CN100346877C - Catalyst for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde, its prepn. method and application thereof - Google Patents
Catalyst for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde, its prepn. method and application thereof Download PDFInfo
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- CN100346877C CN100346877C CNB2005101313610A CN200510131361A CN100346877C CN 100346877 C CN100346877 C CN 100346877C CN B2005101313610 A CNB2005101313610 A CN B2005101313610A CN 200510131361 A CN200510131361 A CN 200510131361A CN 100346877 C CN100346877 C CN 100346877C
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- phenylmethanol
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- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 60
- 230000003647 oxidation Effects 0.000 title claims abstract description 59
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title claims abstract description 50
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 235000019445 benzyl alcohol Nutrition 0.000 title claims abstract description 33
- 229960004217 benzyl alcohol Drugs 0.000 title claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- 239000012153 distilled water Substances 0.000 claims description 50
- 238000006392 deoxygenation reaction Methods 0.000 claims description 46
- 238000005406 washing Methods 0.000 claims description 36
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 27
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 27
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 27
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical group [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 27
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 25
- 235000017281 sodium acetate Nutrition 0.000 claims description 25
- 239000001632 sodium acetate Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000001291 vacuum drying Methods 0.000 claims description 18
- ZLXPLDLEBORRPT-UHFFFAOYSA-M [NH4+].[Fe+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Fe+].[O-]S([O-])(=O)=O ZLXPLDLEBORRPT-UHFFFAOYSA-M 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 9
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910000398 iron phosphate Inorganic materials 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 40
- 239000000243 solution Substances 0.000 description 22
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 12
- 239000005955 Ferric phosphate Substances 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 12
- 229940032958 ferric phosphate Drugs 0.000 description 12
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 12
- 235000012736 patent blue V Nutrition 0.000 description 12
- 238000002156 mixing Methods 0.000 description 10
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- -1 phosphate dihydrogen salt Chemical class 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- YZZMZIAXNHIMTD-UHFFFAOYSA-N [NH4+].P(=O)(O)(O)[O-].[Na] Chemical compound [NH4+].P(=O)(O)(O)[O-].[Na] YZZMZIAXNHIMTD-UHFFFAOYSA-N 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KGYGBOORGRYDGQ-UHFFFAOYSA-N benzene;methanol Chemical compound OC.C1=CC=CC=C1 KGYGBOORGRYDGQ-UHFFFAOYSA-N 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a catalyst for the catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde and the preparation method and the application thereof. In view of the disadvantages of cost being higher and phenylmethanol being not capable of obtaining the benzaldehyde with high selectivity under high conversion rate and gas-phase condition, the formula of the catalyst of the present invention is Fe1-x (2) Fex (3) (PO4) (2+x) /3, wherein x is bigger than 0 and smaller than 1, and 2, 3 are the oxidation states of iron. The present invention uses iron phosphate with low cost as the catalyst, catalyzes the phenylmethanol with high efficiency and manufactures the benzaldehyde through gas-phase selective oxidation, and the activity of the catalyst Fe0.2 (2) Fe0.8 (3) (PO4) 2.8/3 of the present invention is the best. When the conversion rate of the phenylmethanol is 96.6%, the selectivity of the benzaldehyde is 92.3%.
Description
Technical field
The present invention relates to a kind of catalyst and this Preparation of catalysts method and application thereof that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde.
