CN1085115C - Compound oxide catalyst for phenol hydroxylation and its preparing method - Google Patents
Compound oxide catalyst for phenol hydroxylation and its preparing method Download PDFInfo
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- CN1085115C CN1085115C CN98100892A CN98100892A CN1085115C CN 1085115 C CN1085115 C CN 1085115C CN 98100892 A CN98100892 A CN 98100892A CN 98100892 A CN98100892 A CN 98100892A CN 1085115 C CN1085115 C CN 1085115C
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- composite oxide
- oxide catalysts
- phenol
- elements
- hydrogen peroxide
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 230000033444 hydroxylation Effects 0.000 title claims abstract description 12
- 238000005805 hydroxylation reaction Methods 0.000 title claims abstract description 12
- 150000001875 compounds Chemical class 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title abstract description 19
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 230000035484 reaction time Effects 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 28
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000004113 Sepiolite Substances 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 229910052624 sepiolite Inorganic materials 0.000 claims description 6
- 235000019355 sepiolite Nutrition 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000002689 soil Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 98
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 23
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 3
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 24
- 230000009466 transformation Effects 0.000 description 21
- 238000006555 catalytic reaction Methods 0.000 description 14
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 9
- 229910007541 Zn O Inorganic materials 0.000 description 8
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
- 229910002480 Cu-O Inorganic materials 0.000 description 5
- 229910020923 Sn-O Inorganic materials 0.000 description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 5
- 235000011150 stannous chloride Nutrition 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 229910018663 Mn O Inorganic materials 0.000 description 4
- 229910003176 Mn-O Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229910017135 Fe—O Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 101000648997 Homo sapiens Tripartite motif-containing protein 44 Proteins 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 102100028017 Tripartite motif-containing protein 44 Human genes 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a compound oxide catalyst for phenol hydroxylation and a preparing method of the compound oxide catalyst, particularly to a loading type compound oxide catalyst and a preparing method thereof. Soluble salt of required metallic elements is dissolved in water, carriers are added, and then, precipitating agents are added to make active components precipitated on the carriers. Finally, the compound oxide catalyst is prepared through roasting. The active components of the compound oxide catalyst of the present invention can be effectively dispersed on the surfaces of the carriers, and the catalyst has the advantages of large active surface and high activity. If used for the preparation of pyrocatechol and hydroquinone through phenol catalytic oxidation, the conversion rate of phenol can be increased, and the dosage of the catalyst is small. Besides, the reaction temperature can be lowered, and the reaction time can be shortened, so that the ineffective decomposition of hydrogen peroxide can be reduced, and the utilization rate of hydrogen peroxide is increased.
Description
The present invention relates to a kind of Catalysts and its preparation method that is used for the phenol hydroxylation synthesizing benzene diphenol, particularly supported complex oxide Catalysts and its preparation method.
Pyrocatechol and Resorcinol all are fine chemical products of high added value, be widely used in industry such as photographic process, tackiness agent, oxidation inhibitor, additive and dyestuff, the main method of producing dihydroxy-benzene has ortho chloro phenol hydrolysis method, aniline oxidation style, diisopropylbenzene(DIPB) oxidation style and phenol hydroxylation with hydrogen peroxide method etc., at present, extensively adopt the phenol hydroxylation with hydrogen peroxide legal system to be equipped with pyrocatechol and Resorcinol.
European patent EP 122374 discloses a kind of method of phenol-hydrogen peroxide hydroxylation preparing benzenediol, its characteristics by phenol and anhydrous hydrogen peroxide (particularly the content of water is lower than the hydrogen peroxide of 0.5wt%) at SO
2React under catalyzer exists and make dihydroxy-benzene.European patent EP 121693 discloses a kind of method of phenol-hydrogen peroxide hydroxylation preparing benzenediol, its characteristics by phenol and anhydrous hydrogen peroxide organic solution (particularly the content of water is lower than the hydrogen peroxide organic solution of 0.5wt%) at SeO
2React under catalyzer exists and make dihydroxy-benzene.The shortcoming of these two kinds of methods is that the yield of dihydroxy-benzene is lower.
