CN108355703A - A kind of glutaraldehyde oxidation functional mesoporous molecular sieve catalyst of glutaric acid tungstenic processed and preparation method thereof - Google Patents
A kind of glutaraldehyde oxidation functional mesoporous molecular sieve catalyst of glutaric acid tungstenic processed and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 41
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 title claims abstract description 28
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 title abstract description 11
- 230000003647 oxidation Effects 0.000 title abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 41
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 33
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010937 tungsten Substances 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 15
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 235000019441 ethanol Nutrition 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 64
- 239000007787 solid Substances 0.000 claims description 64
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 238000007306 functionalization reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 2
- -1 n-octyl Chemical group 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract 1
- 206010013786 Dry skin Diseases 0.000 description 23
- 238000001035 drying Methods 0.000 description 23
- 239000002253 acid Substances 0.000 description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 241000894007 species Species 0.000 description 3
- KPGXRSRHYNQIFN-UHFFFAOYSA-N 2-oxoglutaric acid Chemical compound OC(=O)CCC(=O)C(O)=O KPGXRSRHYNQIFN-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- BUMGIEFFCMBQDG-UHFFFAOYSA-N dichlorosilicon Chemical compound Cl[Si]Cl BUMGIEFFCMBQDG-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical class CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical class CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- AOQFECIIKLTYEL-UHFFFAOYSA-N C(CCCCCCCCCCC)[Si](OC)(OC)OC.C(CCCCCCC)[Si](OC)(OC)OC Chemical compound C(CCCCCCCCCCC)[Si](OC)(OC)OC.C(CCCCCCC)[Si](OC)(OC)OC AOQFECIIKLTYEL-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- HWXBTNAVRSUOJR-UHFFFAOYSA-N alpha-hydroxyglutaric acid Natural products OC(=O)C(O)CCC(O)=O HWXBTNAVRSUOJR-UHFFFAOYSA-N 0.000 description 1
- 229940009533 alpha-ketoglutaric acid Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002311 glutaric acids Chemical class 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- BHTJEPVNHUUIPV-UHFFFAOYSA-N pentanedial;hydrate Chemical compound O.O=CCCCC=O BHTJEPVNHUUIPV-UHFFFAOYSA-N 0.000 description 1
- IFUXGPHQZVCZMY-UHFFFAOYSA-N pentanedial;pentanedioic acid Chemical compound O=CCCCC=O.OC(=O)CCCC(O)=O IFUXGPHQZVCZMY-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
Abstract
The invention belongs to catalyst technical fields, are related to a kind of glutaraldehyde oxidation functional mesoporous molecular sieve catalyst of glutaric acid tungstenic processed and preparation method thereof.The catalyst is a kind of functional mesoporous 15 supported tungsten oxide catalysts of molecular sieve SBA (W SBA 15), and tungsten is introduced into using rear synthetic method in the skeleton of functional mesoporous molecular sieve SBA 15.Mesopore molecular sieve SBA 15 is scattered in solvent by the method, stirring, and organosilan agent, stirring is added, reflux is filtered, dry, soxhlet type, it is dry, dichloromethane is added, trifluoromethanesulfonic acid is added in stirring, stirring, filtering, ethyl alcohol washing are dry, tungsten source is added, stirs, filtering, washing, it is dry, obtain the catalyst.The method operation is easy.The functional mesoporous 15 heterogeneous catalyst pore passage structure high-sequentials of molecular sieve SBA of tungstenic of preparation, tungsten species high degree of dispersion have ultrastability.15 heterogeneous catalysts of W SBA prepared by the present invention are aoxidized for glutaraldehyde in the reaction of glutaric acid processed, the conversion ratio of glutaraldehyde up to 99% or more, the yield of glutaric acid up to 98% or more, and reusable 20 times or more and activity remains unchanged.
Description
【Technical field】
The present invention relates to a kind of glutaraldehydes to aoxidize the functional mesoporous molecular sieve catalyst of glutaric acid tungstenic processed and its preparation
Method belongs to catalyst technical field.
