CN101618341A - Carbon-based solid acid catalyst and preparation method thereof - Google Patents
Carbon-based solid acid catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN101618341A CN101618341A CN200910023428A CN200910023428A CN101618341A CN 101618341 A CN101618341 A CN 101618341A CN 200910023428 A CN200910023428 A CN 200910023428A CN 200910023428 A CN200910023428 A CN 200910023428A CN 101618341 A CN101618341 A CN 101618341A
- Authority
- CN
- China
- Prior art keywords
- acid
- carbon
- benzene sulfonic
- based solid
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 239000011973 solid acid Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims abstract description 26
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006722 reduction reaction Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 229950000244 sulfanilic acid Drugs 0.000 claims abstract description 13
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940092714 benzenesulfonic acid Drugs 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- SMPBXFFGKXXYOG-UHFFFAOYSA-N N1N=CC=C1.C1=CC=CC(=C1)S(=O)(=O)O Chemical compound N1N=CC=C1.C1=CC=CC(=C1)S(=O)(=O)O SMPBXFFGKXXYOG-UHFFFAOYSA-N 0.000 claims description 35
- 239000012153 distilled water Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 239000003610 charcoal Substances 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003599 detergent Substances 0.000 claims description 9
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 4
- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 claims description 3
- 235000010289 potassium nitrite Nutrition 0.000 claims description 3
- 239000004304 potassium nitrite Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241001330002 Bambuseae Species 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000003245 coal Substances 0.000 claims description 2
- 229960002050 hydrofluoric acid Drugs 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000011257 shell material Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 239000002244 precipitate Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- -1 benzenesulphonic acid diazonium salt Chemical class 0.000 abstract description 3
- 239000012954 diazonium Substances 0.000 abstract 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 abstract 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract 1
- 238000006193 diazotization reaction Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 16
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 230000001195 anabolic effect Effects 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 235000010288 sodium nitrite Nutrition 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a carbon-based solid acid catalyst and a preparation method thereof, and the prepared catalyst takes active carbon as a carrier and benzene sulfonic acid as an acid center, and the active carbon and the benzene sulfonic acid are combined by a firm carbon-carbon covalent bond. The preparation method comprises the steps of firstly carrying out diazotization treatment on sulfanilic acid to obtain benzenesulphonic acid diazonium salt, then using hypophosphorous acid as a reducing agent to carry out reduction reaction on the benzenesulphonic acid diazonium salt on active carbon, and after the reaction is finished, filtering, washing and drying the product to obtain the carbon-based solid acid catalyst. The carbon-based solid acid catalyst has the advantages of stable structure, strong acidity, low cost, good catalytic effect, environmental protection and the like, and can be regenerated and reused.
Description
Technical field
The present invention relates to a kind of catalyst and preparation thereof, particularly a kind of carbon-based solid acid catalyst and preparation method thereof.
Background technology
Traditional homogeneous acid catalyst such as sulfuric acid, phosphoric acid, alchlor etc. are widely used in chemical process such as alkylation, esterification, hydrolysis, hydration, annual sulfuric acid as catalyst consumption just surpasses 1,500 ten thousand tons of (Hara, M, et al.Angew Chem Int Ed, 2004,43:2955-2958).The advantage of these homogeneous acids is that cost is low, acid by force, catalytic efficiency is high, but also has many shortcomings, and as easily causing equipment corrosion, catalyst is difficult to separate with reaction system, is difficult to recycling, easily causes environmental pollution etc.
Under the current overall background of advocating Green Chemistry and sustainable development, the high and eco-friendly solid-acid material of catalytic efficiency becomes the research focus in catalytic science field.Solid-acid material comprises zeolite molecular sieve, acidic oxide, heteropoly acid, phosphate and ion exchange resin etc.At present some solid acid catalysts have been realized commercialization production, be applied in 180 kinds of chemical process such as oil catalytic pyrolysis (Okuhara, T.Chem Rev, 2006,106:4044-4098).The result shows that these solid acid catalysis activity are higher, the easily separated and clean environment firendly of product, its weak point be acidity a little less than, and cost is higher.
Summary of the invention
Defective or deficiency at existing acid catalyst exists the objective of the invention is to, and a kind of with low cost and novel carbon-based solid acid catalyst that catalytic activity is high and preparation method thereof is provided.
