CN106140147B - A kind of p nitro ethylbenzene oxidation p-nitroacetophenone catalyst processed and preparation method thereof - Google Patents
A kind of p nitro ethylbenzene oxidation p-nitroacetophenone catalyst processed and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- YQYGPGKTNQNXMH-UHFFFAOYSA-N 4-nitroacetophenone Chemical compound CC(=O)C1=CC=C([N+]([O-])=O)C=C1 YQYGPGKTNQNXMH-UHFFFAOYSA-N 0.000 title claims abstract description 27
- RESTWAHJFMZUIZ-UHFFFAOYSA-N 1-ethyl-4-nitrobenzene Chemical compound CCC1=CC=C([N+]([O-])=O)C=C1 RESTWAHJFMZUIZ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 title description 11
- 230000003647 oxidation Effects 0.000 title description 10
- 239000000919 ceramic Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 239000004927 clay Substances 0.000 claims abstract description 10
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000000454 talc Substances 0.000 claims abstract description 10
- 229910052623 talc Inorganic materials 0.000 claims abstract description 10
- 235000012222 talc Nutrition 0.000 claims abstract description 10
- 238000001238 wet grinding Methods 0.000 claims abstract description 10
- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims abstract description 5
- 239000007767 bonding agent Substances 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 239000002002 slurry Substances 0.000 claims description 35
- 241000264877 Hippospongia communis Species 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 150000000703 Cerium Chemical class 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 7
- PXWYZLWEKCMTEZ-UHFFFAOYSA-N 1-ethyl-2-nitrobenzene Chemical class CCC1=CC=CC=C1[N+]([O-])=O PXWYZLWEKCMTEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000010304 firing Methods 0.000 abstract 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 6
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 6
- 239000000498 cooling water Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000007710 freezing Methods 0.000 description 6
- 230000008014 freezing Effects 0.000 description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
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Abstract
The present invention provides a kind of p nitro ethylbenzenes to aoxidize p-nitroacetophenone catalyst processed and preparation method thereof, it is one kind using clay, talcum as main composition raw material, be added cerium (+trivalent), manganese (+2) hydroxide in ball milling the powder of wet-milling to less than 320 mesh, it is added with MC or PVA bonding agent as main component, process flow through extrusion molding, honeycomb greenwave is produced, catalyst made of firing by 1240~1280 DEG C.The catalyst includes active catalytic component cerium sesquioxide, manganese dioxide and ceramic monolith.Ce of the invention2O3‑MnO2The ceramic honeycomb catalyst of/ceramic monolith has the characteristics of excellent catalytic effect, long service life.P-nitroacetophenone is prepared for pure oxygen catalytic p nitro ethylbenzene, the yield of p-nitroacetophenone is 65% or more.
Description
Technical field:
The present invention provides a kind of p nitro ethylbenzenes to aoxidize p-nitroacetophenone catalyst processed and preparation method thereof.
Background technique:
P-nitroacetophenone (PNAP) is important organic synthesis intermediate, is widely used in synthesis medicine, pesticide and chirality
The synthesis of intermediate.P nitro ethylbenzene oxidation prepares p-nitroacetophenone, deep by the direct oxidation for controlling aromatic side chain α-H
Degree obtains ketone group.The extremely strong chemical oxidizing agent of some oxidisability of Seedling selection, such as: KMnO4、H2O2With CrO3 etc..And select oxygen
Gas is as oxidant, compared to chemical oxidizing agent, the double dominant with economic cost and environmental protection.Currently, industrial raw
Producing p-nitroacetophenone method is: p nitro ethylbenzene is added in oxidizing tower, cobaltous octadecanate and manganese acetate catalyst are added, to
It is passed through compressed air in tower, makes 0.5 megapascal of tower pressure interior force or so, is warming up to 150 DEG C, provocative reaction, reaction starts rear heat release,
Suitably to reaction tower collet water flowing, decline reaction temperature steadily, so that it is maintained 130~150 DEG C and react 2 hours；When anti-
When process being answered not regenerate water, that is, reach home.Then another reaction kettle is added in reaction solution, stirred, is added in 75~80 DEG C
Sodium carbonate liquor is to pH value=7.5~8；- 6 DEG C are cooled to, filtering；It washes again, methanol is washed, and it is dry, it is obtained to nitro
The yield of acetophenone is between 55~65%.
