CN109608315A - A kind of synthetic method of p-tert-butyl benzaldehyde - Google Patents
A kind of synthetic method of p-tert-butyl benzaldehyde Download PDFInfo
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- CN109608315A CN109608315A CN201811566863.XA CN201811566863A CN109608315A CN 109608315 A CN109608315 A CN 109608315A CN 201811566863 A CN201811566863 A CN 201811566863A CN 109608315 A CN109608315 A CN 109608315A
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- butylbenzaldehyde
- catalyst
- tert
- synthetic method
- molecular sieve
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- OTXINXDGSUFPNU-UHFFFAOYSA-N 4-tert-butylbenzaldehyde Chemical compound CC(C)(C)C1=CC=C(C=O)C=C1 OTXINXDGSUFPNU-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000010189 synthetic method Methods 0.000 title claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 51
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 22
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- QCWXDVFBZVHKLV-UHFFFAOYSA-N 1-tert-butyl-4-methylbenzene Chemical compound CC1=CC=C(C(C)(C)C)C=C1 QCWXDVFBZVHKLV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims abstract description 4
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 30
- 238000013019 agitation Methods 0.000 claims description 16
- 238000002803 maceration Methods 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims 2
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract 1
- 238000003760 magnetic stirring Methods 0.000 abstract 1
- 150000002815 nickel Chemical class 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 239000000376 reactant Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- TWQRQNJOSFBCJV-UHFFFAOYSA-N 2-tert-butylbenzaldehyde Chemical compound CC(C)(C)C1=CC=CC=C1C=O TWQRQNJOSFBCJV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 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 1
- 241000234269 Liliales Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- SDQFDHOLCGWZPU-UHFFFAOYSA-N lilial Chemical compound O=CC(C)CC1=CC=C(C(C)(C)C)C=C1 SDQFDHOLCGWZPU-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UPIJOAFHOIWPLT-UHFFFAOYSA-N methyl 4-tert-butylbenzoate Chemical class COC(=O)C1=CC=C(C(C)(C)C)C=C1 UPIJOAFHOIWPLT-UHFFFAOYSA-N 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明提供了一种对叔丁基苯甲醛的合成方法。采用液相氧化法，以对叔丁基甲苯为原料，氧气为氧化剂，N‑羟基邻苯二甲酰亚胺为引发剂，乙腈为溶剂，在催化剂作用下，于70℃、磁力搅拌转速200r/min下反应7h，可获得对叔丁基苯甲醛。所选择的催化剂为Ni负载的微孔分子筛，其制备原料包括镍盐，分子筛，去离子水，本发明以微孔分子筛为载体，采用浸渍法进行活性组分的负载，制得含有活性组分镍的催化剂，该催化剂有较高的选择性和活性，其在液相氧化制备对叔丁基苯甲醛的反应中原料的转化率达到30.6％，目标产物的选择性达到77.2％。相比较以往其他催化剂来说，选择性提高明显。
The invention provides a method for synthesizing p-tert-butyl benzaldehyde. The liquid-phase oxidation method was adopted, using p-tert-butyltoluene as the raw material, oxygen as the oxidant, N-hydroxyphthalimide as the initiator, and acetonitrile as the solvent, under the action of the catalyst, at 70°C, with a magnetic stirring speed of 200r /min for 7h to obtain p-tert-butylbenzaldehyde. The selected catalyst is Ni-loaded microporous molecular sieve, and its preparation raw materials include nickel salt, molecular sieve, and deionized water. In the present invention, the microporous molecular sieve is used as a carrier, and an impregnation method is used to load the active components, so as to obtain a product containing active components. The nickel catalyst has high selectivity and activity, the conversion rate of the raw material in the reaction of preparing p-tert-butylbenzaldehyde by liquid phase oxidation reaches 30.6%, and the selectivity of the target product reaches 77.2%. Compared with other catalysts in the past, the selectivity is significantly improved.
Description
Technical field
The present invention relates to catalysis oxidation p-tert-butyltoluene high selectivities under a kind of condition of normal pressure to tert-butyl benzene first
The method of aldehyde and its preparation of catalyst.
Background technique
P-t-Butylbenzaldehyde is a kind of important intermediate, and is widely used in drug, dyestuff and other chemicals,
Especially demand is huge in lilial synthesis.
