CN104368340A - Sponge silver catalyst preparation method and application of sponge silver catalyst to oxidation and synthesis of cinnamic acid from cinnamaldehyde - Google Patents
Sponge silver catalyst preparation method and application of sponge silver catalyst to oxidation and synthesis of cinnamic acid from cinnamaldehyde Download PDFInfo
- Publication number
- CN104368340A CN104368340A CN201410718928.3A CN201410718928A CN104368340A CN 104368340 A CN104368340 A CN 104368340A CN 201410718928 A CN201410718928 A CN 201410718928A CN 104368340 A CN104368340 A CN 104368340A
- Authority
- CN
- China
- Prior art keywords
- silver
- reaction
- cinnamic acid
- sponge
- catalyst
- 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
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 title claims abstract description 75
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 title claims abstract description 74
- 229930016911 cinnamic acid Natural products 0.000 title claims abstract description 74
- 235000013985 cinnamic acid Nutrition 0.000 title claims abstract description 74
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000004332 silver Substances 0.000 title claims abstract description 56
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 12
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 title abstract description 4
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 title abstract description 4
- 229940117916 cinnamic aldehyde Drugs 0.000 title abstract description 4
- 230000003647 oxidation Effects 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 17
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 15
- 239000011591 potassium Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 21
- 230000001590 oxidative effect Effects 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- DXIHILNWDOYYCH-UHDJGPCESA-M sodium;(e)-3-phenylprop-2-enoate Chemical compound [Na+].[O-]C(=O)\C=C\C1=CC=CC=C1 DXIHILNWDOYYCH-UHDJGPCESA-M 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 235000002639 sodium chloride Nutrition 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 229960002668 sodium chloride Drugs 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 11
- 229910021607 Silver chloride Inorganic materials 0.000 abstract description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- RPIDHIXGMLSIMK-UHFFFAOYSA-N C=C=O.C(C1=CC=CC=C1)=O Chemical compound C=C=O.C(C1=CC=CC=C1)=O RPIDHIXGMLSIMK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000723347 Cinnamomum Species 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 235000017803 cinnamon Nutrition 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- -1 sodium alkoxide Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MVZXTUSAYBWAAM-UHFFFAOYSA-N iron;sulfuric acid Chemical compound [Fe].OS(O)(=O)=O MVZXTUSAYBWAAM-UHFFFAOYSA-N 0.000 description 1
- 150000002561 ketenes Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- KEWUJFMWXNEDIF-UHFFFAOYSA-N styrene;tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl.C=CC1=CC=CC=C1 KEWUJFMWXNEDIF-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Abstract
The invention provides a sponge silver catalyst preparation method and application of a sponge silver catalyst to oxidation and synthesis of cinnamic acid from cinnamaldehyde. The sponge silver catalyst is prepared by means of adding silver chloride into 5-15% ammonium hydroxide with stirring for more than 30 minutes, then dropwise adding 5-15% of sodium borohydride or potassium borohydride solution, continuing reacting for more than 15 minutes after dropping and performing filtering and washing after action is finished. In the whole reaction process, the mass ratio among ammonia, sodium borohydride or potassium borohydride and the silver chloride is 2-10:0.5-2:10, and the reaction temperature is 0-30 DEG C. The sponge silver is used as the catalyst to be applied to a method for preparing the cinnamic acid from pure oxygen and the cinnamaldehyde. The catalyst prepared by the method can be reused for hundreds of times, and yield of the synthetic cinnamic acid can reach above 95%.
Description
Technical field
The invention belongs to technical field of fine chemical synthesis, specifically provide a kind of preparation of sponge silver catalyst and the application in cinnamic acid oxidative synthesis cinnamic acid thereof.