In order to realize above-mentioned task, the present invention takes following technical solution:
A kind of carbon-based solid acid catalyst is characterized in that, the carrier of this catalyst that makes is an active carbon, and the acid site is a benzene sulfonic acid, between charcoal carrier and the acid site with the carbon-to-carbon covalent bonds.
The preparation method of above-mentioned carbon-based solid acid catalyst, it is characterized in that, at first aminobenzenesulfonic acid being carried out diazotising handles, obtain the benzene sulfonic acid diazol, then with hypophosphorous acid as reducing agent, make the benzene sulfonic acid diazol that reduction reaction take place on active carbon, after reaction finishes, after filtration, promptly get carbon-based solid acid catalyst after washing and the oven dry with active carbon.
Concrete steps are as follows:
The first step, the preparation of benzene sulfonic acid diazol:
In three-necked bottle, add sulfanilic acid and dilute acid soln, fully stir, the temperature of reaction system is controlled at 0-5 ℃, dropwise add the solubility nitrite, stirred again after dripping off 30-90 minute with ice-water bath, white solid, be the benzene sulfonic acid diazol.
Second step, reduction reaction
Add the benzene sulfonic acid diazol that makes in active carbon, distilled water, absolute ethyl alcohol and the first step in three-necked bottle, open electromagnetic agitation, add hypophosphorous acid and carry out reduction reaction, temperature is controlled at 0-5 ℃ in the course of reaction.Reaction is used distilled water and acetone detergent active charcoal after finishing successively, and dry 6h～18h under 120 ℃ obtains carbon-based solid acid catalyst in baking oven.
Described active carbon is to comprise the merchandise active carbon that various timber, bamboo, coal, shell or synthetic high polymer etc. obtain for raw material by various carbon sources, and its specific area is at 500-3000m
2/ g.
Described dilute acid soln is hydrochloric acid, sulfuric acid or boron fluoric acid.
Described solubility nitrite solution is natrium nitrosum or potassium nitrite.
The carbon-based solid acid catalyst that the present invention makes has following advantage:
(1) carrier active carbon mechanical strength height, Heat stability is good, specific area is big and aperture structure is abundant, and is and cheap.
(2) combine with firm covalent bond between carrier active carbon and the acid site benzene sulfonic acid, and unlike loaded catalyst be the simple physics suction-operated like that, thereby catalyst Heat stability is good, used carbon-based solid acid catalyst by simple filtering washing and drying after, promptly renewable and repeat use.
(3) used raw material active carbon, ethanol, hydrochloric acid, sulfanilic acid and hypophosphorous acid etc. are common agents, and are cheap and easy to get, so production cost is very low, has overcome conventional solid acid catalyst shortcoming on the high side, is expected to realize commercialization production.
(4) excellent catalytic effect and applied widely all has very high catalytic activity for general acid catalyzed reaction such as esterification, ester exchange, alkylation and hydration reaction etc.
The specific embodiment
Below the present invention is further elaborated by specific embodiment, need to prove that following embodiment is that the present invention is not limited to these embodiment for those skilled in the art better understands the present invention.
Embodiment 1:
The hydrochloric acid that in three-necked bottle, adds 0.075mol sulfanilic acid and 187ml, 1mol/l, the anabolic reaction system, open electromagnetic agitation, with ice-water bath temperature of reaction system is controlled at 4 ℃, in reaction system, slowly adds the sodium nitrite solution of 80ml, 1mol/l, stirring reaction 30min with separatory funnel, obtain white depositions, be the benzene sulfonic acid diazol,, filter standby with distilled water washing benzene sulfonic acid diazol.
The chemical equation of reaction system is as follows:
In three-necked bottle, add the 1.5g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and the hypophosphorous acid of 400ml, 50wt% and the benzene sulfonic acid diazol that makes, reaction 90min.
The chemical equation of reduction reaction is as follows:
With distilled water and acetone detergent active charcoal, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.
Effect: in round-bottomed flask, add the acetate of 0.1mol, the absolute ethyl alcohol of 1mol, the carbon-based solid acid catalyst of 0.3g, reflux down in 70 ℃, reaction 6h, the acetate conversion ratio is 92%.
