CN112844494B - Method for recycling magnesium alkylation reaction catalyst - Google Patents
Method for recycling magnesium alkylation reaction catalyst Download PDFInfo
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- CN112844494B CN112844494B CN202011564119.3A CN202011564119A CN112844494B CN 112844494 B CN112844494 B CN 112844494B CN 202011564119 A CN202011564119 A CN 202011564119A CN 112844494 B CN112844494 B CN 112844494B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
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- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention provides a method for recycling a magnesium alkylation reaction catalyst, and relates to the technical field of resource utilization of industrial waste residues. The method for recycling the magnesium alkylation reaction catalyst specifically comprises the following operations: drying and crushing the waste magnesium oxide catalyst, roasting the crushed waste magnesium oxide catalyst to remove carbon deposition, adding the crushed waste magnesium oxide catalyst into deionized water, stirring the mixture at a constant temperature to obtain slurry, introducing a proper amount of carbon dioxide into the slurry under high-speed stirring, filtering the slurry to obtain a filter cake, taking a dried powdery solid of the filter cake as a precursor, adding assistants such as copper, graphite and the like, and granulating and tabletting to obtain the regenerated catalyst. The invention can effectively recycle the used waste magnesium oxide catalyst and change waste into valuable; the magnesium compound is subjected to structural transformation by adopting carbon dioxide, so that the consumption of acid and alkali is saved, and the treatment of salt-containing wastewater is avoided; the method has simple process, effectively controls harmful substances in the whole process, and has higher environmental and economic values.
Description
Technical Field
The invention relates to the technical field of resource utilization of industrial waste residues, in particular to a method for recycling a magnesium alkylation reaction catalyst.
Background
Alkylated hydroxyaromatic compounds have a variety of uses. For example, o-cresol, produced by the gas phase reaction of phenol with methanol, is used as a disinfectant and preservative. The alkylation of phenol with methanol also produces 2, 6-dimethylphenol, which is a monomer polymerized to produce polyphenylene ether resins. The high-efficiency alkylation catalyst is the key for the industrial production of 2, 6-dimethylphenol and is also one of the key technologies for the industrial production of polyphenylene ether resin. The magnesium oxide monomer catalyst is one of the most important catalysts for synthesizing 2, 6-dimethylphenol in industry due to simple preparation process and low price.
The magnesium alkylation catalyst is simple to prepare and relatively cheap, but the service life of the catalyst is only about three months. In the latest national records of dangerous wastes, the waste catalyst generated in the process of synthesizing 2, 6-dimethylphenol from phenol and methanol is definitely specified as dangerous waste, the waste category is hour W50 waste catalyst, and the code of the waste is 261-180-50. Therefore, the magnesium-based spent catalyst used in the reaction must be subjected to a harmless treatment and cannot be freely buried.
The waste magnesium oxide catalyst contains a large amount of magnesium resources, and if the waste magnesium oxide catalyst is simply sent to a dangerous waste treatment plant for treatment, the resources can be wasted.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a method for recycling a magnesium alkylation reaction catalyst, which solves the problem that resources are wasted by directly treating a waste magnesium oxide catalyst.
(II) technical scheme
In order to realize the purpose, the invention is realized by the following technical scheme: a method for recycling a magnesium alkylation reaction catalyst comprises the following preparation method:
drying the waste magnesium oxide catalyst, and then crushing and grinding the dried waste magnesium oxide catalyst;
roasting the crushed waste magnesium oxide catalyst to remove carbon deposition;
adding the calcined waste catalyst into deionized water at a certain temperature, and stirring at a constant temperature to obtain slurry;
step four, stirring the slurry obtained in the step three at a high speed under the constant temperature condition, and continuously introducing a proper amount of carbon dioxide;
filtering the slurry obtained in the fourth step to obtain a filter cake, and drying the filter cake to obtain a powdery solid;
and step six, taking the powdery solid as a precursor, adding copper components, graphite and other auxiliaries, and granulating, tabletting and forming to obtain the regenerated catalyst.
Preferably, the size of the crushed particles of the waste magnesium oxide catalyst in the first step is 80-180 mesh.