Technical background
Cinnamic acid (chemical name cinnamic acid) is a kind of very important industrial chemicals, is widely used in the fields such as medicine, spices, food, macromolecular material, photosensitive material and synthetic intermediate.Current cinnamic acid has multiple synthetic route, mainly contains perkin method, benzaldehyde-ketene process, styrene-carbon tetrachloride method, benzaldehyde-acetin method and cinnamic acid oxidizing process etc.Perkin method is that benzaldehyde and acetic anhydride prepare cinnamic acid under the catalytic action of anhydrous sodium acetate, be realize industrialization the 1950's since both at home and abroad produce the topmost method of cinnamic acid, but along with the price of benzaldehyde and acetic anhydride sharp rises, its cost raises gradually, add the method yield low, seriously polluted, lack competitiveness gradually.Styrene-carbon tetrachloride method is that addition under catalyst action generates 1.3.3.3-phenyl tetrachloride propane with styrene and carbon tetrachloride, and then alkaline hydrolysis generates cinnamic acid, and this process environments is seriously polluted, and product quality is poor.Benzaldehyde-acetin method under sodium alkoxide, is condensed into cinnamate with benzaldehyde and ethyl ester methyl ester (or EtOAc), cinnamic acid is generated through acidolysis, alkaline hydrolysis, acidifying, this process by-product 3-methoxyl group-phenylpropionic acid is difficult to be separated, and difficult quality reaches commodity requirement.And benzaldehyde-ketene process, be the technique of BASF Aktiengesellschaft's exploitation, ketenes severe toxicity, industry report is not quite clear.All there is very formidable defect in above-mentioned preparation of cinnamon acid method, is all eliminated gradually.
In recent years, people start to study the technique using cinnamic acid catalytic oxidation to prepare cinnamic acid gradually, as day disclosure report with cinnamic acid and pure oxygen for raw material, Ag/c makes catalyst preparing cinnamic acid, and this method synthesizing cinnamic acid yield is higher, it is little to pollute, but catalyst easily occurs comes off, active carbon easily adsorbs cinnamic acid makes catalysqt deactivation, after catalyst reuses more than 10 times, activity reduces greatly, only has bibliographical information at present, there is no suitability for industrialized production report.Chinese patent (publication number: CN102826992A) report is raw material with cinnamic acid, oxidant made by pure oxygen, make catalyst with nano silver particles to be oxidized under lower than 0.45MPa pressure, its cinnamic acid yield 95.8% of technique disclosed in this patent, but easily blast when being oxidized in this technique, high to equipment requirement.And nano silver particles catalyst preparation conditions is quite harsh, because nanometer-level silver particle granules is very little, run off during filtration serious, number of repetition is restricted, catalyst number of repetition only 48-55 time.
Sponge silver is the Argent grain with sponge structure; the preparation method of existing sponge silver mainly uses reducing agent Reduction of Silver Chloride or silver nitrate; existing reducing agent generally adopts hydrazine hydrate, sodium thiosulfate, iron-sulfuric acid, water soluble aldehyde etc.; the incomplete phenomenon of reaction is often there will be in whole reduction reaction; just there will be a lot of impurity; the sponge silver purity, surface area etc. that cause existing method to be prepared are restricted, activity is little, and even some impurity can use catalyst poisoning as iron, sulphur etc. and lose activity.
Summary of the invention
The present invention provides a kind of preparation of sponge silver catalyst and the application in cinnamic acid oxidative synthesis cinnamic acid thereof according to the deficiencies in the prior art, the preparation method of the sponge silver catalyst provided in the present invention is different from the preparation method of Ag/c catalyst and nano silver particles catalyst, also the preparation method of existing sponge silver is different from, its water absorption rate reaches 60-80%, particle is large, surface area is large, activity is very high, and the yield preparing cinnamic acid is high, and purity is also high, number of repetition is many, is applicable to suitability for industrialized production.
Technical scheme provided by the invention: the preparation of described a kind of sponge silver catalyst, is characterized in that concrete steps are as follows:
(1) get a certain amount of silver chlorate add concentration be in the ammoniacal liquor of 5% ~ 15% stir more than 30 minutes, then sodium borohydride or solution of potassium borohydride that concentration is 5% ~ 15% is dripped, drip off rear continuation reaction more than 15 minutes, ammonia in whole reaction: sodium borohydride or potassium borohydride: the mass ratio of silver chlorate is 2 ~ 10:0.5 ~ 2:10, and reaction temperature is 0 ~ 30 DEG C.Because reaction is exothermic reaction, so whole reaction bulb can be placed in cold water or frozen water in course of reaction, or be provided with interlayer in the outside of reactor, and in interlayer, pass into cold water or other condensate liquid carrys out control temperature.