【Background technology】
Glutaric acid is a kind of important industrial chemicals and organic intermediate.Such as prepare glutaric anhydride, α-ketoglutaric acid, peroxide
Glutaric acid, B- (4- chlorphenyls) glutaric acids and the intermediate that anti-blood pressure agent is made；Such as it is used as synthetic resin, rubber and plasticizer
Initiator；Such as make disinfection solution and cleaning agent material.The method of synthesizing glutaric acid mainly has absorption method and chemistry at present
Synthetic method.Absorption method is primarily adapted for use in industrial production glutaric acid, refers to and recycles glutaric acid from the by-product of production adipic acid, this method
It relies on the production of adipic acid and lacks the method for efficiently separating.Chemical synthesis：Such as oxidizing cyclohexanone method, dihydrofuran method, γ-
Butyrolactone multi-step synthetic method and cyclopentanone liquid phase oxidation etc., because material toxicity is larger, synthesis condition is harsh, and environmental pollution is tight
Weight, applies in general to laboratory and prepares glutaric acid.
Dai Weilin etc. proposes a kind of method of synthesizing amyl acid by catalyzing oxidizing amyl aldehyde of environmental pretection, with phosphotungstic acid or tungsten
Acid is catalyst, and glutaric acid (ZL 200410016887.X) is prepared by oxidant of hydrogen peroxide.This method is in relatively mild condition
Under, the yield of glutaric acid is environmental-friendly up to 97-98%, but catalyst is difficult to recycle.(the Journal of such as small stream ancestral's prestige
Molecular Catalysis A:Chemical,2001,166:It 219-224) is prepared for being suitable for oxidation of cyclopentene system penta 2
Phase transfer catalyst [π-the C of acid5H5NC16H33]3[PW4O16], which is close to 99% to the selectivity of glutaric acid, to ring
The conversion ratio of amylene can reach 100%, but catalyst, after pyroreaction, irreversible variation has occurred in structure.Chen Hui (penta
Diacid green synthesis process and the Shanghai Study of Novel Catalyst [D]:Fudan University, 2007) propose that with 1,2- ring pentanediols be original
Material, using hydrogen peroxide as oxidant, using tungsten-contained mesic porous molecular sieve MCM-41 as catalyst preparation glutaric acid, but 1,2- ring pentanediol valence
Lattice are expensive and synthesis condition is harsh, and the activity of recyclable tungsten-contained mesic porous molecular sieve MCM-41 catalyst is lower than homogeneous catalyst wolframic acid
20% or so.Zhao Dongyuan etc. (Journal of the American Chemical Society, 1998,120:6024-
6036) mesoporous molecular sieve SBA-15 with two-dimentional six side's through-hole structures of synthesis, hydrothermal stability is high, aperture adjustable extent
Greatly, it is with a wide range of applications in fields such as catalysis, separation, biology and nano materials.(the Chemistry of such as Zhao Dongyuan
Materials,2007,19:Functionalization SBA-15 tungsten-containing catalysts 4380-4381) are prepared for, and applied to the oxidation reaction of alcohol
In, wherein commonly reaching 94% to the selectivity of acid, 89% is up to the yield of acid.(the Organic such as Karimi
Letters,2005,7:It 625-628) is prepared for functionalized SiO 2 microballoon tungsten-containing catalyst, and applied to the choosing of sulfide
In selecting property oxidation reaction, catalyst can recycle 8 times.The mesoporous molecular sieve SBA-15 of functionalization can effectively limit work
The loss of property component, and make active specy high degree of dispersion, while improving the stability and activity of catalyst.Therefore functional mesoporous
Molecular sieve SBA-15, which loads tungsten heterogeneous catalyst, has important industrial application value.
【Invention content】
For the shortcoming of existing catalyst, if catalyst activity is low, stability is poor, and the present invention provides a kind of with super
High stability has glutaric acid in the functional mesoporous molecular sieve of tungstenic that glutaric acid processed is aoxidized for glutaraldehyde of very high selectivity
Heterogeneous catalyst and preparation method thereof.
