GB2116974A - Process for hydroxylating aromatic hydrocarbons - Google Patents
Process for hydroxylating aromatic hydrocarbons Download PDFInfo
- Publication number
- GB2116974A GB2116974A GB08307296A GB8307296A GB2116974A GB 2116974 A GB2116974 A GB 2116974A GB 08307296 A GB08307296 A GB 08307296A GB 8307296 A GB8307296 A GB 8307296A GB 2116974 A GB2116974 A GB 2116974A
- Authority
- GB
- United Kingdom
- Prior art keywords
- phenol
- process according
- aromatic hydrocarbon
- reaction
- moles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 22
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 16
- 230000008569 process Effects 0.000 title claims abstract description 16
- 230000000640 hydroxylating effect Effects 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000033444 hydroxylation Effects 0.000 claims abstract description 7
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 7
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 48
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 17
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- -1 misitylene Chemical compound 0.000 claims description 3
- 229960001413 acetanilide Drugs 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 1
- 229940058172 ethylbenzene Drugs 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 16
- 239000006227 byproduct Substances 0.000 description 15
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 229960001867 guaiacol Drugs 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- IRTLGLYSFAKASM-UHFFFAOYSA-N acetic acid;propan-2-ol Chemical compound CC(C)O.CC(O)=O IRTLGLYSFAKASM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by oxidation reactions introducing directly hydroxy groups on a =CH-group belonging to a six-membered aromatic ring with the aid of other oxidants than molecular oxygen or their mixtures with molecular oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/26—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of hydroxy or O-metal groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
A process for the hydroxylation of aromatic hydrocarbons by means of hydrogen peroxide, consisting of reacting the compounds in the presence of synthetic zeolites containing either substituted or exchanged heteroatoms. The reaction is carried out in acetone at a temperature of between 80 and 120 DEG C.
Description
SPECIFICATION
Process for hydroxylating aromatic hydrocarbons
This invention relates to a process for the hydroxy
lation of aromatic hydrocarbons.
The direct hydroxylation of aromatic hydrocarbons with hydrogen peroxide has been known for some time, and is carried out in the presence of a catalyst which is generally chosen from transition metals.
However, this reaction has certain drawbacks, including a low selectivity with respect to the hydrogen peroxide because of the partial decomposition thereof by the metal ions; a low selectivity with respect to the reacted hydrocarbon because of coupling reactions of intermediate organic radicals; and, in the particular case of phenol, the fact that the diphenols which are formed are more easily oxidisable than the phenol itself, resulting in an inevitable reduction in the extent of conversion.
In carrying out the reaction between an aromatic hydrocarbon and hydrogen peroxide, it is known to use an acid aluminosilicate which has been poisoned or partly modified by a rare earth (US-A-3580956).
Although improving the performance of the reaction, the use of this catalytic material does not however completely eliminate the production of considerable quantities of useless by - products, the presence of which negatively influences the final results and the economy of the entire process.
From GB-A-2083816, it is known to be possible to bond hydroxyl groups to aromatic nuclei by reacting the aromatic hydrocarbon concerned with hydrogen peroxide, with none of the aforesaid drawbacks, by carrying out the reaction in the presence of synthetic zeolites containing either substituted or exchanged heteroatoms. Zeolite materials which can be used in this process can be chosen from, for example, those described in GB-A-2024790 and GB-A-2078704, which describe synthetic materials comprising crystalline silica modified by the presence of elements which enter the crystalline silica lattice in place of silicon atoms. The modifying elements may be chosen from Cr, Be, Ti, V, Mn, Fe, Co, Zn, Rh, Ag, Sn,
Sb and B.Also disclosed in GB-A-2024790 and
GB-A-2078704 are methods for preparing these synthetic materials, and reference should be made thereto for the necessary details and for a better understanding of the structure of the material itself.
Returning to the hydroxylation process, as disclosed in GB-A-2083816, it is important to emphasise the great advantage which derives from the use of synthetic zeolites, this advantage consisting of the facility for guiding the reaction towards the formation of one product rather than other by simply choosing a determined modified zeolite. Thus, for example, in the case of phenol hydroxylation, there may be used a porous crystalline synthetic material formed from silicon and titanium oxides, such as disclosed in GB-A-2071071. The use of such a material enables a mixture of hydroquinone and pyrocatechol in a ratio equal to or greater than 1:1 to be obtained.