The synthetic method of p-t-Butylbenzaldehyde is divided into oxidizing process and hydrogenation method, and wherein oxidizing process is divided into chemical oxidation again
Method, air oxidation process and electrochemical oxidation process etc., prepare that p-t-Butylbenzaldehyde mainly uses at present is exactly the method aoxidized.
Once about oxidation to tertiary fourth in the Chinese patent literature that the patent No. is respectively 101440028 A and CN102989499 A of CN
Base toluene synthesizes the report of p-t-Butylbenzaldehyde, and synthetic method is mostly to utilize Co salt load carriers such as HMS, MSU-X, SBA-
15, MCM-41, be as a result all product selectivity 45% or so, and by-product p-tert-butyl benzoic acid is more, and such as SBA-
15 wait carriers, and template is more expensive in manufacture craft, and takes a long time.
In 1944368 A Chinese patent literature of Patent No. CN, it was recently reported that with p-tert-butyl benzoic acid methyl esters be original
Material, in MnO/r-Al2O3、ZnO/r-Al2O3Under catalysis, hydrogenation reaction is carried out using the method for constant-pressure and high-temperature and is prepared to tert-butyl
Benzaldehyde, this method complex process include arene oxidizing carboxylic acid, then through esterification, hydrogenation synthesis aromatic aldehyde, reaction temperature exists
400 DEG C or more, yield is relatively low.In numerous methods that this field uses at present, it is relatively low, selective relatively low that all there is conversion ratios
The problem of.
Summary of the invention
The purpose of the present invention is to provide a kind of catalyst liquid phase oxidation p-tert-butyltoluene high selections in atmospheric conditions
Property synthesis p-t-Butylbenzaldehyde method.
Since the oxidation of p-tert-butyltoluene is stringenter to the amount of oxygen, very few oxidation can not exclusively be generated to tert-butyl
Product p-t-Butylbenzaldehyde can be excessively further oxidized to p-tert-butyl benzoic acid, so that the choosing of target product by benzyl alcohol
Selecting property is not high, meanwhile, the C=H bond energy of p-tert-butyltoluene is big, and it is not easy to break, therefore conversion ratio is relatively low.
To solve the above problems, the present invention adopts the following technical scheme that.
It is a kind of for synthesizing the preparation of the catalyst of p-t-Butylbenzaldehyde, the catalyst is prepared as follows:
Using NaY molecular sieve as carrier, nickel nitrate is presoma, and deionized water is that solvent forms maceration extract, will using equi-volume impregnating
Active component nickel is supported on carrier, 450 DEG C of roasting 4h, is formed with the catalyst of nickel load.
The mass ratio of p-tert-butyltoluene of the present invention, n-Hydroxyphthalimide and catalyst is 1:
0.02:0.04。
The volume ratio of solvent acetonitrile of the present invention and raw material p-tert-butyltoluene is 3:1.
It is of the present invention a kind of for synthesizing the preparation of the catalyst of p-t-Butylbenzaldehyde, it synthesizes to tert-butyl benzene first
The method of aldehyde are as follows: use the heterogeneous liquid-phase oxidation of normal pressure, using p-tert-butyltoluene as raw material, oxygen is oxidant, N- hydroxyl
Base phthalimide is initiator, and acetonitrile is solvent, under the action of catalyst, in 70 DEG C, magnetic agitation rotating speed 200r/
7h is reacted under min, can get p-t-Butylbenzaldehyde, the catalyst is the micro porous molecular sieve of Ni load.When specific operation,
Oxygen is controlled by gas flowmeter, and flow control is in 15ml/min.
The present invention recommends during preparing the micro porous molecular sieve of nickel load, specifically prepares as follows: by Ni
(NO3)2·6H2O is that solute dissolves in deionized water, is made into transparent dipping solution, NaY molecular sieve, magnetic agitation 3 is added
~4h after standing 12h age overnight at room temperature, is filtered, in 80 DEG C~100 DEG C baking 12h, sample roasts in 450 DEG C of Muffle furnace
Burn 4h.Up to the catalyst, the maceration extract is unsaturated solution, the hole of the dipping solution total volume and carrier
Volume is equal, and recommending the concentration of the nickel impregnation solution is 1.0mol/L.