The purpose of the present invention is realized by following technical scheme：
It is in functionalization that glutaraldehyde provided by the invention, which aoxidizes glutaric acid processed with the functional mesoporous molecular sieve catalyst of tungstenic,
Tungsten active component is introduced after mesoporous molecular sieve SBA-15 and is made, and is denoted as W-SBA-15, wherein the molar ratio of Si and W is generally
35-60。
The above-mentioned functional mesoporous molecular sieve catalyst preparation method of tungstenic, the method are as follows：
Mesoporous molecular sieve SBA-15 is scattered in 25-45 DEG C in solvent, 2-5h is stirred, organosilan agent is added, is stirred,
Flow back 8-16h at 110-170 DEG C, filters, dry, obtains solid powder a；The solid powder a is subjected to soxhlet type, is done
It is dry, obtain solid powder b；Dichloromethane is added into the solid powder b, stirs 2-4h, trifluoromethanesulfonic acid is added, stirs 6-
12h, filtering, ethyl alcohol washing is dry, obtains solid powder c；Tungsten source solution is added into the solid powder c, stirs 12-
48h is filtered, and is washed, and dry, it is the catalyst to obtain solid powder d, the solid powder d；
Wherein, the solvent is the one or several kinds among benzene,toluene,xylene, cyclohexylamine, hexane, preferably toluene；
The quality dosage of the solvent is 5-80 times, preferably 10-40 times of the mesoporous molecular sieve SBA-15 quality dosage；
The organosilan agent be 3- aminopropyl triethoxysilanes, n-propyl trimethoxy silane, hexichol dichlorosilane,
Methyltriethoxysilane, n-octyl trimethoxy silane dodecyltrimethoxysilane, preferably 3- aminopropyl-triethoxies
Silane；
The quality dosage of the organosilan agent is 0.01-0.25 times of the mesoporous molecular sieve SBA-15 quality dosage,
It is preferred that 0.05-0.15 times；
The extractant of the soxhlet type is the one or several kinds among benzene,toluene,xylene, cyclohexylamine, hexane, excellent
Select toluene；
The quality dosage of the dichloromethane is 5-85 times of the mesoporous molecular sieve SBA-15 quality dosage, preferably 25-
65 times；
The quality dosage of the trifluoromethanesulfonic acid is 0.05-2 times of mesoporous molecular sieve SBA-15 quality dosage, preferably 0.1-
1 times；
Tungsten source solution is wolframic acid sodium water solution, 12- phosphotungstic acid aqueous solutions, two aqueous tungstic acid solution of 18- phosphorus, ammonium tungstate water
One kind of solution, preferably wolframic acid sodium water solution；
The mass concentration of tungsten source solution is 0.01-2wt%, preferably 0.3-0.8wt%；
The nitrogen adsorption desorption curve figure of W-SBA-15 catalyst is shown in Fig. 1；
The X ray diffracting spectrum of W-SBA-15 catalyst is shown in Fig. 2；
The activity of catalyst provided by the invention can test with the following method：
Glutaraldehyde oxidation reaction in the present invention carries out in three neck round bottom flask, connects condenser pipe, a bite jointing temp flatly
Meter, connects constant pressure funnel, using magnetic agitation flatly.Reaction condition is 30-55 DEG C of water-bath, be added 0.1-2g catalyst and
Then 50% hydrogen peroxide of 1.9-7.9g is added in the glutaraldehyde water solution of 3g50%, stir 0.1-5h, be warming up to 60-100 DEG C,
5-24h is reacted under stirring condition.After reaction, the conversion ratio of reaction solution feed liquor gas Chromatographic Determination glutaraldehyde and glutaric acid
Selectivity, reaction solution feed liquor matter combined instrument determine each component.
The method of the present invention is the introducing active component tungsten after functional mesoporous molecular sieve SBA-15, makes tungsten species height point
It is dispersed in the skeleton of functional mesoporous molecular sieve SBA-15, operation is easy.The catalyst aoxidizes the anti-of glutaric acid processed in glutaraldehyde
Glutaric acid selectivity and stability with superelevation in answering, recycle 20 times and still keep high activity.