China publication CN1134313A discloses the composite oxide catalysts of the synthetic dihydroxy-benzene of a kind of phenol-hydrogen peroxide hydroxylation, and this catalyzer is a kind of A of having
xB
yO
zThe composite oxides of structure, wherein the A position is metal, rare earth metal etc., and the B position is a metal, nonmetal etc., and O is an oxygen; X=0～3, y=0～12, z is the positive number that satisfies the valency requirement.Its shortcoming is that this catalyst activity is lower, and temperature of reaction is higher, and the reaction times is longer; The catalyzer that contains rare earth metal in addition costs an arm and a leg.
The object of the present invention is to provide a kind of supported complex oxide catalyzer of active ingredient high dispersing.
The composite oxide catalysts that provides a kind of activity high is provided another object of the present invention.
A further object of the present invention is to provide a kind of cheap composite oxide catalysts.
Of the present invention also have a purpose to be to provide a kind of supported complex oxide Preparation of catalysts method.
Last purpose of the present invention is that this composite oxide catalysts can be used for hydrogen peroxide oxidation phenol system pyrocatechol and Resorcinol, can improve the per pass conversion of phenol, the selectivity of dihydroxy-benzene and the effective rate of utilization of hydrogen peroxide, also can reduce temperature of reaction, shorten the reaction times.
To achieve the above object of the invention, the technical solution used in the present invention is: the soluble salt of required metallic element is soluble in water, add carrier then, adding precipitation agent again is deposited on the carrier active ingredient, make composite oxide catalysts of the present invention through roasting, this composite oxide catalysts can be used for hydrogen peroxide oxidation phenol system pyrocatechol and Resorcinol.
A kind of composite oxide catalysts, available following empirical formula definition:
A
aB
bC
cD
dO
x/ carrier (I) wherein carrier is a porous material; One or more elements are selected in the A representative in the group VIII from the periodic table of elements; B represents copper; The C representative is selected one or more valencys in IVA, VA, IVB, VB, VIB, the VIIB family and is had the metallic element that appraises at the current rate from the periodic table of elements; The D representative is selected one or more metallic elements in IA, IIA, the IIB family from the periodic table of elements; A is 0.01～20; B is 0.001～10; C is 0～5, is 0.0005～5 preferably; D is 0～5, is 0.0002～5 preferably; The required oxygen atomicity of contained other element valence in the compound is satisfied in the x representative.
A in the composite oxide catalysts of the present invention can select one or both elements from Fe and Co, be preferably Fe; C can select one or more elements from Mn, Sn, V, Ti, Cr, Pb and Sb, be preferably Mn, Sn; D can select one or more elements from Zn, Ba, Mg and K, be preferably Zn, Mg.
Carrier of the present invention is α-Al
2O
3, γ-Al
2O
3, silicon bath soil, sepiolite, polynite or molecular sieve, be γ-Al preferably
2O
3, silicon bath soil or sepiolite.
Effect is preferably in the composite oxide catalysts of the present invention: Fe-Cu-Sn-Zn-O/ γ-Al
2O
3, Fe-Cu-Sn-Zn-O/ α-Al
2O
3, Fe-Cu-Sn-Zn-O/ diatomite, Fe-Cu-Sn-Zn-O/ sepiolite, Fe-Cu-Sn-O/ γ-Al
2O
3, Fe-Cu-Sn-O/ α-Al
2O
3, Fe-Cu-Sn-O/ diatomite, Fe-Cu-Sn-O/ sepiolite, Fe-Cu-Mn-O/ γ-Al
2O
3, Fe-Cu-Mn-O/ α-Al
2O
3, Fe-Cu-Mn-O/ diatomite, Fe-Cu-Sn-Zn-O/ γ-Al
2O
3, Fe-Cu-O/ α-Al
2O
3, Fe-Cu-O/ diatomite, Fe-Cu-O/ sepiolite etc.