The reaction between the aromatic hydrocarbon and hydrogen peroxide is preferably carried out at a temperature of from 80 to 1200C, in the presence of the hydrocarbon either alone or with a solvent chosen from water, methanol, acetic acid isopropanol or acetonitrile. Examples of the aromatic hydrocarbon are phenol, toluene, anisole, xylenes, mesitylene, benzene, nitrobenzene, ethylbenzene and acetanilide.
According to the present invention, there is provided a process for the hydroxylation of an aromatic hydrocarbon, which comprises reacting the aromatic hydrocarbon and hydrogen peroxide in the presence of a synthetic zeolite containing substituted and/or exchanged heteroatoms, the reaction being carried out in the presence of acetone.
Thus, we have now found that by reacting the hydrocarbon concerned in the presence of acetone, e.g. as a solvent, it is possible to carry out the reaction using high feed ratios and with high yields.
The quantity of heavy by-products is usually very low. The reaction is preferably carried out at a temperature of from 80 to 1 200C, more preferably carried out at the reflux temperature.
Examples of the aromatic hydrocarbon are those listed above.
in preferred embodiments, the synthetic zeolite is as claimed in any of claims 1 to 15 and 45 of
GB-A-2024790, or as claimed in any of claims 1,2 and 32 of GB-B-2024790, or as claimed in any of claims 1 to 7 and 29 of GB-A-2078704, or as claimed
in any of claims 1 to 6 and 28 of GB-B-2078704.
The invention will now be illustrated by the following Examples, in which the following terms are used: Feed ratio = Moles of H202 fed
Moles ratio = Moles of phenol fed x 100
Phenol selectivity = Moles of diphenols formed
Moles selectivity = Moles of phenol reacted x 100
Moles of diphenols formed
H202 yield Moles of H202 fed x 100
Moles of H2O2 fed
Phenol conversion = Moles of phenol reacted
Moles conversion Moles of phenol fed
Hydroquinone selectivity = Moles of hydroquinone x 100
Moles of diphenols HMME = hydroquinone monomethylether Anisole yield Moles of HMME formed + moles of guaiacol formed
Anisole yield = x 100.
Moles of anisole reacted EXAMPLE 1
50g of phenol, 39g of acetone and 2.59 of catalyst
were fed into a 250 cc flask. When the system
reached a temperature of 80"C, 10 cc of 36% w/v
H202 were added. The following results were
obtained after two hours of reaction:
Phenol selectivity ........................................ 96.25%
Phenol conversion 18.36% H202 yield 88.5%
Tarry by-product/tarry by-product + diphenols 4.2%
Hydroquinone selectivity 50%
EXAMPLE 2
The procedure of Example 1 was repeated, but 15
cc of 36% w/v H202 were added.The following
results were obtained after two hours:
Phenol selectivity ........................................ 95.45%
Phenol conversion 24.25% H202 yield 79.6%
Tarry by-product/tarry by-product + diphenols 5.1% Hydroquinone selectivity 50%.
EXAMPLE 3
The procedure of Example 2 was repeated, but 20
cc of 36% w/v H202 were added. The following
results were obtained after two hours;
Phenol selectivity ........................................ 92.96%
Phenol conversion 31.28%
H202 yield.................................. 73.9%
Tarry by-product/tarry by-product + diphenols 7.8%
Hydroquinone selectivity 50%.
EXAMPLE 4
The procedure of Example 3 was repeated, but 25
cc of 36% H202 were added. The following results
are obtained after two hours:
Phenol selectivity ........................................ 91.29% H202 yield 68.9%
Tarry by-product/tarry by-product + diphenols 9.7%
Hydroquinone selectivity 50%
Phenol conversion 36.64%.
EXAMPLE 5
The procedure of Example 4 was repeated, but 30
cc of 36% H202 were added. The following results
were obtained after two hours:
Phenol selectivity ........................................ 89.4%
H202 yield.................................. 59.4%
Tarry by-product/tarry by-product + diphenols 12%
Hydroquinone selectivity ........................................ 50%
Phenol conversion 37.76%.
EXAMPLE 6
30 cc of anisole, 70 cc of acetone and 3 g of cataiyst were fed into a 250 cc flask fitted with a bulb
condenser. When a temperature of 7ûDS was
reached, 75 cc of 36% H202 were added in drops.