(2) by solid matter after completion of the reaction in step (1) through filtering, and just obtain sponge silver catalyst by pure water to neutrality.
The silver chlorate of the use of the present invention in step (1) can directly also can be prepared from according to following steps by commodity in use silver chlorate:
(1) a certain amount of argent or recover silver is taken, and slowly add concentration 65% nitric acid, after treating that nitric acid adds, add pure water after starting to be warming up to complete reaction to dilute silver nitrate, silver nitrate ultimate density in reaction is caused to be 20% ~ 30%, filter after reaction and remove insoluble impurity to obtain liquor argenti nitratis ophthalmicus for subsequent use, the temperature-rise period of reaction rises from normal temperature, and its maximum temperature is not higher than 120 DEG C;
(2) sodium chloride is mixed with sodium-chloride water solution, slowly join in the liquor argenti nitratis ophthalmicus in step (1), solid matter after reacting completely to complete reaction, and is passed through filtration, pure water to neutral by rapid stirring, obtains silver chlorate solid.
Best-of-breed technology scheme of the present invention is: silver chlorate being added concentration in step (1) is that in 5% ~ 15% ammoniacal liquor, mixing time is 0.5 ~ 1.2 hour; Drip concentration be 5% ~ 15% sodium borohydride or solution of potassium borohydride after the continuation reaction time be 15 minutes ~ 1 hour.
Another kind of technical scheme provided by the invention is: the application of a kind of sponge silver catalyst in the method for cinnamic acid oxidative synthesis cinnamic acid, is characterized in that concrete steps are as follows:
(1) preparation of sponge silver: (1) get a certain amount of silver chlorate add concentration be in the ammoniacal liquor of 5% ~ 15% stir more than 30 minutes, optimum reacting time is 30 minutes to 1.2 hours, then sodium borohydride or solution of potassium borohydride that concentration is 5% ~ 15% is dripped, drip off rear continuation reaction more than 15 minutes, optimum reacting time be 15 minutes little of complete reaction to 1, ammonia in whole reaction: sodium borohydride or potassium borohydride: the mass ratio of silver chlorate is 2 ~ 10:0.5 ~ 2:10, and reaction temperature is 0 ~ 30 DEG C;
(2) oxidation reaction: with the sponge silver of preparation in step (1) for catalyst, be that oxidant slowly drips cinnamic acid in sodium hydrate aqueous solution with pure oxygen, generates sodium cinnamate; The reactant sponge silver of oxidation reaction: cinnamic acid: NaOH: the mass ratio of water is 0.15 ~ 0.2:0.95 ~ 1:0.3 ~ 0.33:10, reaction temperature 30 ~ 60 DEG C, during the rate of addition 1.5 ~ 2.5L/min of cinnamic acid, oxygen gas flow rate 80 ~ 200L/min.Oxygen in this oxidation reaction passes in reactant liquor under fast stirring;
(3) acid out: sodium cinnamate oxidation reaction generated, through dilute sulfuric acid or hydrochloric acid acid out, generates cinnamic acid.
In the method for above-mentioned cinnamic acid oxidative synthesis cinnamic acid, the concrete reaction equation of oxidation reaction is as follows:
In the method for above-mentioned cinnamic acid oxidative synthesis cinnamic acid, the concrete reaction equation of acid precipitation reaction is as follows:
All solution in the present invention are the aqueous solution, in the present invention the preparation method of cinnamic acid can adopt existing with cinnamic acid and pure oxygen for raw material, silver is catalyst preparing cinnamic acid method, the catalyst in existing method is replaced with the sponge silver prepared according to the present invention.