In the embodiment of the present invention, NaY molecular sieve the preparation method is as follows:
The preparation method of NaY molecular sieve: sodium metasilicate is soluble in water, obtain A liquid；Sodium metaaluminate is dissolved in trimethyl hydroxide
It in ammonium, then is mixed with above-mentioned A liquid, crystallization obtains B liquid in crystallizing kettle；Dodecyl trimethyl ammonium bromide is soluble in water and drips
It adds in B liquid, it is 10 that hydrochloric acid, which is added, and adjusts PH, and age overnight after stirring filters drying, NaY points of 4h are roasted at 550 DEG C
Son sieve.
Advantages of the present invention is shown:
1, using the NaY molecular sieve of nickel load as catalyst, compared to previous catalyst, recycling number is more, target
Product separation is easy.
2, using the NaY molecular sieve of nickel load as catalyst, compared to catalyst used in previous this field, conversion ratio is more
Height, selectivity are more preferable.
3, investigation of the revolving speed to the influence factor of the reaction is increased simultaneously, avoids the occurrence of the deep oxidation of aldehyde.
4, process of the invention is simple, easy to operate, and high income is corrosion-free, and does not produce in operation to environment
It is raw to destroy.
Detailed description of the invention
Fig. 1 is the equipment drawing for synthesizing p-t-Butylbenzaldehyde；1 flowmeter, 2 spherical condensation tubes, 3 oil bath pans, the heating of 4 magnetic force
Blender.
Specific implementation method
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This.
Embodiment 1
The preparation of 15%Ni/NaY: using equi-volume impregnating, by BET detection it is known that the ratio hole of NaY molecular sieve
Holding is 0.36ml/g, then when needing active component content (in terms of oxide) is 15%, it is known that the maceration extract needed is dense
Degree is 0.5mol/L, extrapolates and needs Ni (NO3)2·6H2O 7.25g.By 7.25g Ni (NO3)2·6H2O is dissolved in 50mL's
In deionized water, maceration extract 1 is obtained, 5g NaY molecular sieve magnetic agitation 3h is added, stands 12h age overnight, is filtered, 80 DEG C
12h is dried, 450 DEG C of roasting 4h are up to 15%Ni/NaY catalyst.
Oxidation reaction: being added 6mL p-tert-butyltoluene and 18mL acetonitrile (volume ratio 1:3) in 25mL three-necked flask,
70 DEG C of oil bath heatings, be condensed back, magnetic agitation rotating speed be 200r/min wait for temperature to 70 DEG C, be added 0.2g15%Ni/NaY and
0.1gN- hydroxyphthalimide (mass ratio 2:1), and it is passed through oxygen, it is 15mL/ that flowmeter, which controls gas flow,
Min, after reacting 7h, stopping is passed through oxygen, reactant refrigerated separation, as a result GC detection is listed in table 1.
Embodiment 2
The preparation of 25%Ni/NaY: using equi-volume impregnating, by BET detection it is known that the ratio hole of NaY molecular sieve
Holding is 0.36ml/g, then when needing active component content (in terms of oxide) is 25%, it is known that the maceration extract needed is dense
Degree is 1.0mol/L, extrapolates and needs Ni (NO3)2·6H2O 14.50g.By 14.50g Ni (NO3)2·6H2O is dissolved in 50mL
Deionized water in, obtain maceration extract 2,5g NaY molecular sieve magnetic agitation 3h be added, stand 12h age overnight, filter, 80
DEG C drying 12h, 450 DEG C of roasting 4h are up to 25%Ni/NaY catalyst.
Oxidation reaction: being added 6mL p-tert-butyltoluene and 18mL acetonitrile (volume ratio 1:3) in 25mL three-necked flask,
70 DEG C of oil bath heatings are condensed back, and magnetic agitation rotating speed is that 200r/min waits for that 70 DEG C, 0.2g 25%Ni/NaY is added in temperature
With 0.1gN- hydroxyphthalimide (mass ratio 2:1), and it is passed through oxygen, it is 15mL/ that flowmeter, which controls gas flow,
Min, after reacting 7h, stopping is passed through oxygen, reactant refrigerated separation, as a result GC detection is listed in table 1.
Embodiment 3
The preparation of 35%Ni/NaY: using equi-volume impregnating, by BET detection it is known that the ratio hole of NaY molecular sieve
Holding is 0.36ml/g, then when needing active component content (in terms of oxide) is 35%, it is known that the maceration extract needed is dense
Degree is 1.5mol/L, extrapolates and needs Ni (NO3)2·6H2O 21.75g.By 21.75g Ni (NO3)2·6H2O is dissolved in 50mL
Deionized water in, obtain maceration extract 3,5g NaY molecular sieve magnetic agitation 3h be added, stand 12h age overnight, filter, 80
DEG C drying 12h, 450 DEG C of roasting 4h are up to 35%Ni/NaY catalyst.
