, octanol； Low-carbon alcohols and the molar ratio of acid are 1.2:1-10:1, preferably 2.5：1~3.5：1, reaction temperature is 100-300 DEG C, preferably 160~200 DEG C, pressure 1-3MPa, preferably 2.0~2.5Mpa；The Hydrophobic Catalyst dosage is aromatic acid quality 0.1-100%, preferably 5~10%.

Be catalyzed in the present invention performance of reaction on catalyst the amount of acidic components is related, acidic site is too low, can influence It is catalyzed the selectivity of reaction, dosage is excessively high, and side reaction increases, therefore the mass content of the lewis acidic sites in the present invention is 0.5-30%.

According to the present invention, the amount of organic group can influence the catalytic effect of catalyst, and content can excessively make nano silicon spheres mistake In irregular, the hydrophobic performance on the too low then surface of content improves insufficient, and catalytic effect is all bad, therefore organic group in the present invention Mass content 0.1-60% in the catalyst.

Beneficial effects of the present invention

It is catalyzed reaction effect to improve, Hydrophobic Catalyst of the invention has selected the silica nanometer of good dispersion Grain is used as substrate, and in its bulk phase-doped acid site lewis, links hydrophobic group on the surface thereof；By in lewis acid The heart carrys out catalytic esterification, and the hydrophobicity on surface is improved into making esterification by introducing the organic group of nonpolarity or low pole The water generated in the process is detached from from catalyst surface in time, to improve reaction rate and yield, is dredged using disclosed by the invention Aqueous catalyst, for the high conversion rate of aromatic acid up to 99%, aromatic esters are selectively 95% or more in esterification, and traditional Solid acid catalyst is compared, which has usage amount low, and thermal stability is good, reusable advantage.

Description of the drawings

Fig. 1 is the transmission electron microscope photo of nano particle.

Specific implementation mode

Following example is described in detail method provided by the invention, but the invention is not limited in any way.

1 materials A (TiPh-SiO of embodiment₂(15,15)) preparation

20g surfactants Np-12,25g hexamethylene, 5g ammonium hydroxide and 3g cosurfactant n-octyl alcohols is taken to mix to obtain solution A；20% titanium tetrachloride aqueous solutions of 10g are B；1g ethyl orthosilicates and 0.2g phenyltriethoxysilanes mix to obtain solution C； Solution A and B are quickly uniformly mixed and form D, solution C is added in solution D with vigorous stirring, aging 8h；Then, it is added 8mL acetone, is vigorously stirred 30min, is demulsified.Centrifuge to obtain white powder；60mL ethyl alcohol, heating stirring are added into this solid 15min, centrifugation；This step 3 time is repeated, until removal of surfactant is clean；Obtain white solid powder.80 DEG C dry most Whole nano material TiPh-SiO₂(15,15)。

The preparation of 2 material B-E of embodiment

The same materials A of preparation method of material B-E, the difference is that the type of organosilan, acidic site and organic group Content on, the type of the organosilan specifically used is shown in Table 1, and obtained material is listed in table 1.

The type for the organosilan that 1 material B-E of table is used in preparing

Material number	Source metal	Organosilan	Title material
				B	TiCl₄	Methltriethoxysilone	TiMy-SiO₂(10,20)
C	FeCl₃	One vinyltriethoxysilane	FeVi-SiO₂(1,50)
				D	AlCl₃	One propyl-triethoxysilicane	AlPr-SiO₂(25,10)
E	SnCl₄	Chloroallyl triethoxysilane	SnPc-SiO₂(10,15)

3 materials A (TiFePh-SiO of embodiment₂(15,7.5,15)) preparation

20g surfactants Np-7,30g hexamethylene and 2g cosurfactant n-butanols is taken to mix to obtain solution A；10g 20% titanium tetrachloride, 10g 10%FeCl₃Aqueous solution and 6g ammonium hydroxide are B；Three ethoxy of 1.2g ethyl orthosilicates and mono- phenyl of 0.2g Base silane mixes to obtain solution C；Solution A and B are quickly uniformly mixed and form D, solution C is added in solution D with vigorous stirring, Aging 8h；Then, 8mL acetone is added, is vigorously stirred 30min, is demulsified.Centrifuge to obtain white powder；It is added into this solid 60mL ethyl alcohol, heating stirring 15min, centrifugation；This step 6 time is repeated, until removal of surfactant is clean；Obtain white solid Powder.80 DEG C dry to obtain final nano material TiPh-SiO₂(15,15)。