Sponge silver catalyst in the present invention is obtained with sodium borohydride or potassium borohydride reduction in ammoniacal liquor by silver chlorate, ammoniacal liquor is added in preparation process, dissolving peptizaiton is had to silver chlorate solid, neutralization is had to the hydrogen chloride produced, and sodium borohydride or potassium borohydride reduction time release a large amount of hydrogen, obtained sponge silver granule surface area is increased greatly, obtained sponge silver particle is large, active high, water absorption rate reaches 60 ~ 80%, using this sponge silver as catalyst application in the preparation of cinnamic acid, almost can infinitely reuse, but it is serious to run off because repeatedly repeating rear granularity too little, catalytic effect can be affected, generally reuse 200 ~ 250 times, nitric acid nitrating after washing, react with sodium chloride and generate silver chlorate, silver chloride reduction can repeat to make sponge silver catalyst, continue to use.Through overtesting, use this sponge silver can reach more than 95% as the yield of catalyst preparing cinnamic acid, and purity is also higher, goes for suitability for industrialized production.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated.
Example 1: a kind of sponge silver catalyst preparation process: take argent or recover silver 38 grams, slowly add 60 grams, the nitric acid of 65%, heat up and complete reaction, and add 80 grams of pure water, filter and remove insoluble impurity, obtain liquor argenti nitratis ophthalmicus, 22 grams of sodium chloride are dissolved in 100 grams of pure water, slowly add in liquor argenti nitratis ophthalmicus, rapid stirring, after reacting completely, filtration washing obtains silver chlorate solid to neutral; It is in the ammoniacal liquor of 10% that all silver chlorates obtained are dissolved in 200 grams of concentration, stir 60min, slowly dripping 50 grams of concentration is the sodium borohydride solution of 10%, add rear continuation reaction 30min to complete reaction, reaction temperature controls at 0 ~ 30 DEG C, and after question response, filtration washing obtains sponge silver catalyst to neutral.
Embodiment 2: a kind of sponge silver catalyst preparation process: take silver chlorate 50.5 grams and add in the ammoniacal liquor of 200 gram 10%, stir 60min, cool to 5 ± 1 DEG C, slowly drip the solution of potassium borohydride of 60 gram 10%, add follow-up continuous insulation reaction 30min, filtration washing, to neutral, obtains sponge silver catalyst.
Embodiment 3: a kind of sponge silver catalyst preparation process: take silver chlorate 50.5 grams and add in the ammoniacal liquor of 200 gram 10%, the sodium borohydride solution of 50 gram 10% is slowly dripped temperature about 25 DEG C, add rear continuation and keep temperature about 25 DEG C reaction 30min, filtration washing, to neutral, obtains sponge silver catalyst.
Embodiment 4: the application of a kind of sponge silver catalyst in cinnamic acid oxidative synthesis cinnamic acid, its concrete steps are as follows:
(1) in 3000ml flask, drop into the sponge silver catalyst 38 grams of preparation in embodiment 1, add sodium hydroxide solution (industrial lye) and 2200 grams of pure water that 220 grams of concentration are 32%, pass into oxygen at ambient pressure 5 minutes, and stirring is warmed up to 40 DEG C, start to drip cinnamic acid 210 grams, the speed that adds of cinnamic acid is 2ml/min, oxygen passes into flow velocity 5-10L/h, mixing speed 500 ~ 800r/min, control reaction temperature 40 ~ 50 DEG C, reinforced complete continuation is led to oxygen and is stirred 30min, leave standstill 30min, bottom catalyst sedimentation, the upper strata sodium cinnamate aqueous solution filters and catalyst separation, reusable more than 200 times of catalyst,
(2) the sodium cinnamate aqueous solution that step (1) obtains is poured in another reaction bulb, be warmed up to 65 DEG C, add dilute sulfuric acid and adjust pH value 3 ~ 4, cool to room temperature, crystal filters after separating out, solid purified rinse water more than 3 times, drain when waste liquid pH value reaches 5 ~ 6, dry cinnamic acid 225 grams, content more than 99%, fusing point 133 ~ 135 DEG C, yield 95.6%.