The preparation method of composite oxide catalysts of the present invention, comprise the steps: the soluble salt of required metallic element soluble in water, add carrier, adding precipitation agent again is deposited on the carrier active ingredient, carry out roasting at 300～900 ℃ then, the maturing temperature scope is 400～700 ℃ preferably, and roasting time is 3～36 hours, and roasting time is 6～12 hours preferably.
Precipitation agent of the present invention is ammoniacal liquor, sodium hydroxide, potassium hydroxide, yellow soda ash or carbonic acid ammonia.
Composite oxide catalysts of the present invention is applicable to oxidation of phenol system pyrocatechol and Resorcinol, is specially adapted to hydrogen peroxide hydroxylation phenol system pyrocatechol and Resorcinol.
By oxidation of phenol system pyrocatechol and Resorcinol the time, used water or organic solvent such as alcohols, acetone, acetonitrile, dioxan etc. are solvent, are 10～90 ℃ with the hydrogen peroxide as oxidant temperature of reaction, and temperature of reaction is 40～60 ℃ preferably; Reaction times is 5 minutes～32 hours, and the reaction times is 20 minutes～2 hours preferably.
Because hydrogen peroxide is easy to decompose, unconverted hydrogen peroxide is difficult to recycle in the reaction system, so under the prerequisite that does not reduce the dihydroxy-benzene yield, improve the effective rate of utilization of hydrogen peroxide, is significant.Products therefrom is analyzed with the temperature programming capillary gas chromatograph among the embodiment, does not contain Resorcinol in the product.The optionally method of calculation of the transformation efficiency of the effective rate of utilization of hydrogen peroxide, phenol and dihydroxy-benzene are as follows among the embodiment:
The present invention is further illustrated below in conjunction with embodiment, but not the office in these embodiment.
Embodiment 1
Iron nitrate 4.33g and cupric nitrate 0.76g are dissolved in the 30ml deionized water, add γ-Al
2O
34g stirs, splash into the 2N sodium hydroxide solution to precipitation fully, stirred aging 120 minutes, after filtration, the washing back is 105 ℃ of following constant temperature dryings 3 hours, promptly gets catalyst Fe-Cu-O/ γ-Al in 10 hours 650 ℃ of roastings then in flowing air
2O
3(1).Catalyzer (1) 0.125g that makes is added in the three-necked bottle of band thermometer and agitator, in this reaction flask, add phenol 2.65g, water 8.7ml, concentration is 30% superoxol 2.4ml (mol ratio of phenol and hydrogen peroxide is 1/0.8), reacted 1 hour down at 50 ℃, the products obtained therefrom gas chromatographic analysis, the transformation efficiency that gets phenol more as calculated is 57.35%, the selectivity of dihydroxy-benzene is 98.68%, the utilization ratio of hydrogen peroxide is 70.73%, in the product adjacent diphenol be 1.97 to the mol ratio of diphenol (adjacency pair than).
Embodiment 2
Take by weighing iron nitrate 4.33g, cupric nitrate 0.76g, zinc nitrate 0.225g, tin protochloride 0.208g, can make catalyst Fe-Cu-Sn-Zn-O/ γ-Al by the method for embodiment 1
2O
3(2).
The catalyzer (2) that makes is used for the reaction of catalysis of phenol and hydrogen peroxide, other condition is with embodiment 1, and the transformation efficiency of gained phenol is 58.23%, and the selectivity of dihydroxy-benzene is 100.00%, the effective rate of utilization of hydrogen peroxide is 72.78%, and the adjacency pair ratio is 2.14.
Embodiment 3
Take by weighing iron nitrate 4.33g, cupric nitrate 0.76g, tin protochloride 0.208g, can make catalyst Fe-Cu-Sn-O/ γ-Al by the method for embodiment 1
2O
3(3).
The catalyzer (3) that makes is used for the reaction of catalysis of phenol and hydrogen peroxide, and other condition is with embodiment 1, and the transformation efficiency of gained phenol is 58.37%, and the selectivity of dihydroxy-benzene is 98.69%, and the effective rate of utilization of hydrogen peroxide is 72.01%, and the adjacency pair ratio is 2.27.
