CN102329248B - Method for synthesizing phenylacetonitrile and catalyst used by same - Google Patents
Method for synthesizing phenylacetonitrile and catalyst used by same Download PDFInfo
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- CN102329248B CN102329248B CN201110190564.2A CN201110190564A CN102329248B CN 102329248 B CN102329248 B CN 102329248B CN 201110190564 A CN201110190564 A CN 201110190564A CN 102329248 B CN102329248 B CN 102329248B
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- Prior art keywords
- styrene oxide
- benzyl cyanide
- catalyzer
- oxide 98min
- ammonia
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- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 230000002194 synthesizing effect Effects 0.000 title abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 53
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims abstract description 43
- 230000003197 catalytic effect Effects 0.000 claims abstract description 30
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 47
- 238000002360 preparation method Methods 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 238000004176 ammonification Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 abstract 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- 230000009466 transformation Effects 0.000 description 16
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 12
- 239000011701 zinc Substances 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- LSBDFXRDZJMBSC-UHFFFAOYSA-N 2-phenylacetamide Chemical compound NC(=O)CC1=CC=CC=C1 LSBDFXRDZJMBSC-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 229910052622 kaolinite Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- ATROHALUCMTWTB-WYMLVPIESA-N (z)-n-diethoxyphosphinothioyloxybenzenecarboximidoyl cyanide Chemical compound CCOP(=S)(OCC)O\N=C(/C#N)C1=CC=CC=C1 ATROHALUCMTWTB-WYMLVPIESA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229910007564 Zn—Co Inorganic materials 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical group N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DDBREPKUVSBGFI-UHFFFAOYSA-N phenobarbital Chemical compound C=1C=CC=CC=1C1(CC)C(=O)NC(=O)NC1=O DDBREPKUVSBGFI-UHFFFAOYSA-N 0.000 description 1
- XAMUDJHXFNRLCY-UHFFFAOYSA-N phenthoate Chemical compound CCOC(=O)C(SP(=S)(OC)OC)C1=CC=CC=C1 XAMUDJHXFNRLCY-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for catalytically synthesizing phenylacetonitrile, which comprises the following step: synthesizing the phenylacetonitrile from styrene oxide and ammonia in a fixed bed reactor. A catalyst used by the method consists of a carrier and a catalytic active component, wherein the carrier is gamma-Al2O3 (aluminum oxide) or SiO2 (silicon dioxide); the catalytic active component is an oxide of a metal M; the total content of the catalytic active component is 19%-35% of the total mass of the catalyst; and the sizes of the particles of the catalyst are 4-20 meshes. The catalyst used in the method is simple to prepare, is cheap in price, is obtained easily, and has high catalytic activity; the catalytic activity is stable; the condition of a catalytic reaction is moderate; three wastes (waste water, waste gas and waste residue) are less; the conversion ratio of the styrene oxide is 100%; and the yield of the phenylacetonitrile is 87.91%.
Description
Technical field
The present invention relates to a kind of synthetic technology of intermediate benzyl cyanide of medication chemistry industry, propose first preparation and the application of take Styrene oxide 98min. and ammonia as catalytic material synthetic benzyl cyanide route and catalyzer thereof.
Background technology
Benzyl cyanide is a kind of important fine-chemical intermediate, is mainly used in the production of medicine, agricultural chemicals, spices and dyestuff intermediate, can be used to synthetic phenylethyl barbituric acid, toluylic acid, Tsidial and Volaton.
Prepare benzyl cyanide and mainly contain following several method:
Method 1: take Benzyl Chloride and sodium cyanide as raw material synthesis method, this method is the main method of producing benzyl cyanide both at home and abroad, and relevant report is more.German Patent GB1200970 reported take water as solvent, and the methylamine of 0.001-5mol, dimethylamine or Trimethylamine 99 are catalyzer, back flow reaction 1h, and the yield of benzyl cyanide is 86%.In German patent DE 1083250, with dimethylformamide and benzene, be mixed solvent, back flow reaction 35min, the yield 89% of benzyl cyanide.It is solvent that U.S. Pat 2734908 adopts acetone, and sodium iodide is catalyzer, heating in water bath back flow reaction 24h, benzyl cyanide yield 94%.< < test and research > > 1999,2(80) studied under tertiary amine catalytic effect, with Benzyl Chloride and directly synthetic benzyl cyanide of sodium cyanide, yield is 97.5%, and purity is 98.8%.This class methods technique is simple, and the yield of benzyl cyanide is higher, but raw material sodium cyanide has severe toxicity and serious environment pollution.