Background technology
The selective oxidation of phenmethylol is a representative reaction in oxidation of alcohols research.At present, with H
2O
2, O
2Or air is as cleaning oxidizer, the selective oxidation reaction of phenmethylol is mainly the homogeneous phase and the heterogeneous oxidation of liquid phase, and water/organic biphasic catalysis, reacting employed catalyst and mainly concentrate on Ru, Pd and the compound, metals such as Co, Os, Pt also have some reports in addition.Research report for the gas-solid heterogeneous oxidation is less.People such as Sumathi R. are at Appl.Cataly.A:Gen.1998,172,15-22 Selective oxidationand dehydrogenation of benzyl alcohol on ABB ' O3 (A=Ba, B=Pb, Ce, Ti and B '=Bi, Cu, Sb)-reported that perovskite-like type oxide is in anoxic with there is under the oxygen condition vapor phase catalytic oxidation to phenmethylol among the type perovskite oxides-temperature programmed reduction studies, its best phenmethylol conversion ratio is 92.6%, and the benzaldehyde selectivity is 62.8%.Tsuruya S. research group is at J.Mol.Catal.A:Chem.2004,211,219-226 Effect of alkali metal added to supported La catalystson the catalytic activity in the gas-phase catalytic oxidation of benzyl alcohol; Phys.Chem.Chem.Phys.1999,1,373-381 Influence and role of added alkali metals on thegas-phase oxidation of benzyl alcohol catalyzed by Cu ion-exchanged NaX zeolites and J.Chem.Soc., Faraday Trans.1998,94, among the 473479 Effect of alkali metals added toCu ion-exchanged Y-type zeolite catalysts in the gas-phase catalytic oxidation ofbenzyl alcohol to support type Cu, La, system research has been carried out in the selective oxidation of catalyst gas-phase benzene methyl alcohol such as Ce, can access the benzaldehyde selectivity more than 98%, but the conversion ratio of corresponding phenmethylol is less than 25%.
The shortcoming of these catalyst systems is that cost is higher, and under gas phase condition, phenmethylol can not obtain the benzaldehyde of high selectivity under high conversion.
Summary of the invention
In view of existing catalyst system exists cost higher, and under gas phase condition, phenmethylol can not obtain the shortcoming of the benzaldehyde of high selectivity under high conversion, the objective of the invention is to: one provides a kind of catalyst that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde; Its two, a kind of Preparation of catalysts method that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde is provided; Its three, provide a kind of this catalyst to be used for the application of catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde.
It is catalyst that the present invention selects ferric phosphate, and its molecular formula is: Fe
1-x(II) Fe
x(III) (PO
4)
(2+x)/3, 0<x<1 wherein, II, III represent the oxidation state of Fe.Fe (II) is an iron ammonium sulfate, and Fe (III) is ferric trichloride or ferric nitrate, PO
4 -Be sodium dihydrogen phosphate, potassium dihydrogen phosphate or ammonium dihydrogen phosphate (ADP).
A series of ferric phosphate catalyst of the present invention is synthetic by coprecipitation method, use different amounts+divalent molysite and+3 valency molysite are source of iron, raw material Fe (II) and Fe (III) are according to the synthetic various catalyst precursors of different mol ratios, and its preparation method is: in amount of substance is that the ratio of 1-x: x takes by weighing Fe
2+Molysite and Fe
3+Molysite is dissolved in the distilled water of deoxygenation, and wherein 0<x<1 is protected under the stirring at high pure nitrogen, add the distilled water that contains 0.03~0.05mol sodium acetate and (2+x)/3mol dihydric phosphate of deoxygenation, leave standstill, filter, with deoxygenation distilled water cyclic washing, use absolute ethanol washing at last, vacuum drying; Then under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate in 300~400 ℃ and 450~550 ℃ roasting 1~4 hour respectively, obtaining molecular formula is Fe
1-x(II) Fe
x(III) (PO
4)
(2+x)/3Catalyst.
The application that above-mentioned catalyst is used as catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde shows as: fixed bed reactors are adopted in described gas-phase benzene selective oxidation of methanol reaction, under normal pressure, carry out, phenmethylol per hour sample introduction quality is 1~4 times of catalyst service property (quality), and air velocity is 40mlmin
-1, 200~320 ℃ of reaction temperatures.
Characteristics of the present invention are that with ferric phosphate with low cost be catalyst efficient catalytic phenylmethanol gas phase selective oxidation producing benzaldehyde.Fe of the present invention
0.2(II) Fe
0.8(III) (PO
4)
2.8/3Catalyst activity is best, and when phenmethylol conversion ratio 96.6%, the selectivity that obtains benzaldehyde is 92.3%.
The specific embodiment
The specific embodiment one: the molecular formula of the catalyst that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde of present embodiment is: Fe
1-x(II) Fe
x(III) (PO
4)
(2+x)/3, 0<x<1 wherein, II, III are the oxidation state of Fe.