Preferably, the roasting temperature of the waste magnesium oxide catalyst powder in the second step is 300-700 ℃, and the roasting time is 2-6 hours.
Preferably, the waste magnesium oxide catalyst powder roasted in the third step is added into deionized water at the temperature of 60-100 ℃, the constant-temperature stirring time is 1-5 hours, and the mass of the waste magnesium oxide catalyst powder and the deionized water is 1:5-1:500.
preferably, carbon dioxide gas is introduced into the slurry in the fourth step, the flow rate of the carbon dioxide gas is controlled to be 200-1200 ml per minute per 100 g of the waste magnesium oxide catalyst, the stirring speed is controlled to be more than 300 revolutions per minute, and the constant temperature is controlled to be 60-100 ℃.
Preferably, the slurry in the fifth step is subjected to vacuum filtration, centrifugal separation or plate-and-frame filter pressing to obtain a filter cake, wherein the drying temperature of the filter cake is 60-150 ℃, and the drying time is 6-48 hours.
Preferably, the copper component is added in the form of a salt solution containing copper ions in step six, preferably a copper nitrate solution.
(III) advantageous effects
The invention provides a method for recycling a magnesium alkylation reaction catalyst. The method has the following beneficial effects:
the invention can effectively recycle the used waste magnesium oxide catalyst, and changes waste into valuable; the magnesium compound is subjected to structural transformation by adopting carbon dioxide, and compared with the prior art, the consumption of acid and alkali is saved, so that the treatment of salt-containing wastewater is avoided; the method has simple process, effective control of harmful substances in the whole process, no secondary pollution and high environmental and economic values.
Drawings
FIG. 1 is an XRD diagram of a regenerated catalyst in a method for recycling a magnesium alkylation catalyst.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
as shown in fig. 1, 40 g of waste magnesium oxide catalyst was weighed, dried at 80 ℃, and then put into a ball mill to be pulverized to 80 mesh or more. And (3) roasting the crushed waste magnesium oxide catalyst in a muffle furnace at the temperature of 450 ℃ for 4 hours. The roasted magnesium oxide powder is put into a 1000 ml flask, 500 ml of deionized water with the temperature of 80 ℃ is added, and the mixture is stirred for 1 hour by keeping the temperature of 80 ℃ in a water bath. Then, at a constant temperature of 80 ℃, the stirring speed is adjusted to 400 revolutions per minute, and carbon dioxide gas is introduced into the slurry, wherein the flow rate of the carbon dioxide gas is controlled to be 100 milliliters per minute. Stirring was continued for 4 hours, and then the slurry was suction-filtered with a vacuum pump to obtain a filter cake. And drying the filter cake in a drying box at the temperature of 80 ℃ for 10 hours to obtain a powdery solid.
And taking the powdery solid as a precursor, adding a solution containing 0.02 g of copper nitrate, fully stirring, adding a proper amount of 0.2 g of graphite and 5.6 g of polyethylene glycol, granulating, and tabletting to obtain the regenerated catalyst.
The catalytic performance of the regenerated catalyst is shown in Table 1, and the X-ray diffraction pattern (XRD) of the regenerated catalyst is shown in FIG. 1.
The second embodiment:
60 g of waste magnesium oxide catalyst is weighed, dried at 80 ℃, and then put into a ball mill to be crushed into more than 80 meshes. And (3) roasting the crushed waste magnesium oxide catalyst in a muffle furnace at the roasting temperature of 500 ℃ for 4 hours. The roasted magnesium oxide powder is put into a 1000 ml flask, 600 ml of deionized water with the temperature of 80 ℃ is added, and the mixture is stirred for 1 hour by keeping the temperature of 80 ℃ in a water bath. Then, at a constant temperature of 80 ℃, the stirring speed is adjusted to 300 revolutions per minute, and carbon dioxide gas is introduced into the slurry, wherein the flow rate of the carbon dioxide gas is controlled to be 200 milliliters per minute. Stirring was continued for 6 hours, and then the slurry was suction-filtered with a vacuum pump to obtain a filter cake. And drying the filter cake in a drying oven at 80 ℃ for 10 hours to obtain a powdery solid.