Method 2: German patent DE 1117121 has been reported C
6h
5cH
2nHCOH under silica gel or catalyzed by silicate effect, temperature of reaction 460-560 ℃, rare gas element exist under, normal pressure, pressurization or Depressor response obtain benzyl cyanide.U.S. Pat 3118925 is with C
6h
5cH
2nHCOCCl
3pyrogenically prepared benzyl cyanide.This class methods benzyl amine after formyl again high temperature dehydration make benzyl cyanide, step is relatively many, production cost increase.
Method 3: Japanese Patent GB1075393 reported take ethylbenzene as raw material, activated alumina is catalyzer.In the time of 350 ℃, ethylbenzene 0.173ml/min, ammonia 36ml/min, nitrogen 20ml/min, air 362ml/min, stablizes after 90min, and the yield of benzyl cyanide is only 4.2%.The yield of this class methods benzyl cyanide is too low, unsuitable suitability for industrialized production.
Method 4:J.Am.Chem.Soc.53, (321-330) has reported take toluylic acid as raw material, and silica gel is the synthetic benzyl cyanide of catalyzer, reaction conditions: the toluylic acid of 90 ℃ and excess ammonia are by the layer of silica gel of 500 ℃, and the yield of benzyl cyanide is 87%.In U.S. Pat 3002990,2mol toluylic acid and 1mol mauguinite are dissolved in appropriate benzene, in quartz tube reactor, and 495 ℃, after reaction 7-8s, cooling purification, benzyl cyanide yield is 27%.This class methods Raw toluylic acid strongly-acid, hardware is had to corrosion, and temperature of reaction is higher, higher to equipment requirements.
Method 5:J.Am.Chem.Soc.78, (1066-1068) research phenylacetamide is at 244-279 ℃, through (Me
2n)
3p dehydration, generates benzyl cyanide, and yield is 50%.United States Patent (USP) GB1005647 has reported that phenylacetamide is under the effect of ring-type phosphorus muriate, and 100 ℃ are reacted 1 hour, and the yield of benzyl cyanide is 80%.These class methods are used the catalyzer that price is more expensive, and do not report catalyst life and recycle in document.
Summary of the invention
The object of the invention is to develop a kind of novel method that catalyzes and synthesizes benzyl cyanide, broken the external monopolization to benzyl cyanide synthetic technology.Synthetic benzyl cyanide under the method normal pressure, catalyzer preparation is simple, and catalytic performance is good, reaction conditions gentleness, the three wastes are few, are more applicable to the synthetic benzyl cyanide of fixed-bed catalytic under industrialization.
Technical scheme of the present invention is:
Catalyze and synthesize a novel method for benzyl cyanide, the method is Styrene oxide 98min. and ammonia synthetic benzyl cyanide in fixed-bed reactor.The method used catalyst is comprised of carrier and catalytic active component, and wherein carrier is γ-Al
2o
3or SiO
2, the oxide compound that catalytic active component is metal M, catalytic active component total content is 19%～35% of catalyzer total mass; Catalyst particle size is 4 order～20 orders.
Preferred γ-the Al of described carrier above
2o
3;
Described metal M is one or more in Fe, Ni, Co, Zn, Ni, Cr or Cu;
Catalytic active component is preferably the oxide compound of Zn, Zn/Co or Zn/Cr.
Described for catalyzing and synthesizing the preparation method of catalyzer of benzyl cyanide above, this catalyzer is with kneading extrusion method or pickling process preparation.
Described for catalyzing and synthesizing the application of catalyzer of benzyl cyanide above: adopt fixed-bed reactor, Styrene oxide 98min. and toluene mixing solutions enter reactor through constant-flux pump, and ammonia enters reactor through mass flowmeter, reacts for 300 ℃～450 ℃ of normal pressure, temperature; Styrene oxide 98min. and toluene mass ratio are 1:4, and Styrene oxide 98min. and ammonia mol ratio are 1:10～30; Styrene oxide 98min., toluene and ammonia gas mixture body are 500h by the volume space velocity of beds
-1to 600h
-1, under catalyst action, ammonification obtains benzyl cyanide.