Embodiment 4
Take by weighing iron nitrate 4.33g, cupric nitrate 0.76g, manganese acetate 0.456g, can make catalyst Fe-Cu-Mn-O/ γ-Al by the method for embodiment 1
2O
3(4).
The catalyzer (4) that makes is used for the reaction of catalysis of phenol and hydrogen peroxide, and other condition is with embodiment 1, and the transformation efficiency of gained phenol is 40.56%, and the selectivity of dihydroxy-benzene is 87.82%, and the effective rate of utilization of hydrogen peroxide is 44.52%, and the adjacency pair ratio is 2.14.
Embodiment 5
Take by weighing iron nitrate 4.33g, cupric nitrate 0.76g, α-Al
2O
34g can make catalyst Fe-Cu-O/ α-Al by the method for embodiment 1
2O
3(5).
The catalyzer (5) that makes is used for the reaction of catalysis of phenol and hydrogen peroxide, other condition is with embodiment 1, and the transformation efficiency of gained phenol is 57.24%, and the selectivity of dihydroxy-benzene is 100.00%, the effective rate of utilization of hydrogen peroxide is 71.55%, and the adjacency pair ratio is 2.37.
Embodiment 6～9
Take by weighing iron nitrate 4.33g, cupric nitrate 0.76g, zinc nitrate 0.225g, tin protochloride 0.208g, under 400 ℃, 450 ℃, 500 ℃, 600 ℃, carry out roasting respectively by the method for embodiment 1 and can make catalyst Fe-Cu-Sn-Zn-O/ γ-Al
2O
3(2a, 2b, 2c, 2d).
The catalyzer (2a, 2b, 2c, 2d) that makes is used for the reaction of catalysis of phenol and hydrogen peroxide, and other condition the results are shown in Table 1 with embodiment 1.
Table 1
Embodiment 10～18
| The embodiment numbering | The catalyzer numbering | The transformation efficiency of phenol (%) | The selectivity of dihydroxy-benzene (%) | H 2O 2Effective transformation efficiency (%) | The adjacency pair ratio |
| 6 | 2a | 57.48 | 100.00 | 71.84 | 2.22 |
| 7 | 2b | 67.04 | 100.00 | 83.80 | 2.21 |
| 8 | 2c | 62.92 | 100.00 | 78.65 | 2.36 |
| 9 | 2d | 58.23 | 100.00 | 76.16 | 2.41 |
Change iron nitrate, cupric nitrate, zinc nitrate, tin protochloride, γ-Al
2O
3Add-on can make catalyst Fe-Cu-Sn-Zn-O/ γ-Al by the method for embodiment 1
2O
3(2A, 2B, 2C, 2D, 2E, 2F, 2G, 2H, 2I) (seeing Table 2).