4 materials A (TiPrPh-SiO of embodiment₂(15,15,15)) preparation

15g surfactants Np-7,30g hexamethylene and 8g cosurfactant n-butanols is taken to mix to obtain solution A；10g 20% titanium tetrachloride and 2g ammonium hydroxide are solution B；Mono- phenyl three of 1.2g ethyl orthosilicates, 0.2g propyl-triethoxysilicanes and 0.2g Ethoxysilane mixes to obtain solution C；Solution A and B are quickly uniformly mixed and form D, solution is added in solution C with vigorous stirring In D, aging 8h；Then, 10mL acetone is added, is vigorously stirred 30min, is demulsified.Centrifuge to obtain white powder；Into this solid 60mL ethyl alcohol, heating stirring 15min, centrifugation is added；This step 2 time is repeated, until removal of surfactant is clean；Obtain white Solid powder.80 DEG C dry to obtain final nano material TiPrPh-SiO₂(15,15,15).

Embodiment 5

By the 0.025g TiEt-SiO of synthesis₂The catalyst of (10,15) is added in 5mL methanol, and 2g benzoic acid is added, It is heated to 180 DEG C in oil bath, reacts 5h, after reaction, the conversion ratio of benzoic acid is analyzed with HPLC, and conversion ratio is 99%.The yield of methyl benzoate is quantified with GC, yield 96%.

Embodiment 6

By the 0.035g AlPr-SiO of synthesis₂The catalyst of (10,20) is added in 5mL ethyl alcohol, and 2g O-phthalics are added Acid is heated to 200 DEG C in oil bath, reacts 6h, after reaction, the conversion ratio of benzoic acid is analyzed with HPLC, and conversion ratio is 99%.The yield of diethyl phthalate is quantified with GC, yield 98%.

Embodiment 7

By the 0.1g FeEt-SiO of synthesis₂The catalyst of (5,15) is added in 10mL methanol, and 2g is added to methylbenzene first Acid is heated to 150 DEG C in oil bath, reacts 3h, and after reaction, the conversion ratio of p-methylbenzoic acid is analyzed with HPLC, turns Rate is 99%.The yield of methyl p-methyl benzoate is quantified with GC, yield 96%.

Embodiment 8

By the 0.5g TiPr-SiO of synthesis₂The catalyst of (10,10) is added in 5mL enanthol, and 2g O-phthalics are added Acid is heated to 270 DEG C in oil bath, reacts 6h, and after reaction, the conversion ratio of phthalic acid is analyzed with HPLC, conversion Rate is 99%.The yield of dibutyl phthalate (DHP) is quantified with GC, yield 97%.

Embodiment 9

By the 1g SnEt-SiO of synthesis₂The catalyst of (5,20) is added in 5mL butanol, and 2g M-phthalic acids are added, It is heated to 190 DEG C in oil bath, reacts 5h, after reaction, the conversion ratio of M-phthalic acid is analyzed with HPLC, and conversion ratio is 99%.The yield of M-phthalic acid dibutyl ester is quantified with GC, yield 98%.

Embodiment 10

By the 0.3g TiEt-SiO of synthesis₂The catalyst of (10,10) is added in 5mL methanol, and 1,3,5 triphens of 2g are added Formic acid is heated to 280 DEG C in oil bath, reacts 6h, and after reaction, the conversion ratio of 1,3,5-Benzenetricarboxylic acid is analyzed with HPLC, turns Rate is 99%.The yield of 1,3,5-Benzenetricarboxylic acid trimethyl is quantified with GC, yield 95%.

Embodiment 11

By the 0.025g TiFePh-SiO of synthesis₂The catalyst of (15,15) (5,10) is added in 5mL ethyl alcohol, and 2g is added Benzoic acid is heated to 180 DEG C in oil bath, reacts 10h, and after reaction, the conversion ratio of benzoic acid is analyzed with HPLC, conversion Rate is 99%.The yield of ethyl benzoate is quantified with GC, yield 96%.

Claims

1. a kind of hydrophobic solid acid catalyst, it is characterised in that：With SiO₂Particle is substrate, in SiO₂Bulk phase-doped lewis Acid site, and in SiO₂Hydrophobic group is linked on surface；

The preparation method step of the hydrophobic solid acid catalyst is：

2) B is referred to as with the ammonia spirit of metal soluble-salt；

3) ethyl orthosilicate and organosilan are silicon source, are mixed and made into solution C, and the organosilan is monomethyl triethoxysilicane One kind in alkane, a vinyltriethoxysilane, a propyl-triethoxysilicane, Chloroallyl triethoxysilane；