SU1330128 (publication date: on 2 15th, 1985) discloses a kind of catalytic oxygen or air oxidation p nitro ethylbenzene
The method for preparing p-nitroacetophenone, this method use manganese acetate as catalyst, nickel acetate or tin acetate as co-catalyst,
Catalytic oxygen or air oxidation p nitro ethylbenzene prepare p-nitroacetophenone.It is 140 DEG C of reaction temperature, oxidation reaction 4h, acquired
P-nitroacetophenone yield be 58.6%
CN 201010103450.5 (publication date: on June 23rd, 2010) discloses a kind of bionically catalyzing and oxidizing to nitre
The method that base ethylbenzene prepares p-nitroacetophenone, this method under normal pressure, solvent-free, are selected using p nitro ethylbenzene as raw material
Then metalloporphyrin or metalloporphyrin-transition metal salt composite catalyst exist as catalyst in 150~200 DEG C of initiation reactions
80~128 DEG C of 6~18h of reaction, the yield of obtained p-nitroacetophenone are 61.5%.
Production experience and document report show that current p nitro ethylbenzene oxidation catalytic systems touch and have the following problems:
1, the separation for being scattered in the catalyst and product of system is difficult, is difficult to repeat to recycle；
2, the efficiency of catalyst is lower, and p nitro ethylbenzene oxidation time is long.
Compared with the catalyst that current p nitro ethylbenzene oxidation uses, honeycomb ceramic carrier catalyst then has specific surface
Product is big, and catalytic activity is high, fixed bed reactors is formed, many advantages, such as being recycled.
The content of invention:
The purpose of the present invention is preparing the above problem present in p-nitroacetophenone technology for existing p nitro ethylbenzene,
A kind of p nitro ethylbenzene oxidation p-nitroacetophenone catalyst processed and preparation method thereof, Ce of the invention are provided2O3-MnO2/ pottery
The ceramic honeycomb catalyst of ceramic carrier has the characteristics of excellent catalytic effect, long service life.
The present invention provides a kind of p nitro ethylbenzenes to aoxidize p-nitroacetophenone catalyst processed and preparation method thereof, including
Following steps:
It will be dissolved in deionized water containing soluble cerium salt (+trivalent), solution is made, quickly stirs and be added dropwise 40%NaOH,
PH to 12 is adjusted, it is spare to obtain white slurry.
Soluble manganese salt (+divalent) will be saturated to be dissolved in deionized water, solution is made, quickly stirs and be added dropwise 40%NaOH,
PH to 10 is adjusted, is obtained to the slurry of pink, the slurry for being oxidizing to brown is spare.
Clay, talcum and above two slurry powder of wet-milling to less than 320 mesh in ball milling are added with MC or PVA
Honeycomb greenwave is produced in bonding agent as main component, the process flow through extrusion molding, using box-type drying furnace, through excessively high
Ceramic honeycomb catalyst made of temperature is fired.
The present invention is by by active constituent Ce2O3、MnO2It is carried on ceramic honey comb, the catalyst includes active catalytic
On component cerium sesquioxide, manganese dioxide and ceramic monolith, fixed bed reactors are formed, are used for pure oxygen catalytic p nitro ethylbenzene system
Standby p-nitroacetophenone, the yield of p-nitroacetophenone is 65% or more.
Specific embodiment mode:
Below with reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
Weigh the anhydrous cerous chloride zinc (CeCl of 46g3) be dissolved in the deionized water of 250ml, after being sufficiently uniformly dissolved, fastly
Speed stirs and is added dropwise 40%NaOH, adjusts pH to 12, obtains white slurry.
Weigh 312g manganese sulfate (MnSO4) be dissolved in the deionized water of 1000ml, after being sufficiently uniformly dissolved, quickly stir
And 40%NaOH is added dropwise, pH to 10 is adjusted, obtains to the slurry of pink, is oxidizing to the slurry of brown.