Adopt the beneficial effect that produces of technique scheme to be: the method reported first in invention with Styrene oxide 98min. and the synthetic benzyl cyanide of ammonia.The catalyzer preparation of using in invention is simple, adopts conventional kneading extrusion method or pickling process; Catalytic active component adopts the common metals such as Zn, Zn/Co or Zn/Cr, and carrier and catalytic active component are inexpensive and be easy to buy.Prepared catalyzer is used for catalyzing and synthesizing benzyl cyanide, wherein Styrene oxide 98min. transformation efficiency is 100%, the yield of benzyl cyanide is 87.91%, after non-stop run 200h, the transformation efficiency of Styrene oxide 98min. remains unchanged, benzyl cyanide yield drops to 72.53%, and the catalyst activity after online activation is compared and do not reduced for catalyst activity with new system.Compared with method 1, the yield of benzyl cyanide is more or less the same, but avoid using can serious environment pollution sodium cyanide, and can produce continuously, improved production efficiency.Compared with J.Am.Chem.Soc.53, (321-330) method, the yield of synthetic benzyl cyanide is high, and temperature of reaction is lower.Compared with other synthetic methods, simple to operate, benzyl cyanide yield is higher.This catalyzed reaction is synthesis under normal pressure, less demanding to conversion unit, has improved the security of operating process.In catalytic process, by product is cyanobenzene, and this compound is also the Chemicals that a kind of purposes is wider.Excess of ammonia gas and solvent toluene can recycle and reuse, and the three wastes are few.In sum, in invention, the method for synthetic benzyl cyanide is more novel, and the catalyzer preparation of use is simple, and cheap and easy to get, catalytic activity is high; Catalytic activity is stable; Catalytic reaction condition gentleness, the three wastes are few.
Embodiment
Below in conjunction with concrete example, the preparation process of used catalyst of the present invention is described in detail, various chemical used in enforcement are commercially available prod:
The preparation of catalyzer:
Exemplifying embodiment 1: preparation catalyst Zn/Al
2o
3
50 ℃ of 22.75g zinc nitrate heating are made it to be dissolved in 20ml deionized water, add 20g ball-type γ-Al
2o
3, stir, dipping spends the night, in 110 ℃ at loft drier inner drying 20h, in retort furnace, under air atmosphere 550 ℃ of roasting 5h, obtain required catalyzer, catalyzer size is 4 order～20 orders; Catalyzer consist of ZnO20.2%, Al
2o
379.8%.(catalyst component of the present invention is by ICP(inductively coupled plasma spectrum generator) analyzed and obtained, and following examples are same)
Exemplifying embodiment 2: preparation catalyst Zn/SiO
2
The heating of 22.75g zinc nitrate is dissolved in 20ml deionized water, adds 20g ball-type SiO
2, stir, dipping spends the night, in 110 ℃ at loft drier inner drying 20h, in retort furnace, under air atmosphere 550 ℃ of roasting 5h, obtain required catalyzer, catalyzer size is 4 order～20 orders; The weight of catalyzer consists of ZnO19.7%, SiO
281.3%.
Exemplifying embodiment 3: kneading extrusion method Kaolinite Preparation of Catalyst Zn/Al
2o
3
The heating of 22.75g zinc nitrate is dissolved in 10ml quality percentage composition 1% aqueous nitric acid, adds 20g γ-Al
2o
3powder, stirs, be fully ground to completely mix, extruded moulding, in 110 ℃ at loft drier inner drying 20h, in retort furnace, under air atmosphere 550 ℃ of roasting 5h, obtain required catalyzer, catalyzer size is 4 order～20 orders; The weight of catalyzer consists of ZnO19.9%, Al
2o
380.1%.
Exemplifying embodiment 4: kneading extrusion method Kaolinite Preparation of Catalyst Zn/Al
2o
3
The heating of 34.12g zinc nitrate is dissolved in 15ml quality percentage composition 1% aqueous nitric acid, adds 17.5g γ-Al
2o
3powder, stirs, be fully ground to completely mix, extruded moulding, in 110 ℃ at loft drier inner drying 20h, in retort furnace, under air atmosphere 550 ℃ of roasting 5h, obtain required catalyzer, catalyzer size is 4 order～20 orders; The weight of catalyzer consists of ZnO30.8%, Al
2o
369.2%.
Exemplifying embodiment 5: kneading extrusion method Kaolinite Preparation of Catalyst Zn-Co/Al
2o
3
34.12g zinc nitrate, the heating of 5.56g Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are dissolved in 18ml deionized water, add 16.38g γ-Al
2o
3powder, stirs, be fully ground to completely mix, extruded moulding, in 110 ℃ at loft drier inner drying 20h, in retort furnace, under air atmosphere 550 ℃ of roasting 5h, obtain required catalyzer, catalyzer size is 4 order～20 orders; The weight of catalyzer consists of ZnO29.5%, Co
2o
34.4%, Al
2o
366.1%.