The specific embodiment two: the molecular formula of the catalyst that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde of present embodiment is: Fe (II) (PO
4)
2/3
The specific embodiment three: the molecular formula of the catalyst that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde of present embodiment is: Fe (III) (PO
4).
The specific embodiment four: the molecular formula of the catalyst that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde of present embodiment is: Fe
0.2(II) Fe
0.8(III) (PO
4)
2.8/3
The specific embodiment five: the molecular formula of the catalyst that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde of present embodiment is: Fe
0.5(II) Fe
0.5(IIII) (PO
4)
2.5/3
The specific embodiment six: the molecular formula of the catalyst that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde of present embodiment is: Fe
0.8(II) Fe
0.2(III) (PO
4)
2.2/3
The specific embodiment seven: the molecular formula of the catalyst that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde of present embodiment is: Fe
1-x(II) Fe
x(III) (PO
4)
(2+x)/3X=0~1, these a series of ferric phosphate catalyst are synthetic by coprecipitation method, use different amounts+divalent molysite and+3 valency molysite are source of iron, raw material Fe (II) and Fe (III) are according to different mol ratios and do not add the ferrous phosphate of Fe (III) and do not have the synthetic various catalyst precursors of trivalent ferric phosphate of Fe (II), and they all can be used as the catalyst of catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde.Its preparation method is:
One, when x equals 1, with Fe
3+Molysite and dihydric phosphate respectively are dissolved in the distilled water by mass ratio at 1: 1, then molysite are joined in the phosphate dihydrogen salt solution, stir, and leave standstill, and filter, and with deoxygenation distilled water cyclic washing, use absolute ethanol washing at last, vacuum drying; At last 500~650 ℃ of roasting temperatures 8~15 hours;
Two, when x is not equal to 1, be 1-x by amount of substance: x takes by weighing Fe
2+Molysite and Fe
3+Molysite is dissolved in the distilled water of deoxygenation, under high pure nitrogen (purity 〉=99.99%) protection is stirred, add in the distilled water that contains 0.03~0.05mol sodium acetate and (2+x)/3mol dihydric phosphate of deoxygenation, leave standstill, filter, with deoxygenation distilled water cyclic washing, use absolute ethanol washing at last, vacuum drying; Then under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate in 300~400 ℃ and 450~550 ℃ roasting 1~4 hour respectively.
In the present embodiment, described Fe
3+Molysite is ferric trichloride or ferric nitrate; Fe
2+Molysite is an iron ammonium sulfate; Dihydric phosphate is sodium dihydrogen phosphate, potassium dihydrogen phosphate or ammonium dihydrogen phosphate (ADP).
The specific embodiment eight: the method for utilizing ferric phosphate catalyst phenylmethanol gas phase selective oxidation of preparing benzaldehyde of present embodiment is: fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, under normal pressure, carry out, phenmethylol per hour sample introduction quality is 1~4 times of catalyst service property (quality), and air velocity is 40mlmin
-1, 200~320 ℃ of reaction temperatures.
The specific embodiment nine: respectively 0.03mol iron ammonium sulfate and 0.02mol sodium dihydrogen phosphate are dissolved in the distilled water of 50ml deoxygenation; under logical high pure nitrogen protection is stirred; in 0.04mol sodium acetate vitriolization ferrous ammonium sodium dihydrogen phosphate, then, l ferrous ammonium sulfate solution is added drop-wise to above-mentioned mixed solution; leave standstill; filter,, use absolute ethanol washing at last with deoxygenation distilled water cyclic washing; vacuum drying gets sky blue powder.Then, under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate, 400 ℃ and 450 ℃ respectively roasting obtained catalyst in 2 hours.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.32g, phenmethylol per hour sample introduction quality are 0.64g, and air velocity is 40mlmin
-1, 250 ℃, 275 ℃, 300 ℃ and 320 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 3.9%, 10.8%, 22.2% and 55.5%; The selectivity of benzaldehyde is respectively: 98.3%, 98.2%, 97.6% and 95.5%.