By clay 660g, talcum 130g and above two slurry powder of wet-milling to less than 320 mesh in ball milling, it is added viscous
And honeycomb greenwave is produced in agent, the process flow through extrusion molding, using 105 DEG C of drying 3h of box-type drying furnace, by 1280 DEG C
6h is fired, cylinder ceramic honeycomb catalyst size (mm) 150 × 150 × 300, hole count 25 × 25, wall thickness (mm) 1.0, hole are obtained
It is wide by 2.77, specific surface area (m2/m3) 580, voidage (%) 68.
The content of ceramic honeycomb catalyst active catalytic component are as follows:
Above-mentioned catalyst is fitted into the fixed bed reactors of 6L, addition 4000g p nitro ethylbenzene, under normal pressure, Xiang Fanying
Device is passed through pure oxygen, is warming up to 150 DEG C, and provocative reaction, reaction starts rear heat release, leads to cooling water, dimension to fixed bed reactors collet
Mixture freezing, the centrifugal filtration in 112 DEG C of reaction 1.5h, after reaction are held, then obtains p-nitroacetophenone with ethyl alcohol recrystallization,
Its yield is 65.6, purity 97%.
Embodiment 2
Weigh the anhydrous cerous chloride zinc (CeCl of 52g3) be dissolved in the deionized water of 250ml, after being sufficiently uniformly dissolved, fastly
Speed stirs and is added dropwise 40%NaOH, adjusts pH to 12, obtains white slurry.
Weigh 268g manganese sulfate (MnSO4) be dissolved in the deionized water of 1000ml, after being sufficiently uniformly dissolved, quickly stir
And 40%NaOH is added dropwise, pH to 10 is adjusted, obtains to the slurry of pink, is oxidizing to the slurry of brown.
By clay 665g, talcum 145g and above two slurry powder of wet-milling to less than 320 mesh in ball milling, it is added viscous
And honeycomb greenwave is produced in agent, the process flow through extrusion molding, using 105 DEG C of drying 3h of box-type drying furnace, by 1260 DEG C
6h is fired, cylinder ceramic honeycomb catalyst size (mm) 150 × 150 × 300, hole count 32 × 32, wall thickness (mm) 1.0, hole are obtained
It is wide by 3.66, specific surface area (m2/m3) 695, voidage (%) 61.
The content of ceramic honeycomb catalyst active catalytic component are as follows:
Above-mentioned catalyst is fitted into the fixed bed reactors of 6L, addition 4000g p nitro ethylbenzene, under normal pressure, Xiang Fanying
Device is passed through pure oxygen, is warming up to 150 DEG C, and provocative reaction, reaction starts rear heat release, leads to cooling water, dimension to fixed bed reactors collet
Mixture freezing, the centrifugal filtration in 112 DEG C of reaction 1.5h, after reaction are held, then obtains p-nitroacetophenone with ethyl alcohol recrystallization,
Its yield is 65.4, purity 98%.
Embodiment 3
Weigh the anhydrous cerous chloride zinc (CeCl of 60g3) be dissolved in the deionized water of 250ml, after being sufficiently uniformly dissolved, fastly
Speed stirs and is added dropwise 40%NaOH, adjusts pH to 12, obtains white slurry.
Weigh 248g manganese sulfate (MnSO4) be dissolved in the deionized water of 1000ml, after being sufficiently uniformly dissolved, quickly stir
And 40%NaOH is added dropwise, pH to 10 is adjusted, obtains to the slurry of pink, is oxidizing to the slurry of brown.
By clay 680g, talcum 107g and above two slurry powder of wet-milling to less than 320 mesh in ball milling, it is added viscous
And honeycomb greenwave is produced in agent, the process flow through extrusion molding, using 105 DEG C of drying 3h of box-type drying furnace, by 1260 DEG C
6h is fired, cylinder ceramic honeycomb catalyst size (mm) 150 × 150 × 300, hole count 40 × 40, wall thickness (mm) 0.7, hole are obtained
It is wide by 3.03, specific surface area (m2/m3) 891, voidage (%) 65.