Table 2
The catalyzer (2A, 2B, 2C, 2D, 2E, 2F, 2G, 2H, 2I) that makes is used for the reaction of catalysis of phenol and hydrogen peroxide, and other condition the results are shown in Table 3 with embodiment 1.Table 3
Embodiment 19
| The embodiment numbering | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 |
| The feeding quantity of iron nitrate (g) | 4.06 | 4.06 | 4.06 | 2.71 | 2.71 | 2.71 | 1.35 | 1.35 | 1.35 |
| The feeding quantity of cupric nitrate (g) | 0.71 | 0.48 | 0.24 | 0.71 | 0.48 | 0.24 | 0.71 | 0.48 | 0.24 |
| The feeding quantity of zinc nitrate (g) | 0.21 | 0.14 | 0.068 | 0.068 | 0.21 | 0.14 | 0.14 | 0.035 | 0.21 |
| The feeding quantity of tin protochloride (g) | 0.19 | 0.13 | 0.065 | 0.13 | 0.065 | 0.19 | 0.065 | 0.19 | 0.13 |
| γ-Al 2O 3Feeding quantity (g) | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 | 2.50 |
| The catalyzer numbering | 2A | 2B | 2C | 2D | 2E | 2F | 2G | 2H | 2I |
| The embodiment numbering | The catalyzer numbering | The transformation efficiency of phenol (%) | The selectivity of dihydroxy-benzene (%) | H 2O 2Effective transformation efficiency (%) | The adjacency pair ratio |
| 10 | 2A | 59.21 | 100.00 | 74.02 | 2.08 |
| 11 | 2B | 57.51 | 100.00 | 71.89 | 2.46 |
| 12 | 2C | 57.68 | 100.00 | 72.09 | 2.46 |
| 13 | 2D | 57.43 | 100.00 | 71.79 | 2.32 |
| 14 | 2E | 58.56 | 100.00 | 73.20 | 2.27 |
| 15 | 2F | 57.10 | 100.00 | 71.38 | 2.47 |
| 16 | 2G | 57.89 | 100.00 | 72.36 | 2.33 |
| 17 | 2H | 53.49 | 100.00 | 66.86 | 2.68 |
| 18 | 2I | 59.45 | 100.00 | 74.31 | 2.22 |
The catalyzer (2) that makes is used for the reaction of catalysis of phenol and hydrogen peroxide, catalyst levels is 0.063g, other condition is with embodiment 1, the result is: the transformation efficiency of phenol is 58.80%, the selectivity of dihydroxy-benzene is 100.00%, the effective rate of utilization of hydrogen peroxide is 73.50%, and the adjacency pair ratio is 2.78.
Embodiment 20
The catalyzer (2) that makes is used for the reaction of catalysis of phenol and hydrogen peroxide, catalyst levels is 0.032g, other condition is with embodiment 1, the result is: the transformation efficiency of phenol is 41.84%, the selectivity of dihydroxy-benzene is 62.91%, the effective rate of utilization of hydrogen peroxide is 32.90%, and the adjacency pair ratio is 7.94.
Embodiment 21～23
The catalyzer (2) that makes is used for the reaction of catalysis of phenol and hydrogen peroxide, reaction times difference (seeing Table 4), other condition the results are shown in Table 4 with embodiment 1.Table 4
Embodiment 24
| The embodiment numbering | Reaction times (h) | The transformation efficiency of phenol (%) | The selectivity of dihydroxy-benzene (%) | H 2O 2Effective transformation efficiency (%) | The adjacency pair ratio |
| 21 | 0.5 | 52.66 | 100.00 | 65.83 | 2.23 |
| 22 | 2 | 58.88 | 100.00 | 73.59 | 2.42 |
| 23 | 6 | 54.59 | 100.00 | 68.23 | 3.05 |
The catalyzer (2) that makes is used for the reaction of catalysis of phenol and hydrogen peroxide, the mol ratio of phenol and hydrogen peroxide is 1/2, other condition is with embodiment 1, the transformation efficiency of gained phenol is 77.64%, the selectivity of dihydroxy-benzene is 100.00%, the effective rate of utilization of hydrogen peroxide is 38.82%, and the adjacency pair ratio is 2.78.