Oxidation reaction: being added 6mL p-tert-butyltoluene and 18mL acetonitrile (volume ratio 1:3) in 25mL three-necked flask,
70 DEG C of oil bath heatings, be condensed back, magnetic agitation rotating speed be 200r/min wait for temperature to 70 DEG C, be added 0.2g35%Ni/NaY and
0.1gN- hydroxyphthalimide (mass ratio 2:1), and it is passed through oxygen, it is 15mL/ that flowmeter, which controls gas flow,
Min, after reacting 7h, stopping is passed through oxygen, reactant refrigerated separation, as a result GC detection is listed in table 1.
Embodiment 4
25%Ni/NaY prepares same as Example 2.
Oxidation reaction: being added 6mL p-tert-butyltoluene and 18mL acetonitrile (volume ratio 1:3) in 25mL three-necked flask,
60 DEG C of oil bath heatings, be condensed back, magnetic agitation rotating speed be 200r/min wait for temperature to 60 DEG C, be added 0.2g25%Ni/NaY and
0.1gN- hydroxyphthalimide (mass ratio 2:1), and it is passed through oxygen, it is 15mL/ that flowmeter, which controls gas flow,
Min, after reacting 7h, stopping is passed through oxygen, reactant refrigerated separation, as a result GC detection is listed in table 1.
Embodiment 5
25%Ni/NaY prepares same as Example 2.
Oxidation reaction: being added 6mL p-tert-butyltoluene and 18mL acetonitrile (volume ratio 1:3) in 25mL three-necked flask,
80 DEG C of oil bath heatings, be condensed back, magnetic agitation rotating speed be 200r/min wait for temperature to 80 DEG C, be added 0.2g25%Ni/NaY and
0.1gN- hydroxyphthalimide (mass ratio 2:1), and it is passed through oxygen, it is 15mL/ that flowmeter, which controls gas flow,
Min, after reacting 7h, stopping is passed through oxygen, reactant refrigerated separation, as a result GC detection is listed in table 1.
Embodiment 6
25%Ni/NaY prepares same as Example 2.
Oxidation reaction: being added 6mL p-tert-butyltoluene and 18mL acetonitrile (volume ratio 1:3) in 25mL three-necked flask,
70 DEG C of oil bath heatings, be condensed back, magnetic agitation rotating speed be 200r/min wait for temperature to 70 DEG C, be added 0.2g25%Ni/NaY and
0.1gN- hydroxyphthalimide (mass ratio 2:1), and it is passed through oxygen, it is 10mL/ that flowmeter, which controls gas flow,
Min, after reacting 7h, stopping is passed through oxygen, reactant refrigerated separation, as a result GC detection is listed in table 1.
Embodiment 7
25%Ni/NaY prepares same as Example 2.
Oxidation reaction: being added 6mL p-tert-butyltoluene and 18mL acetonitrile (volume ratio 1:3) in 25mL three-necked flask,
70 DEG C of oil bath heatings are condensed back, and magnetic agitation rotating speed is that 200r/min waits for that 70 DEG C, 0.2g 25%Ni/NaY is added in temperature
With 0.1gN- hydroxyphthalimide (mass ratio 2:1), and it is passed through oxygen, it is 20mL/ that flowmeter, which controls gas flow,
Min, after reacting 7h, stopping is passed through oxygen, reactant refrigerated separation, as a result GC detection is listed in table 1.
Embodiment 8
25%Ni/NaY prepares same as Example 2.
Oxidation reaction: being added 6mL p-tert-butyltoluene and 18mL acetonitrile (volume ratio 1:3) in 25mL three-necked flask,
70 DEG C of oil bath heatings, be condensed back, magnetic agitation rotating speed be 200r/min wait for temperature to 70 DEG C, be added 0.2g25%Ni/NaY and
0.2gN- hydroxyphthalimide (mass ratio 1:1), and it is passed through oxygen, it is 15mL/ that flowmeter, which controls gas flow,
Min, after reacting 7h, stopping is passed through oxygen, reactant refrigerated separation, as a result GC detection is listed in table 1.
Embodiment 9
25%Ni/NaY prepares same as Example 2.