Embodiment 5: the application of a kind of sponge silver catalyst in cinnamic acid oxidative synthesis cinnamic acid, its concrete steps are as follows:
(1) this step is identical with the step (1) in embodiment 4, and catalyst in the oxidation reaction adopts the sponge silver catalyst of preparation in embodiment 2, obtains sodium cinnamate solution after peroxidization;
(2) the sodium cinnamate solution obtained is poured in another reaction bulb, be warmed up to 65 DEG C, add dilute sulfuric acid and adjust pH value 3-4, cool to room temperature, crystal separates out rear filtering solids purified rinse water more than 3 times, drains when waste liquid pH value reaches 5-6, dry cinnamic acid 224.5 grams, content more than 99%, fusing point 133-135 DEG C, yield 95.6%.
Embodiment 6: the application of a kind of sponge silver catalyst in cinnamic acid oxidative synthesis cinnamic acid, its concrete steps are as follows:
(1) this step is identical with the step (1) in embodiment 4, and catalyst in the oxidation reaction adopts the sponge silver catalyst of preparation in embodiment 3, obtains sodium cinnamate solution after peroxidization;
(2) this step is identical with the step (2) in embodiment 4, finally obtains cinnamic acid 223 grams, content 99.1%, fusing point 131-133 DEG C, yield 94.7%.
Applicant adopts the sponge silver oxide catalyst of preparation in embodiment 1, embodiment 2 and embodiment 3 to be applied in the preparation of cinnamic acid, the cinnamic acid yield obtained all reaches more than 94.5%, its yield is very high, and all reusable more than 200 times of catalyst in three embodiments, greatly save cost.
Application also adopts existing preparation of cinnamon acid method to carry out many groups contrast test:
The method concrete steps of contrast test 1 one kinds of synthesizing cinnamic acid by catalyzed oxidation cinnamic aldehyde are as follows:
(1) all silver chlorate solids of preparation in embodiment 1 are joined in the pure water of 200 grams, and add sodium hydroxide solution tune pH value 12, stir 60 minutes, slowly drip the sodium borohydride solution of 50 gram 10%, add rear continuation reaction 30min, filtration washing, to neutral, obtains silver catalyst;
(2) process of the silver catalyst in step (1) being pressed the step (1) in example 2 drops in the oxidation reaction of cinnamic acid, obtain the yellow sodium cinnamate aqueous solution, and step (2) acid out in sodium cinnamate aqueous solution installation embodiment 2 is obtained faint yellow cinnamic acid crystallization 206 grams, content 96.5%, fusing point 123-129 DEG C, yield 87.5%.
Contrast test 2 adopt day disclosure report with cinnamic acid and pure oxygen for raw material, Ag/c makes the method for catalyst preparing cinnamic acid, and concrete steps are as follows:
(1) 20 grams of silver nitrates are dissolved in 300ml distilled water, add active carbon 5 grams, the formalin of 11 gram 37%, the sodium hydroxide solution 16 grams of 50% is dripped under rapid stirring 0 ~ 5 DEG C time, continue stirring 1.5 hours at 0-5 DEG C after dropwising, after filtration, washing, drying, obtain Ag/c catalyst.
(2) in 1000ml flask, add distilled water 600ml, 44 grams, the NaOH (0.55mol) of 50%, 2, surfactant, silicone defoaming agent 1, oxygen is passed under strong agitation, slowly drip cinnamic acid 66 grams (0.5mol), cinnamic acid dropwises simultaneously, then continues logical oxygen stirring 30min, filter after sedimentation, reclaim Ag/c catalyst, filtrate obtains cinnamic acid crystallization through acid out, and washing is dry afterwards obtains 68.2 grams, cinnamic acid crystal, fusing point 131-134 DEG C, yield 92.2%; Ag/c catalyst in the method generally reuses about 10 times.