The present invention has the following advantages that compared with prior art：
1, active component tungsten is introduced into the skeleton of the mesoporous molecular sieve SBA-15 of functionalization by the catalyst, active component
It not easily runs off.
2, high degree of dispersion, six side of two dimension for maintaining functional mesoporous molecular sieve SBA-15 tie tungsten species on the catalyst
Structure.
3, the catalyst is in the reaction that glutaraldehyde aoxidizes glutaric acid processed, to the conversion ratio of glutaraldehyde up to 99% or more,
To the yield of glutaric acid up to 98% or more, there is excellent catalytic performance.
4, the catalyst catalytic performance is reproducible, still keeps high activity reusable 20 times, it is easy to accomplish industry
Amplification.
【Description of the drawings】
Fig. 1 is the nitrogen adsorption desorption curve figure of W-SBA-15 catalyst.
Fig. 2 is the X ray diffracting spectrum of W-SBA-15 catalyst.
【Specific implementation mode】
The present invention is described in detail with specific embodiment below, but not limited to this.
Embodiment 1
1g mesoporous molecular sieve SBA-15s are scattered in 10g benzene, and 0.05g3- aminopropyl-triethoxies are added in 25 DEG C of stirring 2h
Silane, stirring, 110 DEG C of reflux 8h, filtering, 100 DEG C of dryings obtain solid powder a；The solid powder a is carried out in benzene
Soxhlet type, 100 DEG C of dryings, obtains solid powder b；18mL dichloromethane is added into the solid powder b, stirs 2h, adds
Enter 0.1g trifluoromethanesulfonic acids, stir 6h, filtering, ethyl alcohol washs, and 100 DEG C of dryings obtain solid powder c；To the solid powder c
The middle aqueous solution that 66mL sodium tungstates containing 0.2g are added, stirs 12h, filters, washing, and 100 DEG C of dryings obtain solid powder d, described
Solid powder d is the catalyst, number #1.
Embodiment 2
1g mesoporous molecular sieve SBA-15s are scattered in 16g toluene, and 0.07g n-propyl trimethoxies are added in 29 DEG C of stirring 2.6h
Base silane, stirring, 122 DEG C of reflux 9.6h, filtering, 100 DEG C of dryings obtain solid powder a；By the solid powder a in toluene
Middle carry out soxhlet type, 100 DEG C of dryings obtain solid powder b；24mL dichloromethane, stirring are added into the solid powder b
0.28g trifluoromethanesulfonic acids are added in 2.4h, stir 7.2h, filtering, and ethyl alcohol washs, and 100 DEG C of dryings obtain solid powder c；To institute
Addition 37.5mL phosphotungstic acid aqueous solutions containing 0.15g12- in solid powder c are stated, 19.2h is stirred, are filtered, washing, 100 DEG C of dryings,
It is the catalyst, number #2 to obtain solid powder d, the solid powder d.
Embodiment 3
1g mesoporous molecular sieve SBA-15s are scattered in 22g dimethylbenzene, and 0.09g hexichol dichloro silicon is added in 33 DEG C of stirring 3.2h
Alkane, stirring, 134 DEG C of reflux 11.2h, filtering, 100 DEG C of dryings obtain solid powder a；By the solid powder a in dimethylbenzene
Soxhlet type is carried out, 100 DEG C of dryings obtain solid powder b；30mL dichloromethane, stirring are added into the solid powder b
0.46g trifluoromethanesulfonic acids are added in 3.8h, stir 8.4h, filtering, and ethyl alcohol washs, and 100 DEG C of dryings obtain solid powder c；To institute
It states and two aqueous tungstic acid solution of 30mL phosphorus containing 0.15g18- is added in solid powder c, stir 26.4h, filter, washing, 100 DEG C of dryings,
It is the catalyst, number #3 to obtain solid powder d, the solid powder d.