Embodiment 25
The catalyzer (2) that makes is used for the reaction of catalysis of phenol and hydrogen peroxide, the mol ratio of phenol and hydrogen peroxide is 1/1, other condition is with embodiment 1, the transformation efficiency of gained phenol is 64.71%, the selectivity of dihydroxy-benzene is 100.00%, the effective rate of utilization of hydrogen peroxide is 64.71%, and the adjacency pair ratio is 2.38.Comparative example 1 (directly adopting the data among the embodiment 8 among the CN 1134313A)
Catalyzer La-Sr-Fe-O is used for the reaction of catalysis of phenol and hydrogen peroxide, the mol ratio of phenol and hydrogen peroxide is 1/2, temperature of reaction is 70 ℃, reaction times is 5 hours, the transformation efficiency of gained phenol is 66.69%, the selectivity of pyrocatechol is 61.58%, and the selectivity of pyrocatechol is 37.37%.Comparative example 2 (directly adopting the data among the embodiment 8 among the CN 1134313A)
Catalyzer La-Sr-Fe-O is used for the reaction of catalysis of phenol and hydrogen peroxide, the mol ratio of phenol and hydrogen peroxide is 1/1, temperature of reaction is 70 ℃, reaction times is 5 hours, the transformation efficiency of gained phenol is 47.03%, the selectivity of pyrocatechol is 59.22%, and the selectivity of pyrocatechol is 37.96%.Comparative example 3～9
Method by embodiment 1 is prepared as follows several single component catalysts:
Fe
2O
3/γ-Al
2O
3 (6)
CuO/γ-Al
2O
3 (7)
SnO
2/γ-Al
2O
3 (8)
ZnO/γ-Al
2O
3 (9)
PbO
2/γ-Al
2O
3 (10)
MnO
2/γ-Al
2O
3 (11)
The catalyzer (6,7,8,9,10,11) that makes is used for the reaction of catalysis of phenol and hydrogen peroxide, and other condition the results are shown in Table 5 with embodiment 1.
Table 5
| The embodiment numbering | The catalyzer numbering | The transformation efficiency of phenol (%) | The selectivity of dihydroxy-benzene (%) | H 2O 2Effective transformation efficiency (%) | The adjacency pair ratio |
| 1 | 6 | 26.41 | 44.59 | 14.72 | 1.64 |
| 2 | 7 | 40.56 | 87.82 | 44.52 | 2.14 |
| 3 | 8 | 0.00 | 0.00 | 0.00 | - |
| 4 | 9 | 0.00 | 0.00 | 0.00 | - |
| 5 | 10 | 29.54 | 66.35 | 24.50 | 5.54 |
| 6 | 11 | 0.00 | - | 0.00 | - |
Data among data in comparing embodiment, the comparative example and the Chinese patent CN 1134313A embodiment are as can be seen: the active ingredient of composite oxide catalysts of the present invention can be dispersed in carrier surface effectively, and the catalyst activity surface is big, and is active high.Be used for phenol catalyzed oxidation system pyrocatechol and Resorcinol, can improve the transformation efficiency of phenol; Catalyst consumption is few; Also can reduce temperature of reaction, shorten the reaction times, thereby can reduce the invalid decomposition of hydrogen peroxide, improve the utilization ratio of hydrogen peroxide.
Claims (13)
1. composite oxide catalysts that phenol hydroxylation is used is characterized in that available following empirical formula definition:
A
aB
bC
cD
dO
x/ carrier (I) wherein carrier is a porous material; One or more elements are selected in the A representative in the group VIII from the periodic table of elements; B represents copper; The C representative is selected one or more valencys in IVA, VA, IVB, VB, VIB, the VIIB family and is had the metallic element that appraises at the current rate from the periodic table of elements; The D representative is selected one or more metallic elements in IA, IIA, the IIB family from the periodic table of elements; A is 0.01～20; B is 0.001～10; C is 0～5; D is 0～5; The required oxygen atomicity of contained other element valence in the compound is satisfied in the x representative.
2. composite oxide catalysts according to claim 1 is characterized in that c is 0.0005～5.
3. composite oxide catalysts according to claim 1 is characterized in that d is 0.0002～5.
4. according to any one described composite oxide catalysts in the claim 1 to 3, it is characterized in that the A representative selects one or both elements from Fe and Co.
5. according to any one described composite oxide catalysts in the claim 1 to 3, it is characterized in that the C representative selects one or more elements from Mn, Sn, V, Ti, Cr, Pb and Sb.
6. according to any one described composite oxide catalysts in the claim 1 to 3, it is characterized in that the D representative selects one or more elements from Zn, Ba, Mg and K.
7. according to any one described composite oxide catalysts in the claim 1 to 3, it is characterized in that described carrier is α-Al
2O
3, γ-Al
2O
3, silicon bath soil or sepiolite.