The content of ceramic honeycomb catalyst active catalytic component are as follows:
Above-mentioned catalyst is fitted into the fixed bed reactors of 6L, addition 4000g p nitro ethylbenzene, under normal pressure, Xiang Fanying
Device is passed through pure oxygen, is warming up to 150 DEG C, and provocative reaction, reaction starts rear heat release, leads to cooling water, dimension to fixed bed reactors collet
Mixture freezing, the centrifugal filtration in 112 DEG C of reaction 1.5h, after reaction are held, then obtains p-nitroacetophenone with ethyl alcohol recrystallization,
Its yield is 65.8, purity 97%.
Embodiment 4
Weigh the anhydrous cerous chloride zinc (CeCl of 67g3) be dissolved in the deionized water of 250ml, after being sufficiently uniformly dissolved, fastly
Speed stirs and is added dropwise 40%NaOH, adjusts pH to 12, obtains white slurry.
Weigh 238g manganese sulfate (MnSO4) be dissolved in the deionized water of 1000ml, after being sufficiently uniformly dissolved, quickly stir
And 40%NaOH is added dropwise, pH to 10 is adjusted, obtains to the slurry of pink, is oxidizing to the slurry of brown.
By clay 700g, talcum 118g and above two slurry powder of wet-milling to less than 320 mesh in ball milling, it is added viscous
And honeycomb greenwave is produced in agent, the process flow through extrusion molding, using 105 DEG C of drying 3h of box-type drying furnace, by 1260 DEG C
6h is fired, cylinder ceramic honeycomb catalyst size (mm) 150 × 150 × 300, hole count 43 × 43, wall thickness (mm) 0.7, hole are obtained
It is wide by 2.77, specific surface area (m2/m3) 940, voidage (%) 63.
The content of ceramic honeycomb catalyst active catalytic component are as follows:
Above-mentioned catalyst is fitted into the fixed bed reactors of 6L, addition 4000g p nitro ethylbenzene, under normal pressure, Xiang Fanying
Device is passed through pure oxygen, is warming up to 150 DEG C, and provocative reaction, reaction starts rear heat release, leads to cooling water, dimension to fixed bed reactors collet
Mixture freezing, the centrifugal filtration in 112 DEG C of reaction 1.5h, after reaction are held, then obtains p-nitroacetophenone with ethyl alcohol recrystallization,
Its yield is 65.8, purity 97%.
Embodiment 5
Weigh the anhydrous cerous chloride zinc (CeCl of 67g3) be dissolved in the deionized water of 250ml, after being sufficiently uniformly dissolved, fastly
Speed stirs and is added dropwise 40%NaOH, adjusts pH to 12, obtains white slurry.
Weigh 218g manganese sulfate (MnSO4) be dissolved in the deionized water of 1000ml, after being sufficiently uniformly dissolved, quickly stir
And 40%NaOH is added dropwise, pH to 10 is adjusted, obtains to the slurry of pink, is oxidizing to the slurry of brown.
By clay 740g, talcum 80g and above two slurry powder of wet-milling to less than 320 mesh in ball milling, it is added viscous
And honeycomb greenwave is produced in agent, the process flow through extrusion molding, using 105 DEG C of drying 3h of box-type drying furnace, by 1230 DEG C
6h is fired, cylinder ceramic honeycomb catalyst size (mm) 150 × 150 × 300, hole count 50 × 50, wall thickness (mm) 0.6, hole are obtained
It is wide by 2.39, specific surface area (m2/m3) 1090, voidage (%) 63.
The content of ceramic honeycomb catalyst active catalytic component are as follows:
Above-mentioned catalyst is fitted into the fixed bed reactors of 6L, addition 4000g p nitro ethylbenzene, under normal pressure, Xiang Fanying
Device is passed through pure oxygen, is warming up to 150 DEG C, and provocative reaction, reaction starts rear heat release, leads to cooling water, dimension to fixed bed reactors collet
Mixture freezing, the centrifugal filtration in 112 DEG C of reaction 1.5h, after reaction are held, then obtains p-nitroacetophenone with ethyl alcohol recrystallization,
Its yield is 65.4, purity 98%.
Embodiment 6
Weigh the anhydrous cerous chloride zinc (CeCl of 74g3) be dissolved in the deionized water of 250ml, after being sufficiently uniformly dissolved, fastly
Speed stirs and is added dropwise 40%NaOH, adjusts pH to 12, obtains white slurry.
