CN105367389A - Method for preparing hydroquinone by p-benzoquinone - Google Patents
Method for preparing hydroquinone by p-benzoquinone Download PDFInfo
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- CN105367389A CN105367389A CN201510818697.8A CN201510818697A CN105367389A CN 105367389 A CN105367389 A CN 105367389A CN 201510818697 A CN201510818697 A CN 201510818697A CN 105367389 A CN105367389 A CN 105367389A
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- carbon atom
- catalyzer
- present
- para benzoquinone
- gas
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- 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
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
- C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
Abstract
The invention provides a method for preparing hydroquinone by p-benzoquinone. The method is characterized in that in a liquid medium, p-benzoquinone with low purity is taken as a raw material, and under effect of a metal catalyst, hydroquinone is prepared through highly-selective hydrogenation reduction.
Description
Technical field
The present invention relates to a kind of preparation method of Resorcinol, particularly relate to the hydrogenating reduction catalyzer that a kind of cost is lower, lower to para benzoquinone purity requirement.
Background technology
As a kind of important industrial chemicals, Resorcinol is widely used in the industries such as polymer, agricultural chemicals, dyestuff, petrochemical complex.At present, the purposes of Resorcinol mainly comprises following several: the 1) stopper of high polymer monomer, as vinylformic acid, acrylate, vinyl cyanide etc.; 2) antioxidant, as the stablizer/antioxidant and anticoagulant etc. of the anti-aging agent of rubber and plastics, coating lacquer; 3) synthesis material of tertiarybutylhydroquinone; 4) other is as the catalyzer etc. of black-and-white development agent, synthetic gas desulfurization technique.In recent years, along with the range of application of Resorcinol in field of fine chemical is widened gradually, its demand is the steady-state growth impetus.
Process of Hydroquinone Production technique the earliest comes from aniline oxidation style, after namely aniline is oxidized to para benzoquinone by high-valence state metal salts thing in acidic medium, is separated the para benzoquinone obtained uses stoichiometric reduced iron powder process to obtain Resorcinol through " stripping ".But, this raw materials technology high cost, and there is serious pollution problem.
Hydoxylating phenol take phenol as raw material, with H
2o
2reaction generates the mixture of Resorcinol and pyrocatechol.Because the character of Resorcinol and pyrocatechol is close, therefore separating technology is more complicated, and not only equipment investment is large, energy consumption is high, and the tar by product of sepn process is more.
Due to the shortcomings existed in current domestic Process of Hydroquinone Production technique, develop a kind of efficient, succinct Process of Hydroquinone Production technique become this area in the urgent need to.In hydrogenation reduction, noble metal catalyst is widely used in all kinds of reduction system due to its excellent catalytic activity.But, because the price of precious metal is higher, and easily poisoning and deactivation, so also counteracts that its application in some fields, such as: in the para benzoquinone that aniline oxidation style obtains, although greatly reduce the foreign matter content in para benzoquinone through stripping process, noble metal catalyst is used still to occur catalyst levels excessive and rapid deactivation phenomenon when carrying out hydrogenating reduction.Although the purity improving para benzoquinone raw material can avoid Catalysts Deactivation Problems as far as possible, the increase of respective handling expense makes said process and uneconomical.Therefore, exploitation is a kind of cheap, and becomes very necessary to the novel metal catalyzer that para benzoquinone purity has a broad applicability.
Summary of the invention
The present invention is using one or more in transition metal Pd, Pt, Ir, Au, Ru, Rh as catalyzer principal constituent, one or more in use/unuse Cu, Ni, Co, Fe, Zn, as auxiliary component, develop a kind of method using hydrogen reducing para benzoquinone to prepare Resorcinol.Compared with the prior art, the purity requirement of the catalysis that the present invention develops to raw material para benzoquinone is low, active high, and can repeatedly recycle, so the use cost of catalyzer has substantial degradation.The present invention uses homemade para benzoquinone as raw material, para benzoquinone purity≤98%, and containing metal ion, tar and polymer class impurity, so this new catalyst disclosed by the invention is low for the purity requirement of para benzoquinone, its superiority is apparent, has important using value.