The following results were obtained on termination
of the reaction;
Product distribution: HMME .................................... 64%
Guaiacol ................................. 36% H202yield .................................. 72.8% Anisole conversion 22.7% Tarry by-productltarry by-product + phenol product 6.26% Anisole yield................................... SD.6 S.
EXAMPLE7 The procedure of example 6 was repeated, but 10 cc of 36% H202 were added. The results are as
follows:
Product distribution: HMME .................................... 64% Guaicol 36% H202yield 70%
Anisol yield ........................................ 86%
Anisole conversion 24% Tarry by-product/tarry by-product + phenol product 11%.
The catalyst used in all of the above Examples is a titanium silicalite prepared as described in Example 1 of GB-A-2071071.
Claims (8)
1. A process for the hydroxylation of an aromatic hydrocarbon, which comprises reacting the aromatic hydrocarbon and hydrogen peroxide in the presence of a synthetic zeolite containing substituted and/or
exchanged heteroatoms,the reaction being carried out in the presence of acetone.
2. A process according to claim 1, wherein the aromatic hydrocarbon is phenol, toluene, anisole, a
xylene, misitylene, benzene, nitrobenzene, ethylben
zene, or acetanilide
3. A process according to claim 1 or 2, wherein the reaction is carried out at a temperature of from 80to 120'C.
4. A process according to claim 1,2 or 3, wherein
the synthetic zeolite is as clamed in any of claims 1 to 15 and 45 of GBA024790, or as claimed in any of claims 1,2 and 32 of GB-B-2024790.
5. A process according to claim 1,2 or 3, wherein
the synthetic zeolite is as claimed in any of claims 1
to 7 and 29 of GB-A-2078704, or as claimed in any of claims 1 to 6 and 28 GB-B-2078704.
6. A process according to claim 1,2 or 3, wherein the synthetic zeolite is as claimed in any of claims 1
to 5 and 27 of GB-A-207@071 orGB-B-2071071.
7. A process acc - @ claim 1, substantially as described in any oTthe foregoing Examples.
8. A hydroxylated aromatic hydrocarbon when produced by a process according to any of claims 1
to7.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT20262/82A IT1150699B (en) | 1982-03-19 | 1982-03-19 | PROCEDURE FOR THE OXIDRILATION OF AROMATIC HYDROCARBONS |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8307296D0 GB8307296D0 (en) | 1983-04-20 |
| GB2116974A true GB2116974A (en) | 1983-10-05 |
| GB2116974B GB2116974B (en) | 1985-10-02 |
Family
ID=11165238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08307296A Expired GB2116974B (en) | 1982-03-19 | 1983-03-16 | Process for hydroxylating aromatic hydrocarbons |
Country Status (10)
| Country | Link |
|---|---|
| BE (1) | BE896225A (en) |
| CH (1) | CH652114A5 (en) |
| DE (1) | DE3309669A1 (en) |
| DK (1) | DK171933B1 (en) |
| FR (1) | FR2523575B1 (en) |
| GB (1) | GB2116974B (en) |
| IT (1) | IT1150699B (en) |
| NL (1) | NL192876C (en) |
| NO (1) | NO156648C (en) |
| SE (1) | SE461730B (en) |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2618143A1 (en) * | 1987-07-17 | 1989-01-20 | Rhone Poulenc Chimie | PHENOL HYDROXYLATION PROCESS |
| EP0314582A1 (en) * | 1987-10-29 | 1989-05-03 | Rhone-Poulenc Chimie | Method of hydroxylating phenols and phenol ethers |
| EP0314583A1 (en) * | 1987-10-29 | 1989-05-03 | Rhone-Poulenc Chimie | Process for the hydroxylation of phenols and phenol-ethers |
| FR2643633A1 (en) * | 1989-02-28 | 1990-08-31 | Rhone Poulenc Chimie | PROCESS FOR HYDROXYLATION OF PHENOLS AND PHENOL ETHERS |