Contrast test 3 adopts publication number to be that the open method of Chinese patent of CN102826992A prepares cinnamic acid, and concrete steps are as follows:
(1) silver nitrate 20 grams is dissolved in 45 grams of pure water, add sodium hydroxide solution and regulate pH value 10-12, the formalin of 11 gram 37% is dripped in solution, ultrasonic oscillation is carried out in dropping process, time for adding 20-35min, stir 0.5-1 hour, washing is dried, and obtains nano silver particles catalyst 12.7 grams;
(2) that drops into that nano silver particles catalyst carries out cinnamic acid by the step (2) of contrast test 2 is oxidized to obtain the sodium cinnamate aqueous solution, through acid out, washing, dry 70.8 grams, cinnamic acid crystal, fusing point 132-135 DEG C, content 99.3%, yield 95.7%, catalyst is reused 48-55 time.
Can find out that the reusable number of times of sponge silver catalyst prepared by the present invention is much higher than existing several catalyst by above-mentioned contrast test, and adopt the cinnamic acid of the catalyst preparing in the present invention all higher on content, yield.
Claims (4)
1. a preparation for sponge silver catalyst, is characterized in that concrete steps are as follows:
(1) get a certain amount of silver chlorate add concentration be in the ammoniacal liquor of 5% ~ 15% stir more than 30 minutes, then sodium borohydride or solution of potassium borohydride that concentration is 5% ~ 15% is dripped, drip off rear continuation reaction more than 15 minutes, ammonia in whole reaction: sodium borohydride or potassium borohydride: the mass ratio of silver chlorate is 2 ~ 10:0.5 ~ 2:10, and reaction temperature is 0 ~ 30 DEG C;
(2) by solid matter after completion of the reaction in step (1) through filtering, and just obtain sponge silver catalyst by pure water to neutrality.
2. the preparation of a kind of sponge silver catalyst according to claim 1, is characterized in that being prepared from according to following steps of the silver chlorate in step (1):
(1) a certain amount of argent or recover silver is taken, and slowly add the nitric acid of concentration 65%, after treating that nitric acid adds, add pure water after starting to be warming up to complete reaction to dilute the silver nitrate be obtained by reacting, silver nitrate ultimate density in reaction is caused to be 20% ~ 30%, filter after reaction and remove insoluble impurity to obtain liquor argenti nitratis ophthalmicus for subsequent use, the temperature-rise period of reaction rises from normal temperature, and its maximum temperature is not higher than 120 DEG C;
(2) sodium chloride is mixed with sodium-chloride water solution, slowly joins in the liquor argenti nitratis ophthalmicus in step (1), rapid stirring is to complete reaction, and after reacting completely, solid matter passes through filtration, pure water to neutral, obtains silver chlorate solid.
3. the preparation of a kind of sponge silver catalyst according to claim 1, it is characterized in that in step (1) that silver chlorate joins concentration is that after 5% ~ 15% ammoniacal liquor, mixing time is 0.5 ~ 1.2 hour, drip concentration be 5% ~ 15% sodium borohydride or solution of potassium borohydride after to continue the reaction time be 15 minutes ~ 1 hour.