Embodiment 2:
The hydrochloric acid that in three-necked bottle, adds 0.075mol sulfanilic acid and 187ml, 1mol/l, the anabolic reaction system, open electromagnetic agitation, with ice-water bath temperature of reaction system is controlled at 2 ℃, with separatory funnel slow sodium nitrite solution that adds 80ml, 1mol/l in reaction system, stirring reaction 60min, obtain white depositions, be the benzene sulfonic acid diazol,, filter standby with distilled water washing benzene sulfonic acid diazol.The chemical equation of reaction system is with embodiment 1.
In three-necked bottle, add the 1.5g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and the hypophosphorous acid of 400ml, 50wt% and the benzene sulfonic acid diazol that makes, reaction 90min.With distilled water and acetone detergent active charcoal, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.The chemical equation of reduction reaction is with embodiment 1.
Effect: in round-bottomed flask, add the acetate of 0.1mol, the absolute ethyl alcohol of 1mol, the carbon-based solid acid catalyst of 0.3g, reflux down in 70 ℃, reaction 6h, the acetate conversion ratio is 94%.
Embodiment 3:
The sulfuric acid that in three-necked bottle, adds 0.075mol sulfanilic acid and 187ml, 0.5mol/l, the anabolic reaction system, open electromagnetic agitation, with ice-water bath temperature of reaction system is controlled at 2 ℃, in reaction system, slowly adds 80ml, 1mol/l potassium nitrite solution, stirring reaction 90min with separatory funnel, obtain white depositions, be the benzene sulfonic acid diazol,, filter standby with distilled water washing benzene sulfonic acid diazol.The chemical equation of reaction system is with embodiment 1.
In three-necked bottle, add the 2.0g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and the hypophosphorous acid of 400ml, 50wt% and the benzene sulfonic acid diazol that makes, reaction 120min.With distilled water and acetone washing, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.The chemical equation of reduction reaction is with embodiment 1.
Effect: in round-bottomed flask, add the acetate of 0.1mol, the absolute ethyl alcohol of 1mol, the carbon-based solid acid catalyst of 0.3g, reflux down in 70 ℃, reaction 6h, the acetate conversion ratio is 92%.
Embodiment 4:
The sulfuric acid that in three-necked bottle, adds 0.075mol sulfanilic acid and 187ml, 0.5mol/l, the anabolic reaction system, open electromagnetic agitation, with ice-water bath temperature of reaction system is controlled at about 2 ℃, in reaction system, adds 80ml, 1mol/l sodium nitrite solution, stirring reaction 90min with separatory funnel, obtain white depositions, be the benzene sulfonic acid diazol,, filter standby with distilled water washing benzene sulfonic acid diazol.The chemical equation of reaction system is with embodiment 1.
In three-necked bottle, add the 1.5g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and the hypophosphorous acid of 400ml, 50wt% and the benzene sulfonic acid diazol that makes, reaction 120min.With distilled water and acetone detergent active charcoal, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.The chemical equation of reduction reaction is with embodiment 1.
Effect: in round-bottomed flask, add the oleic acid of 28.2g (0.1mol), the absolute ethyl alcohol of 60ml (1mol), the catalyst of 1.0g, reflux down in 80 ℃, reaction 8h, the oleic acid conversion ratio is 89%.
Embodiment 5:
The sulfuric acid that in three-necked bottle, adds 0.075mol sulfanilic acid and 187ml, 0.5mol/l, the anabolic reaction system, open electromagnetic agitation, with ice-water bath temperature of reaction system is controlled at about 2 ℃, in reaction system, adds 80ml, 1mol/l sodium nitrite solution, stirring reaction 90min with separatory funnel, obtain white depositions, be the benzene sulfonic acid diazol,, filter standby with distilled water washing benzene sulfonic acid diazol.The chemical equation of reaction system is with embodiment 1.
In three-necked bottle, add the 1.5g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and the hypophosphorous acid of 400ml, 50wt% and the benzene sulfonic acid diazol that makes, reaction 120min.With distilled water and acetone detergent active charcoal, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.The chemical equation of reduction reaction is with embodiment 1.
Effect: in round-bottomed flask, add the palmitic acid of 25.6g (0.1mol), the absolute ethyl alcohol of 60ml (1mol), the carbon-based solid acid catalyst of 1.0g, reflux down in 80 ℃, reaction 8h, esterification yield is 91%.