| FR2666333A1 (en) * | 1990-08-31 | 1992-03-06 | Rhone Poulenc Chimie | Process for the hydroxylation of phenols and phenol ethers |
| EP0543247A1 (en) | 1991-11-21 | 1993-05-26 | BASF Aktiengesellschaft | Method for preparing titanium silicate crystals of zeolite structure and being essentially free of alkali metals |
| US5233097A (en) * | 1992-10-15 | 1993-08-03 | Uop | Oxidation of aromatics to hydroxyaromatics using aluminosilicates containing framework titanium |
| US5246688A (en) * | 1990-08-29 | 1993-09-21 | Rhone-Poulenc Chimie | Production of silica-based mfi zeolites |
| US5254746A (en) * | 1987-10-29 | 1993-10-19 | Rhone-Poulenc Chimie | Hydroxylation of phenols/phenol ethers |
| EP0567827A1 (en) * | 1992-04-30 | 1993-11-03 | BASF Aktiengesellschaft | Process for preparation of N-hydroxyazoles |
| FR2693457A1 (en) * | 1992-07-10 | 1994-01-14 | Rhone Poulenc Chimie | Phenolic cpds. hydroxylation for phenol(s) and phenolic ether(s) hydroxylation - by hydrogen peroxide with mineral acidic catalyst and in ketone cpd., for esp. phenol to form hydroquinone and pyrocatechol, for improved yields of di:phenol(s) and easy sepn. of acid catalyst |
| US5399336A (en) * | 1990-06-29 | 1995-03-21 | Rhone-Poulenc Chimie | Stannozeosilite/zirconozeosilite zeolites and catalytic hydroxylation of phenolics therewith |
| US5426244A (en) * | 1991-12-20 | 1995-06-20 | Mitsubishi Gas Chemical Company, Inc. | Method for preparing dihydric phenols |
| US5672777A (en) * | 1994-04-12 | 1997-09-30 | Monsanto Company | Catalysts for production of phenol and its derivatives |
| US5712402A (en) * | 1994-08-22 | 1998-01-27 | Board Of Trustees Operating Michigan State University | Catalytic applications of mesoporous metallosilicate molecular sieves and methods for their preparation |
| WO1998005616A1 (en) * | 1996-08-07 | 1998-02-12 | Monsanto Company | Preparation of phenol or phenol derivatives |
| US5736479A (en) * | 1992-12-03 | 1998-04-07 | Leuna-Katalysatoren Gmbh | Oxidation catalysts |
| US5756861A (en) * | 1994-04-12 | 1998-05-26 | Monsanto Company | Method for production for phenol and its derivatives |
| US5808167A (en) * | 1996-08-20 | 1998-09-15 | Solutia Inc. | Selective introduction of active sites for hydroxylation of benzene |
| US5874647A (en) * | 1996-08-20 | 1999-02-23 | Solutia Inc. | Benzene hydroxylation catalyst stability by acid treatment |
| US5892132A (en) * | 1996-08-08 | 1999-04-06 | Solutia Inc. | Transport hydroxylation reactor |
| US6106797A (en) * | 1996-02-29 | 2000-08-22 | Basf Aktiengesellschaft | Gauze catalyst based on titanium or vanadium zeolites and inert gauze fabrics for accelerating oxidation reactions |
| US6156938A (en) * | 1997-04-03 | 2000-12-05 | Solutia, Inc. | Process for making phenol or phenol derivatives |
| US6255539B1 (en) | 1996-10-07 | 2001-07-03 | Solutia Inc. | Chemical composition and process |
| WO2001081275A3 (en) * | 2000-04-27 | 2002-03-14 | Shell Int Research | Process for catalytic hydroxylation of aromatic compounds |
| RU2185368C2 (en) * | 1997-11-27 | 2002-07-20 | ЭНИКЕМ С.п.А. | Method of oxidation of aromatic compounds to hydroxyaromatic compounds |
| US6805851B1 (en) | 1999-08-20 | 2004-10-19 | Basf Aktiengesellschaft | Method for producing crystalline, zeolitic solid matter |
| WO2005063664A1 (en) * | 2003-12-31 | 2005-07-14 | Council Of Scientific & Industrial Research | Process for conversion of phenol to hydroquinone and quinones |
| US8198479B2 (en) | 2005-02-17 | 2012-06-12 | Monsanto Technology Llc | Transition metal-containing catalysts and catalyst combinations including transition metal-containing catalysts and processes for their preparation and use as oxidation catalysts |