Weigh 208g manganese sulfate (MnSO4) be dissolved in the deionized water of 1000ml, after being sufficiently uniformly dissolved, quickly stir
And 40%NaOH is added dropwise, pH to 10 is adjusted, obtains to the slurry of pink, is oxidizing to the slurry of brown.
By clay 740g, talcum 80g and above two slurry powder of wet-milling to less than 320 mesh in ball milling, it is added viscous
And honeycomb greenwave is produced in agent, the process flow through extrusion molding, using 105 DEG C of drying 3h of box-type drying furnace, by 1230 DEG C
6h is fired, cylinder ceramic honeycomb catalyst size (mm) 150 × 150 × 300, hole count 60 × 60, wall thickness (mm) 0.5, hole are obtained
It is wide by 1.99, specific surface area (m2/m3) 1303, voidage (%) 63.
The content of ceramic honeycomb catalyst active catalytic component are as follows:
Above-mentioned catalyst is fitted into the fixed bed reactors of 6L, addition 4000g p nitro ethylbenzene, under normal pressure, Xiang Fanying
Device is passed through pure oxygen, is warming up to 150 DEG C, and provocative reaction, reaction starts rear heat release, leads to cooling water, dimension to fixed bed reactors collet
Mixture freezing, the centrifugal filtration in 112 DEG C of reaction 1.5h, after reaction are held, then obtains p-nitroacetophenone with ethyl alcohol recrystallization,
Its yield is 65.8, purity 98%.
Claims (5)
1. a kind of p nitro ethylbenzene aoxidizes p-nitroacetophenone catalyst processed, which is characterized in that active catalytic component is three oxygen
Change two cerium Ce2O3, manganese dioxide MnO2And ceramic monolith；
The preparation method of the catalyst, comprising the following steps:
It will be dissolved in deionized water containing solubility+trivalent cerium salt, solution is made, and quickly stir and be added dropwise 40%NaOH, and adjust pH
To 12, it is spare to obtain white slurry；Saturation solubility+divalent manganese salt is dissolved in deionized water, solution is made, is quickly stirred simultaneously
40%NaOH is added dropwise, adjusts pH to 10, obtains to the slurry of pink, the slurry for being oxidizing to brown is spare；By clay, talcum with it is upper
Two kinds of slurries powder of wet-milling to less than 320 mesh in ball milling is stated, is added with MC or PVA bonding agent as main component, through squeezing
Honeycomb greenwave is produced in molding process flow out, using box-type drying furnace, the catalysis of ceramic honey comb made of being fired by high temperature
Agent.
2. catalyst according to claim 1, which is characterized in that by weight percentage, the content of active catalytic component
Are as follows:
Ce2O33~5%
MnO212~18%.
3. the according to claim 1, preparation method of catalyst described in 2, it is characterised in that include the following steps:
Solubility+trivalent cerium salt is dissolved into solution according to the ratio, quickly stirs and be added dropwise 40%NaOH, pH to 12 is adjusted, obtains white
Mill base material is spare；Solubility+divalent manganese salt is dissolved into solution according to the ratio again, quickly stirs and be added dropwise 40%NaOH, adjust pH to
10, it obtains to the slurry of pink, the slurry for being oxidizing to brown is spare, is uniformly mixed with clay, talcum with above-mentioned slurry, in ball milling
The process flow through extrusion molding with MC or PVA bonding agent as main component is added in the powder of middle wet-milling to less than 320 mesh,
And be dried and roast, obtain catalyst.
4. according to the method described in claim 3, it is characterized in that, maturing temperature is 1240~1280 DEG C, the time 4~6 hours.
5. according to the method described in claim 3, it is characterized in that, the process flow through extrusion molding, and being dried and roasting
It burns, obtained cylinder ceramic honey comb, cylinder ceramic honey comb 150 × 150 × 300mm of size, hole count 25~60, wall thickness 0.5~
1.99~4.96mm of 1.0mm, Kong Kuan, 580~1303m of specific surface area2/m3, voidage 61~68%.
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