Embodiment 4
1g mesoporous molecular sieve SBA-15s are scattered in 28g cyclohexylamine, and three ethoxy of 0.11g methyl is added in 37 DEG C of stirring 3.8h
Base silane, stirring, 146 DEG C of reflux 12.8h, filtering, 100 DEG C of dryings obtain solid powder a；By the solid powder a in hexamethylene
Soxhlet type is carried out in amine, 100 DEG C of dryings obtain solid powder b；36mL dichloromethane is added into the solid powder b, stirs
3.2h is mixed, 0.64g trifluoromethanesulfonic acids are added, stirs 9.6h, filtering, ethyl alcohol washs, and 100 DEG C of dryings obtain solid powder c；To
25mL ammonium tungstate aqueous solutions containing 0.15g are added in the solid powder c, stir 33.6h, filter, washing, 100 DEG C of dryings obtain
Solid powder d, the solid powder d are the catalyst, number #4.
Embodiment 5
1g mesoporous molecular sieve SBA-15s are scattered in 34g hexanes, and 0.13g n-octyl trimethoxies are added in 41 DEG C of stirring 4.4h
Base silane, stirring, 158 DEG C of reflux 14.4h, filtering, 100 DEG C of dryings obtain solid powder a；By the solid powder a in hexane
Middle carry out soxhlet type, 100 DEG C of dryings obtain solid powder b；42mL dichloromethane, stirring are added into the solid powder b
0.82g trifluoromethanesulfonic acids are added in 3.6h, stir 10.8h, filtering, and ethyl alcohol washs, and 100 DEG C of dryings obtain solid powder c；To institute
The aqueous solution that 28.5mL sodium tungstates containing 0.2g are added in solid powder c is stated, 40.8h is stirred, is filtered, washing, 100 DEG C of dryings obtain
It is the catalyst, number #5 to solid powder d, the solid powder d.
Embodiment 6
1g mesoporous molecular sieve SBA-15s are scattered in the mixed solution formed by 20g toluene and 20g cyclohexylamine, 45 DEG C of stirrings
5h, is added 0.15g dodecyltrimethoxysilanes, stirring, and 170 DEG C of reflux 16h are filtered, 100 DEG C of dryings obtain solid powder
Last a；The solid powder a is subjected to soxhlet type in toluene, 100 DEG C of dryings obtain solid powder b；To the solid powder
49mL dichloromethane is added in last b, stirs 4h, 1g trifluoromethanesulfonic acids are added, stirs 12h, filtering, ethyl alcohol washing, 100 DEG C dry
It is dry, obtain solid powder c；The aqueous solution of 25mL sodium tungstates containing 0.2g is added into the solid powder c, stirs 48h, filters,
Washing, 100 DEG C of dryings, it is the catalyst, number #6 to obtain solid powder d, the solid powder d.
Embodiment 7
#1 catalyst in embodiment 1 is repeated glutaraldehyde oxidation glutaric acid processed to react 5 times, then carries out active testing, is remembered
For #1 (5).
Embodiment 8
#1 (5) catalyst in embodiment 7 is repeated glutaraldehyde oxidation glutaric acid processed to react 5 times, then carries out active testing,
It is denoted as #1 (10).
Embodiment 9
#1 (10) catalyst in embodiment 8 is repeated glutaraldehyde oxidation glutaric acid processed to react 5 times, then carries out active survey
Examination, is denoted as #1 (15).
Embodiment 10
#1 (15) catalyst in embodiment 9 is repeated glutaraldehyde oxidation glutaric acid processed to react 5 times, then carries out active survey
Examination, is denoted as #1 (20)
The catalyst performance parameter prepared in 1~embodiment of above-described embodiment 6 is as shown in table 1：
The functional mesoporous molecular sieve catalyst performance parameter of 1 tungstenic of table
10 catalyst activity test results in 1~embodiment of above-described embodiment 10 are as shown in table 2：
The functional mesoporous activity of molecular sieve catalysts test result of 2 tungstenic of table
The present invention includes but not limited to above example, it is every carried out under the principle of spirit of that invention it is any equivalent
Replacement or local improvement, all will be regarded as within protection scope of the present invention.
Claims (11)
1. a kind of glutaraldehyde aoxidizes the functional mesoporous molecular sieve catalyst of glutaric acid tungstenic processed, it is characterised in that：In functionalization
Tungsten active component is introduced after mesoporous molecular sieve SBA-15 and is made, wherein the molar ratio of Si and W is 35-60.