Oxidation reaction: being added 6mL p-tert-butyltoluene and 18mL acetonitrile (volume ratio 1:3) in 25mL three-necked flask,
70 DEG C of oil bath heatings, be condensed back, magnetic agitation rotating speed be 200r/min wait for temperature to 70 DEG C, be added 0.2g25%Ni/NaY and
0g n-Hydroxyphthalimide (mass ratio 0), and it is passed through oxygen, it is 15mL/min that flowmeter, which controls gas flow, instead
After answering 7h, stopping is passed through oxygen, reactant refrigerated separation, as a result GC detection is listed in table 1.
1 experimental result of table
Claims (10)
1. a kind of synthetic method of p-t-Butylbenzaldehyde, it is characterised in that: the method are as follows: use the heterogeneous liquid phase of normal pressure
Method for oxidation, using p-tert-butyltoluene as raw material, oxygen is oxidant, and n-Hydroxyphthalimide is initiator, acetonitrile
7h is reacted under 70 DEG C, magnetic agitation rotating speed 200r/min under the action of catalyst for solvent, can get to tert-butyl benzene first
Aldehyde, the catalyst are the micro porous molecular sieve of Ni load.
2. the synthetic method of p-t-Butylbenzaldehyde as described in claim 1, it is characterised in that the p-tert-butyltoluene,
The mass ratio of n-Hydroxyphthalimide and catalyst is 1:0.02:0.04.
3. the synthetic method of p-t-Butylbenzaldehyde as described in claim 1, it is characterised in that solvent acetonitrile and raw material are to uncle
The volume ratio of butyl toluene is 3:1.
4. the synthetic method of p-t-Butylbenzaldehyde as described in claim 1, it is characterised in that the oxidant oxygen stream
Amount is in 5~25ml/min.
5. the synthetic method of p-t-Butylbenzaldehyde as described in claim 1, it is characterised in that reaction uses magnetic agitation, turns
Speed is in 0~400r/min.
6. the synthetic method of p-t-Butylbenzaldehyde as described in claim 1, it is characterised in that the catalyst is by as follows
Method preparation: using NaY molecular sieve as carrier, nickel nitrate is presoma, and deionized water is that solvent forms maceration extract, using infusion process
Active component nickel is supported on carrier, 450 DEG C of roasting 4h, is formed with the catalyst of nickel load.
7. the synthetic method of p-t-Butylbenzaldehyde as claimed in claim 6, it is characterised in that described infusion process use etc.
Volume impregnation, the maceration extract are unsaturated solution.
8. the synthetic method of p-t-Butylbenzaldehyde as described in claim 1, it is characterised in that the catalyst is negative for nickel
Micro porous molecular sieve of the mounted mass (in terms of oxide) 15~35%.
9. the synthetic method of p-t-Butylbenzaldehyde as claimed in claim 6, it is characterised in that the presoma is Ni
(NO3)2·6H2O, impregnation concentration are 0.5~1.5mol/L.
10. the synthetic method of p-t-Butylbenzaldehyde as claimed in claim 6, it is characterised in that the catalyst preparation
In, the molecular sieve is the NaY molecular sieve with FAU structure.
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| CN101440028A (en) * | 2008-11-06 | 2009-05-27 | 浙江工业大学 | Process for synthesizing p-tertiary butyl benzaldehyde |
| CN102989499A (en) * | 2012-12-18 | 2013-03-27 | 陕西省石油化工研究设计院 | Catalyst for preparing p-tertbutyl benzaldehyde and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440028A (en) * | 2008-11-06 | 2009-05-27 | 浙江工业大学 | Process for synthesizing p-tertiary butyl benzaldehyde |
| CN102989499A (en) * | 2012-12-18 | 2013-03-27 | 陕西省石油化工研究设计院 | Catalyst for preparing p-tertbutyl benzaldehyde and preparation method |
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| QIAN YIN等: "Study on the Liquid Phase Oxidation of p-Tert-butyltoluene Over Ni/NaY", 《CATALYSIS LETTERS》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113617363A (en) * | 2021-08-30 | 2021-11-09 | 武汉强丰新特科技有限公司 | Supported multi-metal oxide catalyst and preparation method and application thereof |
| CN113617363B (en) * | 2021-08-30 | 2023-03-17 | 武汉强丰新特科技有限公司 | Supported multi-metal oxide catalyst and preparation method and application thereof |
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