Catalyzer used in the present invention can adopt and support or unsupported form, and carrier can be silicon oxide, aluminum oxide, gac, diatomite, molecular sieve, clay, resin or above-mentioned several mixture.Further, the loading of the catalyzer that present method uses is generally at 0.1-30%, and preferably, loading is at 1-10%.
The reaction medium that the present invention uses is liquid, can be the halogenated alkane containing 1-3 carbon atom, comprise about 2 to about 8 carbon atom alkane nitriles, aromatic nitriles or organic amides, straight chain, side chain or ring-type organic (polynary) alcohol containing 1 to 8 carbon atom, the heterogeneous ring compound containing 4-8 carbon atom or the ether containing 2-8 carbon atom, or the combination of aforementioned solvents.
The present invention uses hydrogen as reductive agent, can be pure hydrogen, also can be the gas mixture containing hydrogen, and the gas as blending ingredients can be the combination of nitrogen, argon gas, helium, neon or above-mentioned gas.When reactant gases is hydrogen, pressure is usually at 1-60atm, and preferably, pressure is 5-50atm.When gas is mixed gas, need corresponding raising pressure condition according to hydrogen partial pressure.
In order to realize the object of foregoing invention, the present invention adopts following operation steps: after para benzoquinone, catalyzer being mixed with liquid medium, add autoclave, off-response device is also filled with hydrogen-containing gas and reaches specified pressure, react after certain hour at a certain temperature and be cooled to room temperature, be vented and measure the quality of Resorcinol.Wherein, all there is material impact to reaction result in catalyst component, temperature of reaction and hydrogen pressure, and these factors are also the technology contents that the present invention relates to.
One of feature of the present invention temperature of reaction is gentle, can at 40-150
ocarry out under C.Preferably, temperature is at 40-100
oc.
Reaction times of the present invention, preferably, the time was 2-24 hour usually at 1-48 hour.
The reaction process occurred in reactor can represent in order to lower equation:
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described in further detail.To contribute to understanding the present invention by following embodiment, but not limit technical scheme of the present invention in any form.
Embodiment 1-8.
Homemade para benzoquinone (1.2g, 11.1mmol), metal catalyst (0.12g) and THF(44.0g, 50mL is added in 250mL reactor), after mixing, off-response still is also filled with 40atm hydrogen, stirs and is heated to 70
oc, reacts and is cooled to room temperature after 24 hours, takes out mixture and analyze after exhaust.
| Project | Catalyzer | Resorcinol yield (%) |
| 1. | 1%Pd/C | 94 |
| 2. | 3%Pd/C | 97 |
| 3. | 5%PtFe/C | 94 |
| 4. | 5%IrFe/C | 86 |
| 5. | 5%PdNi/C | 96 |
| 6. | 5%RuNi/C | 60 |
| 7. | Raney's nickel | 95 |
| 8. | 10%Ni/C | 92 |
Embodiment 9-13.
Experimental procedure is identical with embodiment 8, and only replaced by other solvent of the THF in experimental procedure three, reaction result is as shown in the table.
| Project | Solvent (mL) | Yield (%) |
| 1. | Methylene dichloride (50) | 98 |
| 2. | DMF（50） | 98 |
| 3. | Ethanol (50) | 82 |
| 4. | Dioxane (50) | 80 |
| 5. | Glycol dimethyl ether (50) | 84 |
Embodiment 14-16.
Experimental procedure is identical with embodiment 8, only changes the temperature of reaction in experimental procedure three, as shown in the table on the impact of reaction result.
| Project | Temperature ( oC） | Yield (%) |
| 1. | 40 | 52 |
| 2. | 80 | 96 |
| 3. | 150 | 90 |
Embodiment 17-19.