| US9206101B2 (en) | 2012-10-04 | 2015-12-08 | China Petrochemical Development Corporation | Method for hydroxylation of phenol |
| CN105523898A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Phenol oxidation method |
| US9682909B2 (en) | 2012-02-17 | 2017-06-20 | Rhodia Operations | Process for hydroxylation of aromatic compounds, hydroxylation catalyst and process for preparing same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4419195A1 (en) * | 1993-07-12 | 1995-01-19 | Degussa | Structured catalyst consisting of microporous oxides of silicon, aluminum and titanium |
| KR20010032082A (en) | 1997-11-14 | 2001-04-16 | 블레어 큐. 퍼거슨 | Process for the Selective Oxidation of Organic Compounds |
| EP1044196A2 (en) * | 1997-11-24 | 2000-10-18 | E.I. Du Pont De Nemours And Company | Process for the selective oxidation of organic compounds |
| JP2005060384A (en) * | 2003-07-30 | 2005-03-10 | Ube Ind Ltd | Method for producing phenolic compound |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1448358A (en) * | 1974-04-04 | 1976-09-08 | Ube Industries | Process for preparint dihydric phenol derivatives |
| US4013727A (en) * | 1974-11-07 | 1977-03-22 | Ube Industries, Ltd. | Process for preparing hydroxyphenyl ethers |
| IT1195029B (en) * | 1980-09-09 | 1988-09-28 | Anic Spa | PROCEDURE FOR THE OXIDRILATION OF AROMATIC HYDROCARBONS |
-
1982
- 1982-03-19 IT IT20262/82A patent/IT1150699B/en active
-
1983
- 1983-03-16 GB GB08307296A patent/GB2116974B/en not_active Expired
- 1983-03-16 CH CH1454/83A patent/CH652114A5/en not_active IP Right Cessation
- 1983-03-16 NO NO830926A patent/NO156648C/en not_active IP Right Cessation
- 1983-03-17 DE DE19833309669 patent/DE3309669A1/en active Granted
- 1983-03-17 NL NL8300962A patent/NL192876C/en not_active IP Right Cessation
- 1983-03-17 DK DK123783A patent/DK171933B1/en not_active IP Right Cessation
- 1983-03-18 SE SE8301492A patent/SE461730B/en not_active IP Right Cessation
- 1983-03-18 FR FR8304502A patent/FR2523575B1/en not_active Expired
- 1983-03-21 BE BE0/210368A patent/BE896225A/en not_active IP Right Cessation
Cited By (54)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0299893A3 (en) * | 1987-07-17 | 1990-08-16 | Rhone-Poulenc Chimie | Process for hydroxylating phenols and phenol ethers |
| FR2618143A1 (en) * | 1987-07-17 | 1989-01-20 | Rhone Poulenc Chimie | PHENOL HYDROXYLATION PROCESS |
| US5160496A (en) * | 1987-07-17 | 1992-11-03 | Rhone-Poulenc Chimie | Hydroxylation of phenols/phenol ethers |
| US5254746A (en) * | 1987-10-29 | 1993-10-19 | Rhone-Poulenc Chimie | Hydroxylation of phenols/phenol ethers |
| EP0314582A1 (en) * | 1987-10-29 | 1989-05-03 | Rhone-Poulenc Chimie | Method of hydroxylating phenols and phenol ethers |
| EP0314583A1 (en) * | 1987-10-29 | 1989-05-03 | Rhone-Poulenc Chimie | Process for the hydroxylation of phenols and phenol-ethers |
| FR2622575A1 (en) * | 1987-10-29 | 1989-05-05 | Rhone Poulenc Chimie | PROCESS FOR HYDROXYLATION OF PHENOLS AND PHENOL ETHERS |
| FR2622574A1 (en) * | 1987-10-29 | 1989-05-05 | Rhone Poulenc Chimie | PROCESS FOR HYDROXYLATION OF PHENOLS AND PHENOL ETHERS |
| FR2643633A1 (en) * | 1989-02-28 | 1990-08-31 | Rhone Poulenc Chimie | PROCESS FOR HYDROXYLATION OF PHENOLS AND PHENOL ETHERS |
| EP0385882A1 (en) * | 1989-02-28 | 1990-09-05 | Rhone-Poulenc Chimie | Method for the hydroxylation of phenols and phenol ethers |
| US5149888A (en) * | 1989-02-28 | 1992-09-22 | Rone-Poulenc Chimie | Hydroxylation of phenols/phenol ethers |