2. a kind of preparation method of catalyst as described in claim 1, it is characterised in that：It is as follows：
Mesoporous molecular sieve SBA-15 is scattered in 25-35 DEG C in solvent, 2-5h is stirred, organosilan agent is added, is stirred,
110-135 DEG C of reflux 8-16h, is filtered, dry, obtains solid powder a；The solid powder a is subjected to soxhlet type, it is dry,
Obtain solid powder b；Dichloromethane is added into the solid powder b, stirs 2-4h, trifluoromethanesulfonic acid is added, stirs 6-
12h, filtering, ethyl alcohol washing is dry, obtains solid powder c；Tungsten source solution is added into the solid powder c, stirs 12-
48h is filtered, and is washed, and dry, it is the catalyst to obtain solid powder d, the solid powder d.
3. the preparation method of catalyst according to claim 2, it is characterised in that；The solvent is benzene, toluene, diformazan
One or several kinds among benzene, cyclohexylamine, hexane.
4. the preparation method of catalyst according to claim 2, it is characterised in that：The quality dosage of the solvent is described
5-80 times of mesoporous molecular sieve SBA-15 quality dosage.
5. the preparation method of catalyst according to claim 2, it is characterised in that：The organosilan agent is 3- aminopropyls
Triethoxysilane, n-propyl trimethoxy silane, hexichol dichlorosilane, methyltriethoxysilane, n-octyl trimethoxy
One kind of silane, dodecyltrimethoxysilane.
6. the preparation method of catalyst according to claim 2, it is characterised in that：The quality dosage of the organosilan agent
It is 0.01-0.25 times of the mesoporous molecular sieve SBA-15 quality dosage.
7. the preparation method of catalyst according to claim 2, it is characterised in that：The extractant of the soxhlet type is
One or several kinds among benzene,toluene,xylene, cyclohexylamine, hexane.
8. the preparation method of catalyst according to claim 2, it is characterised in that：The quality dosage of the dichloromethane is
5-85 times of the mesoporous molecular sieve SBA-15 quality dosage.
9. the preparation method of catalyst according to claim 2, it is characterised in that：The quality dosage of the trifluoromethanesulfonic acid
It is 0.05-2 times of mesoporous molecular sieve SBA-15 quality dosage.
10. the preparation method of catalyst according to claim 2, it is characterised in that：Tungsten source solution is sodium tungstate water
One kind of solution, 12- phosphotungstic acid aqueous solutions, two aqueous tungstic acid solution of 18- phosphorus, ammonium tungstate aqueous solution.
11. the preparation method of catalyst according to claim 2, it is characterised in that：The mass concentration of tungsten source solution
For 0.01-2wt%.
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Citations (4)
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| IT979637B (en) * | 1972-02-29 | 1974-09-30 | Ceskoslovenska Akademie Ved | PROCEDURE FOR THE PREPARATION OF SOLUBLE WATER-BASED POLYMERS |
| CN1560014A (en) * | 2004-03-11 | 2005-01-05 | 复旦大学 | Process for synthesizing amyl acid by catalyzing oxidizing amyl aldehyde of environmental pretection |
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- 2018-02-09 CN CN201810131730.3A patent/CN108355703A/en active Pending
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| IT979637B (en) * | 1972-02-29 | 1974-09-30 | Ceskoslovenska Akademie Ved | PROCEDURE FOR THE PREPARATION OF SOLUBLE WATER-BASED POLYMERS |
| CN1560014A (en) * | 2004-03-11 | 2005-01-05 | 复旦大学 | Process for synthesizing amyl acid by catalyzing oxidizing amyl aldehyde of environmental pretection |
| CN1903823A (en) * | 2006-08-03 | 2007-01-31 | 复旦大学 | Method of large scale synthesizing glutaric acid by environment friendly catalyzing and oxidizing cyclopentene |
| CN101570479A (en) * | 2009-06-15 | 2009-11-04 | 上海华谊丙烯酸有限公司 | Method for preparing glutaric acid through oxidation of glutaral pentanedial |
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