Embodiment 6:
The hydrochloric acid that in three-necked bottle, adds 0.075mol sulfanilic acid and 187ml, 0.5mol/l, the anabolic reaction system, open electromagnetic agitation, with ice-water bath temperature of reaction system is controlled at about 4 ℃, in reaction system, adds 80ml, 1mol/l sodium nitrite solution, stirring reaction 90min with separatory funnel, obtain white depositions, be the benzene sulfonic acid diazol,, filter standby with distilled water washing benzene sulfonic acid diazol.The chemical equation of reaction system is with embodiment 1.
In three-necked bottle, add the 1.5g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and the hypophosphorous acid of 400ml, 50wt% and the benzene sulfonic acid diazol that makes, reaction 120min.With distilled water and acetone detergent active charcoal, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.The chemical equation of reduction reaction is with embodiment 1.
Effect: in round-bottomed flask, add the palmitic acid of 25.6g (0.1mol), the methyl alcohol of 41ml (1mol), the catalyst of 1.0g, reflux down in 80 ℃, reaction 8h, esterification yield is 91%.
Embodiment 7:
The hydrochloric acid that in three-necked bottle, adds 0.075mol sulfanilic acid and 187ml, 0.5mol/l, the anabolic reaction system, open electromagnetic agitation, with ice-water bath temperature of reaction system is controlled at about 2 ℃, in reaction system, adds 80ml, 1mol/l sodium nitrite solution, stirring reaction 90min with separatory funnel, obtain white depositions, be the benzene sulfonic acid diazol,, filter standby with distilled water washing benzene sulfonic acid diazol.The chemical equation of reaction system is with embodiment 1.
In three-necked bottle, add the 1.5g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and the hypophosphorous acid of 400ml, 50wt% and the benzene sulfonic acid diazol that makes, reaction 120min.With distilled water and acetone detergent active charcoal, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.The chemical equation of reduction reaction is with embodiment 1.
Effect: in round-bottomed flask, add the stearic acid of 28.4g (0.1mol), the absolute ethyl alcohol of 60ml (1mol), the carbon-based solid acid catalyst of 1.0g, reflux down in 80 ℃, reaction 8h, esterification yield is 89%.
Embodiment 8:
The hydrochloric acid that in three-necked bottle, adds 0.075mol sulfanilic acid and 187ml, 0.5mol/l, the anabolic reaction system, open electromagnetic agitation, with ice-water bath temperature of reaction system is controlled at about 2 ℃, in reaction system, adds 80ml, 1mol/l sodium nitrite solution, stirring reaction 90 minutes with separatory funnel, obtain white depositions, be the benzene sulfonic acid diazol,, filter standby with distilled water washing benzene sulfonic acid diazol.The chemical equation of reaction system is with embodiment 1.
In three-necked bottle, add the 1.5g active carbon then, 100ml absolute ethyl alcohol, 100ml distilled water, and the hypophosphorous acid of 400ml, 50wt% and the benzene sulfonic acid diazol that makes, reaction 120min.With distilled water and acetone detergent active charcoal, dry 12h under 120 ℃ can obtain carbon-based solid acid catalyst in baking oven.The chemical equation of reduction reaction is with embodiment 1.
Effect: in round-bottomed flask, add the stearic acid of 28.4g (0.1mol), the methyl alcohol of 41ml (1mol), the carbon-based solid acid catalyst of 1.0g, reflux down in 80 ℃, reaction 8h, esterification yield is 91%.
Claims (6)
1. a carbon-based solid acid catalyst is characterized in that, the carrier of this catalyst that makes is an active carbon, and the acid site is a benzene sulfonic acid, between charcoal carrier and the acid site with the carbon-to-carbon covalent bonds.
2. carbon-based solid acid catalyst as claimed in claim 1 is characterized in that described active carbon is is the extensive stock active carbon that raw material obtains by timber, bamboo, coal, shell and synthetic high polymer, and its specific area is at 500m
2/ g～3000m
2/ g.
3. the preparation method of the described carbon-based solid acid catalyst of claim 1, it is characterized in that, at first sulfanilic acid being carried out diazotising handles, obtain the benzene sulfonic acid diazol, then with hypophosphorous acid as reducing agent, make the benzene sulfonic acid diazol that reduction reaction take place on active carbon, after reaction finishes, after filtration, promptly get carbon-based solid acid catalyst after washing and the oven dry with active carbon.