The specific embodiment ten: 0.04mol iron ammonium sulfate and 0.01mol ferric trichloride are dissolved in the distilled water of 50ml deoxygenation; 0.04mol sodium acetate and 0.0367mol sodium dihydrogen phosphate also are dissolved in the distilled water of 50ml deoxygenation; then under the high pure nitrogen protection is stirred; be added drop-wise in the solution of sodium acetate and sodium dihydrogen phosphate mixing ferrous solution, leave standstill, filter; with deoxygenation distilled water cyclic washing; use absolute ethanol washing at last, vacuum drying gets sky blue powder.Then, under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate, 400 ℃ and 450 ℃ respectively roasting obtained catalyst in 2 hours.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.32g, phenmethylol per hour sample introduction quality are 0.64g, and air velocity is 40mlmin
-1, 250 ℃, 275 ℃ and 300 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 8.3%, 14% and 70.2%; The selectivity of benzaldehyde is respectively: 98.2%, 98.1% and 98%.
The specific embodiment 11: 0.03mol iron ammonium sulfate and 0.02mol ferric trichloride are dissolved in the distilled water of 50ml deoxygenation; 0.04mol sodium acetate and 0.0367mol sodium dihydrogen phosphate also are dissolved in the distilled water of 50ml deoxygenation; then under the high pure nitrogen protection is stirred; be added drop-wise in the solution of sodium acetate and sodium dihydrogen phosphate mixing ferrous solution, leave standstill, filter; with deoxygenation distilled water cyclic washing; use absolute ethanol washing at last, vacuum drying gets sky blue powder.Then, under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate, 400 ℃ and 450 ℃ respectively roasting obtained catalyst in 2 hours.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.32g, phenmethylol per hour sample introduction quality are 0.64g, and air velocity is 40mlmin
-1, 250 ℃, 275 ℃, 300 ℃ and 320 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 10.7%, 17.6%, 37.9% and 74.7%; The selectivity of benzaldehyde is respectively: 97.9%, 97.7%, 97% and 95.8%.
The specific embodiment 12: 0.02mol iron ammonium sulfate and 0.03mol ferric trichloride are dissolved in the distilled water of 50ml deoxygenation; 0.04mol sodium acetate and 0.0367mol sodium dihydrogen phosphate also are dissolved in the distilled water of 50ml deoxygenation; then under the high pure nitrogen protection is stirred; be added drop-wise in the solution of sodium acetate and sodium dihydrogen phosphate mixing ferrous solution, leave standstill, filter; with deoxygenation distilled water cyclic washing; use absolute ethanol washing at last, vacuum drying gets sky blue powder.Then, under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate, 400 ℃ and 450 ℃ respectively roasting obtained catalyst in 2 hours.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.32g, phenmethylol per hour sample introduction quality are 0.64g, and air velocity is 40mlmin
-1, 200 ℃, 225 ℃ and 250 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 6.2%, 17% and 38.6%; The selectivity of benzaldehyde is respectively: 97.4%, 96.3% and 96%.
The specific embodiment 13: 0.01mol iron ammonium sulfate and 0.04mol ferric trichloride are dissolved in the distilled water of 50ml deoxygenation; 0.04mol sodium acetate and 0.0367mol sodium dihydrogen phosphate also are dissolved in the distilled water of 50ml deoxygenation; then under the high pure nitrogen protection is stirred; be added drop-wise in the solution of sodium acetate and sodium dihydrogen phosphate mixing ferrous solution, leave standstill, filter; with deoxygenation distilled water cyclic washing; use absolute ethanol washing at last, vacuum drying gets sky blue powder.Then, under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate, 400 ℃ and 450 ℃ respectively roasting obtained catalyst in 2 hours.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.32g, phenmethylol per hour sample introduction quality are 0.64g, and air velocity is 40mlmin
-1, 250 ℃, 275 ℃, 300 ℃ and 320 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 32.1%, 53.5%, 81.6% and 96.5%; The selectivity of benzaldehyde is respectively: 98%, 97.4%, 96.1% and 92.3%.
The specific embodiment 14: 0.05mol ferric nitrate and 0.05mol ammonium dihydrogen phosphate (ADP) are dissolved in respectively in the 50ml distilled water, then ferric nitrate are joined in the ammonium dihydrogen phosphate, stir, 80 ℃ of slow evaporates to dryness get the ferric phosphate presoma.Presoma is through 600 ℃, and roasting got the ferric phosphate catalyst in 12 hours under the air.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.32g, phenmethylol per hour sample introduction quality are 0.64g, and air velocity is 40mlmin
-1, 250 ℃, 275 ℃, 300 ℃ and 320 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 11.4%, 18.9%, 35.1% and 58.5%; The selectivity of benzaldehyde is respectively: 96.2%, 94.2%, 93% and 90.5%.