4. the application of sponge silver catalyst in the method for cinnamic acid oxidative synthesis cinnamic acid, is characterized in that concrete steps are as follows:
(1) preparation of sponge silver: get a certain amount of silver chlorate add concentration be in 5% ~ 15% ammoniacal liquor stir more than 30 minutes, then sodium borohydride or solution of potassium borohydride that concentration is 5% ~ 15% is dripped, drip off rear continuation reaction more than 15 minutes, after question response, by the solid matter be obtained by reacting through filtering, and pure water just obtains sponge silver to neutrality; Ammonia in whole reaction: sodium borohydride or potassium borohydride: the mass ratio of silver chlorate is 2 ~ 10:0.5 ~ 2:10, reaction temperature 0 ~ 30 DEG C;
(2) oxidation reaction: with the sponge silver of preparation in step (1) for catalyst, be that oxidant slowly drips cinnamic acid in sodium hydrate aqueous solution with pure oxygen, generates sodium cinnamate; The reactant sponge silver of oxidation reaction: cinnamic acid: NaOH: the mass ratio of water is 0.15 ~ 0.2:0.95 ~ 1:0.3 ~ 0.33:10, reaction temperature 30 ~ 60 DEG C, during the rate of addition 1.5 ~ 2.5L/min of cinnamic acid, oxygen passes into flow velocity 80 ~ 200L/min;
(3) acid out: sodium cinnamate oxidation reaction generated, through dilute sulfuric acid or hydrochloric acid acid out, generates cinnamic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410718928.3A CN104368340B (en) | 2014-12-01 | 2014-12-01 | A kind of preparation of sponge silver catalyst and the application in cinnamic acid oxidation synthesizing cinnamic acid thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410718928.3A CN104368340B (en) | 2014-12-01 | 2014-12-01 | A kind of preparation of sponge silver catalyst and the application in cinnamic acid oxidation synthesizing cinnamic acid thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104368340A true CN104368340A (en) | 2015-02-25 |
| CN104368340B CN104368340B (en) | 2016-05-18 |
Family
ID=52547686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410718928.3A Active CN104368340B (en) | 2014-12-01 | 2014-12-01 | A kind of preparation of sponge silver catalyst and the application in cinnamic acid oxidation synthesizing cinnamic acid thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104368340B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146296A (en) * | 2015-04-21 | 2016-11-23 | 昆药集团股份有限公司 | A kind of preparation method of caffeic acid derivative |
| CN108250069A (en) * | 2018-01-22 | 2018-07-06 | 万华化学集团股份有限公司 | A kind of preparation method of isooctyl acid |
| CN108971512A (en) * | 2018-09-14 | 2018-12-11 | 江西科技师范大学 | A kind of the green preparation and its application of the rectangular particle of porous spongy Ag |
| CN110114175A (en) * | 2016-10-13 | 2019-08-09 | LS-Nikko铜制炼株式会社 | High temperature sintering type silver powder and its manufacturing method |
| CN110560050A (en) * | 2019-08-22 | 2019-12-13 | 浙江工业大学 | boron-doped silver nano spongy catalyst for electrochemical synthesis of ammonia and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095422A (en) * | 1993-05-20 | 1994-11-23 | 薛光 | The full wet method gold and silver of gold mud separating technology |
| RU2413778C1 (en) * | 2009-11-30 | 2011-03-10 | Государственное образовательное учреждение высшего профессионального образования "Санкт-Петербургский Государственный политехнический университет" (ГОУ "СПбГПУ") | Procedure for production of high porous silver sponge out of silver containing materials (versions) |
| CN102826992A (en) * | 2012-09-28 | 2012-12-19 | 湖北远成药业有限公司 | Novel industrialized synthesis technique for preparing cinnamic acid from cinnamic aldehyde by catalytic oxidation |
| CN103898325A (en) * | 2012-12-27 | 2014-07-02 | 深圳市格林美高新技术股份有限公司 | Method for recovering valuable metals from scraped auto parts |
-
2014
- 2014-12-01 CN CN201410718928.3A patent/CN104368340B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095422A (en) * | 1993-05-20 | 1994-11-23 | 薛光 | The full wet method gold and silver of gold mud separating technology |
| RU2413778C1 (en) * | 2009-11-30 | 2011-03-10 | Государственное образовательное учреждение высшего профессионального образования "Санкт-Петербургский Государственный политехнический университет" (ГОУ "СПбГПУ") | Procedure for production of high porous silver sponge out of silver containing materials (versions) |