| US5399336A (en) * | 1990-06-29 | 1995-03-21 | Rhone-Poulenc Chimie | Stannozeosilite/zirconozeosilite zeolites and catalytic hydroxylation of phenolics therewith |
| US5246688A (en) * | 1990-08-29 | 1993-09-21 | Rhone-Poulenc Chimie | Production of silica-based mfi zeolites |
| FR2666333A1 (en) * | 1990-08-31 | 1992-03-06 | Rhone Poulenc Chimie | Process for the hydroxylation of phenols and phenol ethers |
| EP0543247A1 (en) | 1991-11-21 | 1993-05-26 | BASF Aktiengesellschaft | Method for preparing titanium silicate crystals of zeolite structure and being essentially free of alkali metals |
| US5401486A (en) * | 1991-11-21 | 1995-03-28 | Basf Aktiengesellschaft | Preparation of essentially alkali-free titanium zeolites |
| US5426244A (en) * | 1991-12-20 | 1995-06-20 | Mitsubishi Gas Chemical Company, Inc. | Method for preparing dihydric phenols |
| EP0567827A1 (en) * | 1992-04-30 | 1993-11-03 | BASF Aktiengesellschaft | Process for preparation of N-hydroxyazoles |
| US5332830A (en) * | 1992-04-30 | 1994-07-26 | Basf Aktiengesellschaft | Preparation of N-hydroxyazoles |
| FR2693457A1 (en) * | 1992-07-10 | 1994-01-14 | Rhone Poulenc Chimie | Phenolic cpds. hydroxylation for phenol(s) and phenolic ether(s) hydroxylation - by hydrogen peroxide with mineral acidic catalyst and in ketone cpd., for esp. phenol to form hydroquinone and pyrocatechol, for improved yields of di:phenol(s) and easy sepn. of acid catalyst |
| US5233097A (en) * | 1992-10-15 | 1993-08-03 | Uop | Oxidation of aromatics to hydroxyaromatics using aluminosilicates containing framework titanium |
| US5736479A (en) * | 1992-12-03 | 1998-04-07 | Leuna-Katalysatoren Gmbh | Oxidation catalysts |
| US5756861A (en) * | 1994-04-12 | 1998-05-26 | Monsanto Company | Method for production for phenol and its derivatives |
| USRE36856E (en) * | 1994-04-12 | 2000-09-05 | Kharitonov; Alexander Sergeevich | Catalysts for production of phenol and its derivatives |
| US5672777A (en) * | 1994-04-12 | 1997-09-30 | Monsanto Company | Catalysts for production of phenol and its derivatives |
| US5855864A (en) * | 1994-08-22 | 1999-01-05 | Board Of Trustees Operating Michigan State University | Catalytic applications of mesoporous metallosilicate molecular sieves and methods for their preparation |
| US6413902B1 (en) | 1994-08-22 | 2002-07-02 | Board Of Trustees Of Michigan State University | Catalytic applications of mesoporous metallosilicate molecular sieves and methods for their preparation |
| US6391278B1 (en) | 1994-08-22 | 2002-05-21 | Board Of Trustees Operating Michigan State University | Catalytic applications of mesoporous metallosilicate molecular sieves and methods for their preparation |
| US6193943B1 (en) | 1994-08-22 | 2001-02-27 | Board Of Trustees Operating Michigan State University | Catalytic applications of mesoporous metallosilicate molecular sieves and methods for their preparation |
| US5712402A (en) * | 1994-08-22 | 1998-01-27 | Board Of Trustees Operating Michigan State University | Catalytic applications of mesoporous metallosilicate molecular sieves and methods for their preparation |
| US6106797A (en) * | 1996-02-29 | 2000-08-22 | Basf Aktiengesellschaft | Gauze catalyst based on titanium or vanadium zeolites and inert gauze fabrics for accelerating oxidation reactions |
| WO1998005616A1 (en) * | 1996-08-07 | 1998-02-12 | Monsanto Company | Preparation of phenol or phenol derivatives |
| US5874646A (en) * | 1996-08-07 | 1999-02-23 | Solutia Inc. | Preparation of phenol or phenol derivatives |
| US5892132A (en) * | 1996-08-08 | 1999-04-06 | Solutia Inc. | Transport hydroxylation reactor |