The specific embodiment 15: 0.01mol iron ammonium sulfate and 0.04mol ferric trichloride are dissolved in the distilled water of 50ml deoxygenation; 0.04mol sodium acetate and 0.0367mol sodium dihydrogen phosphate also are dissolved in the distilled water of 50ml deoxygenation; then under the high pure nitrogen protection is stirred; be added drop-wise in the solution of sodium acetate and sodium dihydrogen phosphate mixing ferrous solution, leave standstill, filter; with deoxygenation distilled water cyclic washing; use absolute ethanol washing at last, vacuum drying gets sky blue powder.Then, under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate, 400 ℃ and 450 ℃ respectively roasting obtained catalyst in 2 hours.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.32g, phenmethylol per hour sample introduction quality are 1.28g, and air velocity is 40mlmin
-1, 250 ℃, 275 ℃, 300 ℃ and 320 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 18.2%, 35.5%, 61.4% and 86.1%; The selectivity of benzaldehyde is respectively: 99%, 98.3%, 97.1% and 95.2%.
The specific embodiment 16: 0.01mol iron ammonium sulfate and 0.04mol ferric trichloride are dissolved in the distilled water of 50ml deoxygenation; 0.04mol sodium acetate and 0.0367mol sodium dihydrogen phosphate also are dissolved in the distilled water of 50ml deoxygenation; then under the high pure nitrogen protection is stirred; be added drop-wise in the solution of sodium acetate and sodium dihydrogen phosphate mixing ferrous solution, leave standstill, filter; with deoxygenation distilled water cyclic washing; use absolute ethanol washing at last, vacuum drying gets sky blue powder.Then, under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate, 400 ℃ and 450 ℃ respectively roasting obtained catalyst in 2 hours.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.32g, phenmethylol per hour sample introduction quality are 0.96g, and air velocity is 40mlmin
-1, 250 ℃, 275 ℃, 300 ℃ and 320 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 22.7%, 43.2%, 72.8% and 89.6%; The selectivity of benzaldehyde is respectively: 98.6%, 98%, 97.1% and 94.2%.
The specific embodiment 17: 0.01mol iron ammonium sulfate and 0.04mol ferric trichloride are dissolved in the distilled water of 50ml deoxygenation; 0.04mol sodium acetate and 0.0367mol sodium dihydrogen phosphate also are dissolved in the distilled water of 50ml deoxygenation; then under the high pure nitrogen protection is stirred; be added drop-wise in the solution of sodium acetate and sodium dihydrogen phosphate mixing ferrous solution, leave standstill, filter; with deoxygenation distilled water cyclic washing; use absolute ethanol washing at last, vacuum drying gets sky blue powder.Then, under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate, 400 ℃ and 450 ℃ respectively roasting obtained catalyst in 2 hours.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.64g, phenmethylol per hour sample introduction quality are 0.64g, and air velocity is 40mlmin
-1, 250 ℃, 275 ℃, 300 ℃ and 320 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 43.2%, 63.6%, 89.4% and 98.6%; The selectivity of benzaldehyde is respectively: 94.8%, 90.4%, 89.6% and 87.9%.
The specific embodiment 18: 0.01mol iron ammonium sulfate and 0.04mol ferric trichloride are dissolved in the distilled water of 50ml deoxygenation; 0.04mol sodium acetate and 0.0367mol sodium dihydrogen phosphate also are dissolved in the distilled water of 50ml deoxygenation; then under the high pure nitrogen protection is stirred; be added drop-wise in the solution of sodium acetate and sodium dihydrogen phosphate mixing ferrous solution, leave standstill, filter; with deoxygenation distilled water cyclic washing; use absolute ethanol washing at last, vacuum drying gets sky blue powder.Then, under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate, 400 ℃ and 450 ℃ respectively roasting obtained catalyst in 2 hours.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.45g, phenmethylol per hour sample introduction quality are 0.60g, and air velocity is 40mlmin
-1, 250 ℃, 275 ℃, 300 ℃ and 320 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 36.8%, 57.6%, 85.5% and 98.1%; The selectivity of benzaldehyde is respectively: 96.3%, 95.5%, 92.8% and 89.2%.