4) solution A and B are mixed to get solution D；Under conditions of being vigorously stirred, solution C is added in solution D, aging 2- 48h；

5) acetone demulsification is added, solid is collected by centrifugation, the surfactant in removal solid is washed with ethyl alcohol, in 80-150 DEG C of baking It is dry, finally obtain a kind of granular nano material of uniform size；

Wherein：In step 1), surfactant：Ammonium hydroxide：Organic phase：The mass ratio of cosurfactant is 0.1~8：0~4:1 ~4:0.5~6, the mass concentration of the ammonium hydroxide is 25-28%；In step 2), metal ion and ethyl orthosilicate in source metal Mass ratio be 0.5~6：1；In step 3), the mass ratio of ethyl orthosilicate and organosilan is 1：0.05~1.5；Step 5) In, the acetone quality is 5-10 times of ethyl orthosilicate quality.

2. catalyst described in accordance with the claim 1, it is characterised in that：Hydrophobic Catalyst formula M Og-SiO₂(X, Y) table Showing, wherein M is the acid sites lewis, and Og is hydrophobic group, one kind or two or more in M Zr, Cr, Fe, Ti, Sn or Al, Og is methyl (Me), ethyl (Et), propyl (Pr), vinyl (Vi), Chloroallyl (Pc), naphthalene (Na), phenyl (Ph), trifluoro One or more of propyl (Fp), phenyl-monofluoride base (Fb) and pentafluorophenyl group (Pf), X are that the quality in the acid sites lewis contains Amount, Y are the mass content of hydrophobic group.

3. according to catalyst as claimed in claim 1 or 2, it is characterised in that：The acid sites lewis matter in the Hydrophobic Catalyst Amount content is 0.5-30%；The mass content of hydrophobic group is 0.1-60%；The quality in the acid sites lewis and hydrophobic group Content summation accounts for the 1-60% of catalyst total amount.

4. according to catalyst as claimed in claim 1 or 2, it is characterised in that：The acid sites lewis matter in the Hydrophobic Catalyst It is 5~10% to measure content；The mass content of hydrophobic group is 20~25%；The quality in the acid sites lewis and hydrophobic group Content summation accounts for the 20~30% of catalyst total amount.

5. according to catalyst described in claim 1, it is characterised in that：Surfactant described in step 1) is anionic surface C8-20 sodium n-alkylbenzenesulfonates in activating agent or α-sodium olefin sulfonate, alternatively, for the C8- in nonionic surfactant Organic primary amine, Np series or the TWEEN Series surfactant of 20 long-chains, alternatively, for the hexadecane in cationic surfactant Base trimethyl amine bromide；The organic phase is hexamethylene, n-hexane or toluene；Cosurfactant is n-butanol, n-amyl alcohol, just Hexanol or n-octyl alcohol.

6. according to catalyst described in claim 1, it is characterised in that：The ammonia complexing solution of metal described in step 2) is metal The clear solution that salt is formed with ammonium hydroxide and water, metal salt：Water：The mass ratio of ammonium hydroxide is 0.01~1：1~4:0~4；Wherein, golden Belong to is Zr, Cr, Fe, Ti, one or more of Sn or Al.

7. a kind of any hydrophobic solid acid catalysts of claim 1-3 are in catalysis aromatic acid and low-carbon alcohols esterification In application.

8. applying according to claim 7, it is characterised in that：The aromatic acid includes benzoic acid, methyl benzoic acid, benzene Dioctyl phthalate, one or more of benzenetricarboxylic acid, wherein the methyl benzoic acid is p-methylbenzoic acid, adjacent methyl One or more of benzoic acid or m-methyl benzoic acid, the phthalic acid are terephthalic acid (TPA), phthalic acid Or one or more of M-phthalic acid, the benzenetricarboxylic acid are 1,3,5- tri- benzoic acid, 1,2,3- tri- benzoic acid Or one or more of tri- benzoic acid of 1,2,4-.

9. applying according to claim 7, it is characterised in that：The low-carbon alcohols are C1-C8 alcohol；Low-carbon alcohols are rubbed with acid You are than being 1.2:1-10:1, reaction temperature is 100-300 DEG C, pressure 1-3MPa；The Hydrophobic Catalyst dosage is virtue The 0.1-100% of fragrant acid quality.

10. applying according to claim 7, it is characterised in that：The low-carbon alcohols are C1-C8 alcohol；Low-carbon alcohols and acid Molar ratio is 2.5：1~3.5：1, reaction temperature is 160~200 DEG C, and pressure is 2.0~2.5MPa；The hydrophobic catalyst Agent dosage is the 5~10% of aromatic acid quality.