And adding a solution containing 0.03 g of copper nitrate into the powdery solid serving as a precursor, fully stirring, adding a proper amount of 0.4 g of graphite and 7.2 g of polyethylene glycol, granulating, and tabletting to obtain the regenerated catalyst.
The catalytic performance of the regenerated catalyst is shown in Table 1, and the X-ray diffraction pattern (XRD) of the regenerated catalyst is shown in FIG. 1.
TABLE 1 shows the catalytic performance of the regenerated catalysts of examples 1-2
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (2)
1. A method for recycling a magnesium alkylation reaction catalyst is characterized by comprising the following preparation steps:
drying the waste magnesium oxide catalyst, and then crushing and grinding the dried waste magnesium oxide catalyst;
roasting the crushed waste magnesium oxide catalyst to remove carbon deposition;
adding the roasted waste magnesium oxide catalyst into deionized water at a certain temperature, and stirring at a constant temperature to obtain slurry;
step four, stirring the slurry obtained in the step three at a high speed under the constant temperature condition, and continuously introducing a proper amount of carbon dioxide;
filtering the slurry obtained in the fourth step to obtain a filter cake, and drying the filter cake to obtain a powdery solid;
taking the powdery solid as a precursor, adding a copper component, graphite and polyethylene glycol, and granulating, tabletting and forming to obtain a regenerated catalyst;
the specification of the crushed particles of the waste magnesium oxide catalyst in the first step is that the crushed particles are sieved by a sieve of 80-180 meshes;
in the second step, the roasting temperature of the waste magnesium oxide catalyst powder is 300-700 ℃, and the roasting time is 2-6 hours;
adding the calcined waste magnesium oxide catalyst powder into deionized water at the temperature of 60-100 ℃, stirring at constant temperature for 1-5 hours, wherein the mass of the waste magnesium oxide catalyst powder and the deionized water is 1:5-1:500, a step of;
introducing carbon dioxide gas into the slurry in the fourth step, wherein the flow rate of the carbon dioxide gas is controlled to be 200-1200 ml per minute per 100 g of waste magnesium oxide catalyst, the stirring speed is controlled to be more than 300 revolutions per minute, and the constant temperature is controlled to be 60-100 ℃;
and fifthly, obtaining a filter cake by performing vacuum filtration, centrifugal separation or plate-and-frame filter pressing on the slurry in the step five, wherein the drying temperature of the filter cake is 60-150 ℃, and the drying time is 6-48 hours.
2. The method for recycling the magnesium-based alkylation reaction catalyst according to claim 1, wherein the method comprises the following steps: in the sixth step, the copper component is added in the form of a salt solution containing copper ions.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3962126A (en) * | 1974-11-25 | 1976-06-08 | General Electric Company | Reactivation of a magnesium oxide catalyst |
| US6291724B1 (en) * | 1997-09-24 | 2001-09-18 | General Electric Company | Suppression of highly alkylated phenols in the catalytic alkylation reaction of phenol |
| CN102417195B (en) * | 2010-09-28 | 2014-02-26 | 高佳令 | Improvement of production process for producing magnesium oxide by carbonization method |
| CN103483157A (en) * | 2013-10-21 | 2014-01-01 | 连云港阳方催化科技有限公司 | Synthesis method of ortho-cresol |
| CN107267200B (en) * | 2016-04-06 | 2019-03-08 | 中国石油化工股份有限公司 | A method of it is alkylated by alkane and alkene |
| JP2019523131A (en) * | 2016-07-29 | 2019-08-22 | サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ | Phenol alkylation catalyst precursor and catalyst, catalyst formation method, catalyst regeneration method, and phenol alkylation method |
| CN111518584A (en) * | 2020-05-15 | 2020-08-11 | 浙江工业大学 | Method for producing high-octane aromatic gasoline by alkylating benzene and methanol |
| CN111777085B (en) * | 2020-06-12 | 2022-09-27 | 江苏理工学院 | Method for preparing magnesium-aluminum hydrotalcite from waste dehydrogenation catalyst |
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