The specific embodiment 19: respectively 0.03mol iron ammonium sulfate and 0.02mol sodium dihydrogen phosphate are dissolved in the distilled water of 50ml deoxygenation; under logical high pure nitrogen protection is stirred; in 0.05mol sodium acetate vitriolization ferrous ammonium sodium dihydrogen phosphate, then, l ferrous ammonium sulfate solution is added drop-wise to above-mentioned mixed solution; leave standstill; filter,, use absolute ethanol washing at last with deoxygenation distilled water cyclic washing; vacuum drying gets sky blue powder.Then, under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate, 300 ℃ of roastings 4 hours, 500 ℃ of roastings obtained catalyst in 1 hour.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.32g, phenmethylol per hour sample introduction quality are 0.64g, and air velocity is 40mlmin
-1, 250 ℃, 275 ℃, 300 ℃ and 320 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 3.6%, 9.5%, 20.4% and 50.5%; The selectivity of benzaldehyde is respectively: 98.8%, 98.0%, 96.5% and 96.0%.
The specific embodiment 20: 0.01mol iron ammonium sulfate and 0.04mol ferric trichloride are dissolved in the distilled water of 50ml deoxygenation; 0.05mol sodium acetate and 0.0367mol sodium dihydrogen phosphate also are dissolved in the distilled water of 50ml deoxygenation; then under the high pure nitrogen protection is stirred; be added drop-wise in the solution of sodium acetate and sodium dihydrogen phosphate mixing ferrous solution, leave standstill, filter; with deoxygenation distilled water cyclic washing; use absolute ethanol washing at last, vacuum drying gets sky blue powder.Then, under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate, obtained catalyst in 4 hours in 350 ℃ of roastings 1 hour and 500 ℃ of roastings.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.32g, phenmethylol per hour sample introduction quality are 0.64g, and air velocity is 40mlmin
-1, 250 ℃, 275 ℃, 300 ℃ and 320 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 28.2%, 47.5%, 77.3% and 91.6%; The selectivity of benzaldehyde is respectively: 99%, 98.4%, 94.7% and 90%.
The specific embodiment 21: 0.01mol iron ammonium sulfate and 0.04mol ferric trichloride are dissolved in the distilled water of 50ml deoxygenation; 0.05mol sodium acetate and 0.0367mol sodium dihydrogen phosphate also are dissolved in the distilled water of 50ml deoxygenation; then under the high pure nitrogen protection is stirred; be added drop-wise in the solution of sodium acetate and sodium dihydrogen phosphate mixing ferrous solution, leave standstill, filter; with deoxygenation distilled water cyclic washing; use absolute ethanol washing at last, vacuum drying gets sky blue powder.Then, under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate, obtained catalyst in roasting l hour 350 ℃ of roastings 4 hours and 550 ℃.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.32g, phenmethylol per hour sample introduction quality are 0.64g, and air velocity is 40mlmin
-1, 250 ℃, 275 ℃, 300 ℃ and 320 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 25.3%, 42.5%, 67.3% and 86.1%; The selectivity of benzaldehyde is respectively: 97.8%, 96.7%, 91.4% and 87.8%.
The specific embodiment 22: 0.05mol ferric trichloride and 0.05mol sodium dihydrogen phosphate are dissolved in respectively in the 50ml distilled water, then molysite is joined in the phosphate dihydrogen salt solution, stir, leave standstill, filter,, use absolute ethanol washing at last with deoxygenation distilled water cyclic washing, vacuum drying gets the ferric phosphate presoma.Presoma is through 500 ℃, and roasting got the ferric phosphate catalyst in 15 hours under the air.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.32g, phenmethylol per hour sample introduction quality are 0.64g, and air velocity is 40mlmin
-1, 250 ℃, 275 ℃, 300 ℃ and 320 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 8.4%, 12.5%, 25.8% and 50%; The selectivity of benzaldehyde is respectively: 98.4%, 96.5%, 94.7% and 92.6%.