Exemplifying embodiment 6: kneading extrusion method Kaolinite Preparation of Catalyst Zn-Cr/Al
2o
3
34.12g zinc nitrate, the heating of 8.65g chromium nitrate are dissolved in 18ml deionized water, add 16.38g γ-Al
2o
3powder, stirs, be fully ground to completely mix, extruded moulding, with 110 ℃ at loft drier inner drying 20h, in retort furnace, 550 ℃ of roasting 5h under air atmosphere, obtain required catalyzer, catalyzer size is 4 order～20 orders; The weight of catalyzer consists of ZnO30.7%, Cr
2o
34.7%, Al
2o
364.6%.
Below in conjunction with concrete example, catalyzer prepared by the present invention is applied to catalyzed oxidation vinylbenzene and the synthetic benzyl cyanide of ammonia:
Exemplifying embodiment 7:
Fixed-bed reactor (reactor is long is 1100mm, and internal diameter is 15mm, and catalyst volume is 30ml, particle diameter 2-3mm, following examples with) in add the catalyzer 30ml that adopts exemplifying embodiment 1 to prepare, at N
2under protection, be warming up to 350～450 ℃, with gas space velocity 500h
-1to inputting Styrene oxide 98min. and toluene mixing solutions and ammonia in fixed-bed reactor, (toluene mass content accounts for 80% of Styrene oxide 98min. and toluene mixture liquid quality sum, in below implementing, the percentage composition of toluene is identical), wherein Styrene oxide 98min. and ammonia mol ratio are 1:15, through catalytic ammoniation, obtain reaction solution, rectifying obtains products benzene acetonitrile.Through gc analysis, detect, wherein the transformation efficiency of Styrene oxide 98min. is 100%, and benzyl cyanide yield is 75.4%.
Exemplifying embodiment 8:
In fixed-bed reactor, add the catalyzer 30ml that adopts exemplifying embodiment 2 to prepare, at N
2under protection, be warming up to 350～450 ℃, with gas space velocity 550h
-1, in fixed-bed reactor, input Styrene oxide 98min. and toluene mixing solutions and ammonia, wherein Styrene oxide 98min. and ammonia mol ratio are 1:25, through catalytic ammoniation, obtain reaction solution, rectifying obtains products benzene acetonitrile.Through gc analysis, detect, wherein the transformation efficiency of Styrene oxide 98min. is 100%, and benzyl cyanide yield is 73.7%.
Exemplifying embodiment 9:
In fixed-bed reactor, add the catalyzer 30ml that adopts exemplifying embodiment 3 to prepare, at N
2under protection, be warming up to 350～450 ℃, with gas space velocity 500h
-1, in fixed-bed reactor, input Styrene oxide 98min. and toluene mixing solutions and ammonia, wherein Styrene oxide 98min. and ammonia mol ratio are 1:25, through catalytic ammoniation, obtain reaction solution, rectifying obtains products benzene acetonitrile.Through gc analysis, detect, wherein the transformation efficiency of Styrene oxide 98min. is 100%, and benzyl cyanide yield is 77.4%.
Exemplifying embodiment 10:
In fixed-bed reactor, add the catalyzer 30ml that adopts exemplifying embodiment 4 to prepare, at N
2under protection, be warming up to 380～450 ℃, with gas space velocity 600h
-1, in fixed-bed reactor, input Styrene oxide 98min. and toluene mixing solutions and ammonia, wherein Styrene oxide 98min. and ammonia mol ratio are 1:20, through catalytic ammoniation, obtain reaction solution, rectifying obtains products benzene acetonitrile.Through gc analysis, detect, wherein the transformation efficiency of Styrene oxide 98min. is 100%, and benzyl cyanide yield is 79.28%.
Exemplifying embodiment 11:
In fixed-bed reactor, add the catalyzer 30ml that adopts exemplifying embodiment 5 to prepare, at N
2under protection, be warming up to 380～450 ℃, with gas space velocity 600h
-1, in fixed-bed reactor, input Styrene oxide 98min. and toluene mixing solutions and ammonia, wherein Styrene oxide 98min. and ammonia mol ratio are 1:20, through catalytic ammoniation, obtain reaction solution, rectifying obtains products benzene acetonitrile.Through gc analysis, detect, wherein the transformation efficiency of Styrene oxide 98min. is 100%, and benzyl cyanide yield is 84.33%.
Exemplifying embodiment 12:
In fixed-bed reactor, add the catalyzer 30ml that adopts exemplifying embodiment 6 to prepare, at N
2under protection, be warming up to 380～450 ℃, with gas space velocity 600h
-1, in fixed-bed reactor, input Styrene oxide 98min. and toluene mixing solutions and ammonia, wherein Styrene oxide 98min. and ammonia mol ratio are 1:20, through catalytic ammoniation, obtain reaction solution, rectifying obtains products benzene acetonitrile.Through gc analysis, detect, wherein the transformation efficiency of Styrene oxide 98min. is 100%, and benzyl cyanide yield is 87.91%.