4, method as claimed in claim 3 is characterized in that, comprises the steps:
The first step, the preparation of benzene sulfonic acid diazol:
In flask, add sulfanilic acid and dilute acid soln, fully stir, make temperature of reaction system remain on 0～5 ℃ with ice-water bath, under agitation drip an amount of solubility nitrite solution, reaction 30min～90min obtains white precipitate, i.e. the benzene sulfonic acid diazol;
To the filtration of benzene sulfonic acid diazol, washing, the drying that obtains;
Second step, reduction reaction:
Adding the benzene sulfonic acid diazol that makes in active carbon, distilled water, absolute ethyl alcohol and the first step in flask, is reducing agent with the hypophosphorous acid, reacts 30min～120min down at 0～5 ℃; Reaction is used distilled water and acetone detergent active charcoal after finishing successively, and dry 6h～18h under 120 ℃ promptly obtains carbon-based solid acid catalyst in baking oven.
5. method as claimed in claim 4 is characterized in that, described dilute acid soln is hydrochloric acid, sulfuric acid or boron fluoric acid.
6. method as claimed in claim 4 is characterized in that, described solubility nitrite is natrium nitrosum or potassium nitrite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100234287A CN101618341B (en) | 2009-07-27 | 2009-07-27 | Carbon-based solid acid catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100234287A CN101618341B (en) | 2009-07-27 | 2009-07-27 | Carbon-based solid acid catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101618341A true CN101618341A (en) | 2010-01-06 |
| CN101618341B CN101618341B (en) | 2012-05-23 |
Family
ID=41511850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100234287A Expired - Fee Related CN101618341B (en) | 2009-07-27 | 2009-07-27 | Carbon-based solid acid catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101618341B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029188A (en) * | 2010-11-15 | 2011-04-27 | 西北农林科技大学 | Carbon-based solid acid catalyst with high specific surface area and preparation method thereof |
| CN102491322A (en) * | 2011-12-12 | 2012-06-13 | 福建农林大学 | Preparation method of active carbon fixed with organic functional group on surface |
| CN102600893A (en) * | 2012-03-02 | 2012-07-25 | 宁夏大学 | Carbon-based solid acid catalyst and preparation method thereof |
| CN103084187A (en) * | 2012-12-17 | 2013-05-08 | 常州大学 | Carbon-based solid acid and preparation method thereof |
| CN103878025A (en) * | 2014-03-31 | 2014-06-25 | 福建农林大学 | Activated carbon-based solid acid catalyst and preparation method thereof |
| CN105130783A (en) * | 2015-09-24 | 2015-12-09 | 中国科学技术大学 | Preparation method of succinic acid |
| CN105289722A (en) * | 2015-11-04 | 2016-02-03 | 常州大学 | Catalyst used for synthesizing methyl ethyl carbonate by ester exchange and preparation method of catalyst |
| CN108786738A (en) * | 2018-07-03 | 2018-11-13 | 西北农林科技大学 | A kind of magnesium salts modification biological charcoal and its application |
| CN109777896A (en) * | 2019-02-27 | 2019-05-21 | 天津大学 | The method that magnetic solid acid catalyzing cellulose hydrolysis prepares glucose |
| CN110190290A (en) * | 2019-06-12 | 2019-08-30 | 浙江科技学院 | The preparation method of sulfonated platinum carbon catalyst |
| CN115304480A (en) * | 2022-08-12 | 2022-11-08 | 浙江嘉澳环保科技股份有限公司 | Preparation method of tributyl citrate and acetyl tributyl citrate |
-
2009
- 2009-07-27 CN CN2009100234287A patent/CN101618341B/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029188A (en) * | 2010-11-15 | 2011-04-27 | 西北农林科技大学 | Carbon-based solid acid catalyst with high specific surface area and preparation method thereof |
| CN102491322A (en) * | 2011-12-12 | 2012-06-13 | 福建农林大学 | Preparation method of active carbon fixed with organic functional group on surface |
| CN102600893B (en) * | 2012-03-02 | 2014-05-07 | 宁夏大学 | Carbon-based solid acid catalyst and preparation method thereof |
| CN102600893A (en) * | 2012-03-02 | 2012-07-25 | 宁夏大学 | Carbon-based solid acid catalyst and preparation method thereof |
| CN103084187B (en) * | 2012-12-17 | 2015-07-01 | 常州大学 | Carbon-based solid acid and preparation method thereof |