| CN102826992A (en) * | 2012-09-28 | 2012-12-19 | 湖北远成药业有限公司 | Novel industrialized synthesis technique for preparing cinnamic acid from cinnamic aldehyde by catalytic oxidation |
| CN103898325A (en) * | 2012-12-27 | 2014-07-02 | 深圳市格林美高新技术股份有限公司 | Method for recovering valuable metals from scraped auto parts |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106146296A (en) * | 2015-04-21 | 2016-11-23 | 昆药集团股份有限公司 | A kind of preparation method of caffeic acid derivative |
| CN106146296B (en) * | 2015-04-21 | 2019-02-26 | 昆药集团股份有限公司 | A kind of preparation method of caffeic acid derivative |
| CN110114175A (en) * | 2016-10-13 | 2019-08-09 | LS-Nikko铜制炼株式会社 | High temperature sintering type silver powder and its manufacturing method |
| CN108250069A (en) * | 2018-01-22 | 2018-07-06 | 万华化学集团股份有限公司 | A kind of preparation method of isooctyl acid |
| CN108250069B (en) * | 2018-01-22 | 2021-01-15 | 万华化学集团股份有限公司 | Preparation method of isooctanoic acid |
| CN108971512A (en) * | 2018-09-14 | 2018-12-11 | 江西科技师范大学 | A kind of the green preparation and its application of the rectangular particle of porous spongy Ag |
| CN108971512B (en) * | 2018-09-14 | 2021-04-02 | 江西科技师范大学 | Green preparation method and application of porous spongy Ag square particles |
| CN110560050A (en) * | 2019-08-22 | 2019-12-13 | 浙江工业大学 | boron-doped silver nano spongy catalyst for electrochemical synthesis of ammonia and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104368340B (en) | 2016-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104368340B (en) | A kind of preparation of sponge silver catalyst and the application in cinnamic acid oxidation synthesizing cinnamic acid thereof | |
| CN104557639B (en) | Method of preparing 2-nitro-4-methylsulfonyl benzoic acid | |
| CN106431887B (en) | Preparation method of trimesic acid | |
| CN102399182A (en) | Production method of quinaldinic acid | |
| CN111747840A (en) | Preparation method of 1, 4-naphthalenedicarboxylic acid | |
| CN102336658A (en) | Production method of 3,5-dimethylbenzoic acid | |
| CN108996475B (en) | Method for preparing high-purity potassium iodate | |
| CN104529822B (en) | A kind of citronellal prepares the production technology of 3,7-Dimethyl-6-octenenitrile | |
| CN101565400B (en) | Preparation method of 4-amino-3, 5, 6-chloropyridine-2-methanoic acid | |
| CN101066780A (en) | Process of preparing manganous manganic oxide product possessing low sulfur content with manganese sulfate solution | |
| CN113634274B (en) | Method for efficiently decomposing hydrogen peroxide by graphene-coated cobalt catalyst under acidic condition | |
| CN102249993A (en) | Method for treating waste water generated from production of 3-cyanopyridine and recovering nicotinic acid | |
| CN112574043B (en) | Production process of basic red intermediate 3-ethylamino-p-methylphenol | |
| CN104513198A (en) | 2-chloronicotinic acid synthetic method | |
| CN101270041A (en) | Catalytic oxidation method of preparing a-methyl cinnamic acid | |
| US20220324718A1 (en) | Method for preparing basic copper carbonate | |
| CN102229621B (en) | Method for preparing glyphosate by catalyzing and oxidizing glyphosine in the presence of ultraviolet light source | |
| CN116332220B (en) | Synthesis method of lanthanum (III) chloride bis (lithium chloride) | |
| CN111138268A (en) | Preparation method of 4,4' -biphenyldicarboxylic acid | |
| CN113582860B (en) | Preparation method of N-methyl monoethanolamine | |
| CN115869950B (en) | Method for preparing Fenton-like catalyst from fluorine-containing silicon slag and preparing byproduct fluoride salt product | |
| CN112111659B (en) | Method for recovering rhodium from rhodium-containing waste liquid | |
| CN103877965B (en) | A kind of preparation and application of tin dioxide solid super basic catalyst | |
| CN113816879B (en) | Method for preparing calcium taurate and taurine through photocatalysis | |
| CN101643399B (en) | Method for preparing cobalt acetate solution |
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 | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231224 Address after: 434200 No.1 Binhu Avenue, Lingang New Area, Songzi City, Jingzhou City, Hubei Province (Lingang New Area Command Headquarters) Patentee after: Hubei xinimei flavor Co.,Ltd. Address before: 432405, No. 2 Development Avenue, Changjiang Port, Yingcheng City, Hubei Province Patentee before: YINGCHENG WUHAN ORGANIC MATERIAL Co.,Ltd. |