8. according to the preparation method of any one described composite oxide catalysts in the claim 1 to 3, comprise the steps: the soluble salt of required metallic element soluble in water, add carrier then, adding precipitation agent again is deposited on the carrier active ingredient, carry out roasting at 300～900 ℃ then, roasting time is 3～36 hours.
9. the preparation method of composite oxide catalysts according to claim 8 is characterized in that described maturing temperature is 400～700 ℃, and roasting time is 6～12 hours.
10. the preparation method of composite oxide catalysts according to claim 9 is characterized in that described precipitation agent is ammoniacal liquor, sodium hydroxide, potassium hydroxide, yellow soda ash or carbonic acid ammonia.
11. the purposes of any one described composite oxide catalysts is characterized in that in the claim 1 to 3, and any one described composite oxide catalysts in the claim 1 to 3 is used for phenol hydroxylation system pyrocatechol and Resorcinol.
12. the purposes of composite oxide catalysts according to claim 11 is characterized in that the reaction times is 5 minutes～32 hours, temperature of reaction is 10～90 ℃.
13. the purposes of composite oxide catalysts according to claim 12 is characterized in that the reaction times is 20 minutes～2 hours, temperature of reaction is 40～60 ℃.
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| CN98100892A CN1085115C (en) | 1998-03-10 | 1998-03-10 | Compound oxide catalyst for phenol hydroxylation and its preparing method |
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| CN98100892A CN1085115C (en) | 1998-03-10 | 1998-03-10 | Compound oxide catalyst for phenol hydroxylation and its preparing method |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1096293C (en) * | 2000-05-24 | 2002-12-18 | 中国石油化工集团公司 | Phenyl hydroxylating catalyst |
| CN1130259C (en) * | 2000-06-15 | 2003-12-10 | 中国石油化工集团公司 | Catalyst for preparing benzene diphenol by means of direct oxidation of phenol |
| CN1130258C (en) * | 2000-06-15 | 2003-12-10 | 中国石油化工集团公司 | Catalyst for preparing benzene diphenol by means of oxidation of phenol |
| CN103055931B (en) * | 2013-01-22 | 2015-01-07 | 天津市达利嘉化工科技有限公司 | Low-capacity solid acid catalyst for hydroxylation of phenol reaction and preparation method thereof |
| CN103394353A (en) * | 2013-08-13 | 2013-11-20 | 唐山师范学院 | Catalyst for preparing benzenediol through phenol hydroxylation and preparation method of catalyst |
| CN105032442B (en) * | 2015-07-23 | 2017-10-20 | 中国蓝星（集团）股份有限公司 | A kind of gas phase reaction catalyst, preparation method and application |
| CN105597755B (en) * | 2015-11-10 | 2018-06-29 | 扬州大学 | A kind of cubic phase CuO catalyst and preparation method thereof |
| CN105618130A (en) * | 2015-12-23 | 2016-06-01 | 东南大学 | Preparation method and application of catalyst for phenol hydroxylation reaction |
| CN107670665A (en) * | 2017-11-02 | 2018-02-09 | 肇庆高新区国专科技有限公司 | A kind of diatomite catalyst for phenol hydroxylation |
| CN110698666A (en) * | 2019-09-27 | 2020-01-17 | 天津大学 | Composite catalyst and application thereof in preparation of polyphenol by oxidative polymerization of phenol-containing wastewater |
| CN110947393A (en) * | 2019-12-09 | 2020-04-03 | 华东理工大学 | Heterogeneous Fenton catalyst with high hydrogen peroxide utilization rate and preparation method and application thereof |
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| CN1134313A (en) * | 1995-12-16 | 1996-10-30 | 吉林大学 | Compound oxide catalyst for synthesizing benzene diphenol by phenol-hydrogen peroxide hydroxylation |
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Patent Citations (5)
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| US4578521A (en) * | 1985-02-04 | 1986-03-25 | Mobil Oil Corporation | Shape-selective catalytic oxidation of phenol |
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