| US5977008A (en) * | 1996-08-20 | 1999-11-02 | Solutia Inc. | Selective introduction of active sites for hydroxylation of benzene |
| US5874647A (en) * | 1996-08-20 | 1999-02-23 | Solutia Inc. | Benzene hydroxylation catalyst stability by acid treatment |
| US5808167A (en) * | 1996-08-20 | 1998-09-15 | Solutia Inc. | Selective introduction of active sites for hydroxylation of benzene |
| US6255539B1 (en) | 1996-10-07 | 2001-07-03 | Solutia Inc. | Chemical composition and process |
| US6156938A (en) * | 1997-04-03 | 2000-12-05 | Solutia, Inc. | Process for making phenol or phenol derivatives |
| RU2185368C2 (en) * | 1997-11-27 | 2002-07-20 | ЭНИКЕМ С.п.А. | Method of oxidation of aromatic compounds to hydroxyaromatic compounds |
| EP2347997A2 (en) | 1999-08-20 | 2011-07-27 | Basf Se | Method for producing a crystalline, zeolithic solid |
| US7081237B2 (en) | 1999-08-20 | 2006-07-25 | Basf Aktiengesellschaft | Preparation of a crystalline, zeolitic solid |
| US6805851B1 (en) | 1999-08-20 | 2004-10-19 | Basf Aktiengesellschaft | Method for producing crystalline, zeolitic solid matter |
| US6437197B1 (en) | 2000-04-27 | 2002-08-20 | Shell Oil Company | Process for catalytic hydroxylation of aromatic hydrocarbons |
| US6900358B2 (en) | 2000-04-27 | 2005-05-31 | Shell Oil Company | Process for catalytic hydroxylation of benzene |
| WO2001083415A3 (en) * | 2000-04-27 | 2002-03-14 | Shell Int Research | Process for catalytic hydroxylation of benzene |
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| WO2005063664A1 (en) * | 2003-12-31 | 2005-07-14 | Council Of Scientific & Industrial Research | Process for conversion of phenol to hydroquinone and quinones |
| US8198479B2 (en) | 2005-02-17 | 2012-06-12 | Monsanto Technology Llc | Transition metal-containing catalysts and catalyst combinations including transition metal-containing catalysts and processes for their preparation and use as oxidation catalysts |
| US8962513B2 (en) | 2005-02-17 | 2015-02-24 | Monsanto Technology Llc | Transition metal-containing catalysts and catalyst combinations including transition metal-containing catalysts and processes for their preparation and use as oxidation catalysts |
| US9682909B2 (en) | 2012-02-17 | 2017-06-20 | Rhodia Operations | Process for hydroxylation of aromatic compounds, hydroxylation catalyst and process for preparing same |
| US9206101B2 (en) | 2012-10-04 | 2015-12-08 | China Petrochemical Development Corporation | Method for hydroxylation of phenol |
| CN105523898A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Phenol oxidation method |
| CN105523898B (en) * | 2014-09-29 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of method of oxidation of phenol |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1150699B (en) | 1986-12-17 |
| NO830926L (en) | 1983-09-20 |
| DK123783D0 (en) | 1983-03-17 |
| SE8301492L (en) | 1983-09-20 |
| NL8300962A (en) | 1983-10-17 |
| DE3309669A1 (en) | 1983-09-29 |
| DE3309669C2 (en) | 1990-10-25 |
| DK123783A (en) | 1983-09-20 |
| NL192876B (en) | 1997-12-01 |
| SE8301492D0 (en) | 1983-03-18 |
| NO156648C (en) | 1987-10-28 |
| SE461730B (en) | 1990-03-19 |
| CH652114A5 (en) | 1985-10-31 |
| FR2523575A1 (en) | 1983-09-23 |
| FR2523575B1 (en) | 1986-10-10 |
| IT8220262A0 (en) | 1982-03-19 |
| NO156648B (en) | 1987-07-20 |
| IT8220262A1 (en) | 1983-09-19 |
| GB8307296D0 (en) | 1983-04-20 |
| NL192876C (en) | 1998-04-02 |
| GB2116974B (en) | 1985-10-02 |
| BE896225A (en) | 1983-09-21 |
| DK171933B1 (en) | 1997-08-18 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| PE20 | Patent expired after termination of 20 years |
Effective date: 20030315 |