| CN103084187A (en) * | 2012-12-17 | 2013-05-08 | 常州大学 | Carbon-based solid acid and preparation method thereof |
| CN103878025A (en) * | 2014-03-31 | 2014-06-25 | 福建农林大学 | Activated carbon-based solid acid catalyst and preparation method thereof |
| CN105130783A (en) * | 2015-09-24 | 2015-12-09 | 中国科学技术大学 | Preparation method of succinic acid |
| CN105289722A (en) * | 2015-11-04 | 2016-02-03 | 常州大学 | Catalyst used for synthesizing methyl ethyl carbonate by ester exchange and preparation method of catalyst |
| CN105289722B (en) * | 2015-11-04 | 2017-08-01 | 常州大学 | It is a kind of for catalyst of ester exchange Catalysts of Preparing Methyl Ethyl Carbonate and preparation method thereof |
| CN108786738A (en) * | 2018-07-03 | 2018-11-13 | 西北农林科技大学 | A kind of magnesium salts modification biological charcoal and its application |
| CN109777896A (en) * | 2019-02-27 | 2019-05-21 | 天津大学 | The method that magnetic solid acid catalyzing cellulose hydrolysis prepares glucose |
| CN110190290A (en) * | 2019-06-12 | 2019-08-30 | 浙江科技学院 | The preparation method of sulfonated platinum carbon catalyst |
| CN115304480A (en) * | 2022-08-12 | 2022-11-08 | 浙江嘉澳环保科技股份有限公司 | Preparation method of tributyl citrate and acetyl tributyl citrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101618341B (en) | 2012-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101618341B (en) | Carbon-based solid acid catalyst and preparation method thereof | |
| Zhang et al. | Functionalized organic–inorganic hybrid porous coordination polymer-based catalysts for biodiesel production via trans/esterification | |
| CN102153465B (en) | Method for preparing low acid-value fatty acid methyl ester | |
| CN101890364B (en) | Method of using agricultural and forestry waste to prepare solid-acid catalyst | |
| Zhang et al. | An overview of metal-organic frameworks-based acid/base catalysts for biofuel synthesis | |
| Zhang et al. | Recent advances in supported acid/base ionic liquids as catalysts for biodiesel production | |
| CN105112170A (en) | Method for preparing biodiesel through sulfonic acid type phosphotungstic acid ionic liquid in catalysis mode | |
| CN107413382B (en) | Acid-base double-center solid catalyst for synthesizing biodiesel and preparation method thereof | |
| Bhagat et al. | Carbon‐based nanocatalysts in biodiesel production | |
| CN101338214A (en) | Method for preparing biodiesel using acidizing oil as raw material under normal pressure | |
| CN102029188A (en) | Carbon-based solid acid catalyst with high specific surface area and preparation method thereof | |
| CN114602512B (en) | Preparation method of esterification catalyst | |
| CN102701907B (en) | Green method for preparing nopol | |
| CN106268938B (en) | A kind of bisgallic acid position solid-carrying type ionic-liquid catalyst of biodiesel synthesis and preparation method thereof | |
| CN102505186B (en) | Magnetic sulphonated carbon-based nanofiber, preparation method for same and application thereof | |
| CN103614244A (en) | Method for preparing biodiesel by using carbon-based sulfonic acid functionalized solid acid as catalyst | |
| CN110437892B (en) | Biodiesel preparation process | |
| CN101225324B (en) | One-step method for preparing biodiesel by low-acid catalytic fatty or fatty acid | |
| CN104194948B (en) | Method for catalyzing phosphotungstic acid ionic liquid to prepare biodiesel | |
| CN110090662B (en) | Preparation method and catalytic application of sulfonic group covalent modified vacancy polyacid composite material | |
| CN110624608A (en) | Preparation process and application of Fe-based metal organic framework solid acid catalyst | |
| CN102125876B (en) | Method for preparing biodiesel by microwave solid alkali ester exchange method | |
| CN104399515A (en) | High-efficiency composite catalyst for preparing acrylic acid by using lactic acid for catalytic dehydration and preparation method and application of high-efficiency composite catalyst | |
| CN103285883A (en) | Preparation method of carbon-based sulfoacid solid acid catalyst | |
| CN109438232A (en) | A kind of preparation method of tributyl citrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20130727 |