The specific embodiment 23: 0.05mol ferric trichloride and 0.05mol sodium dihydrogen phosphate are dissolved in respectively in the 50ml distilled water, then molysite is joined in the phosphate dihydrogen salt solution, stir, leave standstill, filter,, use absolute ethanol washing at last with deoxygenation distilled water cyclic washing, vacuum drying gets the ferric phosphate presoma.Presoma is through 650 ℃, and roasting got the ferric phosphate catalyst in 8 hours under the air.Fixed bed reactors are adopted in the reaction of gas-phase benzene selective oxidation of methanol, carry out under normal pressure.Catalyst amount 0.32g, phenmethylol per hour sample introduction quality are 0.64g, and air velocity is 40mlmin
-1, 250 ℃, 275 ℃, 300 ℃ and 320 ℃ of reaction temperatures, the conversion ratio of phenmethylol is respectively: 10.1%, 13.7%, 23.5% and 48.5%; The selectivity of benzaldehyde is respectively: 97.5%, 95.2%, 91.2% and 89.0%.
Claims (9)
1, a kind of catalyst that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde is characterized in that the molecular formula of described catalyst is: Fe
1-x(II) Fe
x(III) (PO
4)
(2+x)/3, 0<x<1 wherein, II, III are the oxidation state of Fe.
2, the catalyst that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde according to claim 1 is characterized in that the molecular formula of described catalyst is: Fe
0.2(II) Fe
0.8(III) (PO
4)
2.8/3
3, the catalyst that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde according to claim 1 is characterized in that the molecular formula of described catalyst is: Fe
0.5(II) Fe
0.5(III) (PO
4)
2.5/3
4, the catalyst that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde according to claim 1 is characterized in that the molecular formula of described catalyst is: Fe
0.8(II) Fe
0.2(III) (PO
4)
2.2/3
5, the described Preparation of catalysts method that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde of claim 1 is characterized in that described preparation method is as follows: in amount of substance is that the ratio of 1-x: x takes by weighing Fe
2+Molysite and Fe
3+Molysite is dissolved in the distilled water of deoxygenation, and wherein 0<x<1 is protected under the stirring at high pure nitrogen, add the distilled water that contains 0.03~0.05mol sodium acetate and (2+x)/3mol dihydric phosphate of deoxygenation, leave standstill, filter, with deoxygenation distilled water cyclic washing, use absolute ethanol washing at last, vacuum drying; Then under the high pure nitrogen protection, with 10 ℃ of min
-1Heating rate in 300~400 ℃ and 450~550 ℃ roasting 1~4 hour respectively, obtaining molecular formula is Fe
1-x(II) Fe
x(III) (PO
4)
(2+x)/3Catalyst.
6, the Preparation of catalysts method that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde according to claim 5 is characterized in that described Fe
3+Molysite is ferric trichloride or ferric nitrate.
7, the Preparation of catalysts method that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde according to claim 5 is characterized in that described Fe
2+Molysite is an iron ammonium sulfate.
8, the Preparation of catalysts method that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde according to claim 5 is characterized in that described dihydric phosphate is sodium dihydrogen phosphate, potassium dihydrogen phosphate or ammonium dihydrogen phosphate (ADP).
9, the described Application of Catalyst that is used for catalytic phenylmethanol gas phase selective oxidation of preparing benzaldehyde of claim 1, it is characterized in that described gas-phase benzene selective oxidation of methanol reaction employing fixed bed reactors, under normal pressure, carry out, phenmethylol per hour sample introduction quality is 1~4 times of catalyst service property (quality), and air velocity is 40mlmin
-1, 200~320 ℃ of reaction temperatures.
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CN1203828A (en) * | 1997-06-27 | 1999-01-06 | 中国石化齐鲁石油化工公司 | Catalyst for vecovering elemental sulphur selective oxidation of hydrogen sulfide and its preparing method |
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Gas-Phase Selective Oxidation of p-Cresol in the presence ofAcetic Acid over Iron Phosphate Catalyst. ZHU,Yujun eta,etal.催化学报,第26卷第4期 2005 * |
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