Exemplifying embodiment 13:
By selected catalyzer and the reaction conditions of above-mentioned exemplifying embodiment 12, at interval of sampling in 20 hours, through gc analysis, detect, the transformation efficiency of Styrene oxide 98min. and the selectivity of benzyl cyanide, investigate catalyst stability and life-span, the results are shown in Table 1.
Table 1: catalyst stability and life experiment result
★
| Reaction times (h) | 20 | 40 | 60 | 80 | 100 | 120 | 140 | 160 | 180 | 200 |
| Benzyl cyanide yield (%) | 87.7 | 87.6 | 86.8 | 86.0 | 82.2 | 79.0 | 76.1 | 73.4 | 72.5 | 71.5 |
★styrene oxide 98min. transformation efficiency is 100%
As can be seen from Table 1, after catalyzer successive reaction 200h, Styrene oxide 98min. transformation efficiency is 100%, and benzyl cyanide yield is down to 71.5%, and therefore this catalyst activity is more stable.
Exemplifying embodiment 14:
After above-mentioned embodiment 13 used catalyst successive reaction 200h, stop logical ammonia and liquid material, fill N
2be cooled to 300～450 ℃, with pneumatic pump to blowing air in system, gas speed is 300～400ml/min, after reaction 4h, by the selected reaction conditions of above-mentioned exemplifying embodiment 12, at interval of sampling in 20 hours, through gc analysis, detect the transformation efficiency of Styrene oxide 98min. and the selectivity of benzyl cyanide, catalytic activity and stability to the catalyzer after activating and regenerating are investigated, and the results are shown in Table 2.
Table 2: catalyst stability and life experiment result
★
| Reaction times (h) | 20 | 40 | 60 | 80 | 100 | 120 | 140 | 160 | 180 | 200 |
| Benzyl cyanide yield (%) | 87.6 | 87.8 | 86.5 | 85.8 | 83.0 | 78.7 | 75.6 | 73.8 | 72.5 | 71.5 |
★styrene oxide 98min. transformation efficiency is 100%
As can be seen from Table 2, after the catalyzer successive reaction 200h after regeneration, Styrene oxide 98min. transformation efficiency is still 100%, and benzyl cyanide yield does not reduce for catalyst activity with new system, therefore this catalyzer reusable edible.
By above-mentioned concrete exemplifying embodiment, can be obtained, the method for the synthetic benzyl cyanide of the present invention is more novel, and catalyzer preparation is simple, cheap and easy to get, catalytic activity is higher, and wherein Styrene oxide 98min. transformation efficiency is 100%, and the yield of benzyl cyanide is 87.91%, after non-stop run 200h, the transformation efficiency of Styrene oxide 98min. remains unchanged, and benzyl cyanide yield drops to 72.53%, and the catalyst activity after online activation is compared and do not reduced for catalyst activity with new system, the good stability of catalyzer, reusable edible.
Ball-type, powder γ-Al that the present invention uses
2o
3and ball-type SiO
2being Catalyst Factory, Nankai Univ buys.
Claims (3)
1. the method for a synthetic benzyl cyanide, it is characterized by raw materials used is Styrene oxide 98min. and ammonia, comprise the steps: to adopt fixed-bed reactor, Styrene oxide 98min. and toluene mixing solutions enter reactor through constant-flux pump, ammonia enters reactor through mass flowmeter, reacts for 300 ℃～450 ℃ of normal pressure, temperature; Styrene oxide 98min. and toluene mass ratio are 1:4, and Styrene oxide 98min. and ammonia mol ratio are 1:10～30; Styrene oxide 98min., toluene and ammonia gas mixture body are 500h by the volume space velocity of beds
-1to 600h
-1, under catalyst action, ammonification obtains benzyl cyanide;
The catalyzer that this reaction is used is comprised of carrier and catalytic active component, and wherein carrier is γ-Al
2o
3or SiO
2, the oxide compound that catalytic active component is metal M, catalytic active component total content is 19%～35% of catalyzer total mass; Catalyst particle size is 4 order～20 orders;
Described metal M is one or more in Fe, Ni, Co, Zn, Ni, Cr or Cu.
2. the method for synthetic benzyl cyanide as claimed in claim 1, is characterized by the oxide compound that catalytic active component is Zn, Zn/Co or Zn/Cr.
3. the method for synthetic benzyl cyanide as claimed in claim 1, is characterized by described catalyzer with kneading extrusion method or pickling process preparation.
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