Experimental procedure is identical with embodiment 8, only changes the hydrogen pressure in experimental procedure three, as shown in the table on the impact of reaction result.
| Project | Gas (atm) | Yield (%) |
| 1. | H 2（5） | 45 |
| 2. | H 2（60） | 96 |
| 3. | H 2:N 2=1:1（80） | 91 |
Because of length restriction, the present invention does not illustrate one by one to all examples, but the technical scheme adopting the mode of carrying out equivalent replacement or equivalent transformation to the key element of this technology to obtain all is in protection scope of the present invention.
Claims (6)
1. the invention provides a kind of preparation method of Resorcinol, it is characterized in that: using the lower para benzoquinone of purity as raw material, under metal catalyst effect, in liquid medium, carry out the technology that hydrogenation reduction prepares Resorcinol.
2. method according to claim 1, catalyzer used in the present invention is using one or more in transition metal Pd, Pt, Ir, Au, Ru, Rh as principal constituent, and one or more in use/unuse Cu, Ni, Co, Fe, Zn are as auxiliary component; Catalyzer can adopt unsupported or supported form, carrier can be silicon oxide, aluminum oxide, gac, diatomite, molecular sieve, clay, resin or above-mentioned several mixture, the loading of catalyzer is generally 0.1-30%, and preferably, loading is at 1-10%.
3. method according to claim 1, catalyzer used in the present invention can use para benzoquinone that purity is lower as raw material, and the impurity in para benzoquinone can be metal ion, tar or high score subclass material.
4. method according to claim 1, described reaction medium can be halogenated alkane containing 1-3 carbon atom, comprise 2 to about 8 carbon atom alkane nitriles, aromatic nitriles or organic amides, straight chain, side chain or ring-type organic (polynary) alcohol containing 1-8 carbon atom, the heterogeneous ring compound containing 4-8 carbon atom or the ether containing 2-8 carbon atom, or the combination of aforementioned solvents.
5. method according to claim 1, described hydrogen can be pure hydrogen, also can use the gas mixture containing hydrogen, and the gas as blending ingredients can be the combination of nitrogen, argon gas, helium, neon or above-mentioned gas.
6. method according to claim 1, the reduction reaction of present method can at 40-150
ocarry out under C, preferable temperature is at 40-100
oc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510818697.8A CN105367389A (en) | 2015-11-24 | 2015-11-24 | Method for preparing hydroquinone by p-benzoquinone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510818697.8A CN105367389A (en) | 2015-11-24 | 2015-11-24 | Method for preparing hydroquinone by p-benzoquinone |
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| Publication Number | Publication Date |
|---|---|
| CN105367389A true CN105367389A (en) | 2016-03-02 |
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|---|---|---|---|
| CN201510818697.8A Pending CN105367389A (en) | 2015-11-24 | 2015-11-24 | Method for preparing hydroquinone by p-benzoquinone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107649170A (en) * | 2017-09-30 | 2018-02-02 | 宝鸡文理学院 | A kind of carried molecular sieve catalyst for synthesizing the DI-tert-butylphenol compounds of 4 methyl 2,6 and its application |
| CN114621060A (en) * | 2020-12-12 | 2022-06-14 | 中国科学院大连化学物理研究所 | Method for preparing hydroquinone by hydrogenation of p-benzoquinone |
-
2015
- 2015-11-24 CN CN201510818697.8A patent/CN105367389A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107649170A (en) * | 2017-09-30 | 2018-02-02 | 宝鸡文理学院 | A kind of carried molecular sieve catalyst for synthesizing the DI-tert-butylphenol compounds of 4 methyl 2,6 and its application |
| CN107649170B (en) * | 2017-09-30 | 2020-02-21 | 宝鸡文理学院 | Supported molecular sieve catalyst for synthesizing 4-methyl-2, 6-di-tert-butylphenol and application thereof |
| CN114621060A (en) * | 2020-12-12 | 2022-06-14 | 中国科学院大连化学物理研究所 | Method for preparing hydroquinone by hydrogenation of p-benzoquinone |
| CN114621060B (en) * | 2020-12-12 | 2023-07-07 | 中国科学院大连化学物理研究所 | Method for preparing hydroquinone by p-benzoquinone hydrogenation |
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Application publication date: 20160302 |