CN112551489B - Modified Y-type molecular sieve regenerant, preparation method and application thereof - Google Patents
Modified Y-type molecular sieve regenerant, preparation method and application thereof Download PDFInfo
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- CN112551489B CN112551489B CN202011444668.7A CN202011444668A CN112551489B CN 112551489 B CN112551489 B CN 112551489B CN 202011444668 A CN202011444668 A CN 202011444668A CN 112551489 B CN112551489 B CN 112551489B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/022—Preparation from organic compounds
- C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
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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
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Abstract
The invention discloses a modified Y-type molecular sieve regenerant, a preparation method and application thereof. The modified Y-type molecular sieve regenerant consists of a Y-type molecular sieve, a binder and an auxiliary agent, wherein the auxiliary agent is water or graphite powder. The invention modifies the Y-type molecular sieve, so that the micropores of the Y-type molecular sieve are more uniform, and the Y-type molecular sieve has a larger cavity and a three-dimensional twelve-membered ring channel system. The modified Y-type molecular sieve regenerant can enable various organic molecules to enter the supercage and perform catalytic reaction. The modified Y-type molecular sieve can increase the effective anthraquinone content of hydrogen peroxide working solution by 10-17% under the condition of lower regeneration temperature. The regenerant can be recycled and has high stability.
Description
Technical Field
The invention relates to a regenerant for preparing hydrogen peroxide working solution by an anthraquinone process, a preparation method and application thereof.
Background
The hydrogen peroxide is a strong oxidant, is an inorganic chemical raw material with high industrial application value, is widely applied to the fields of industry, medicine, military use and the like, and is green. Therefore, the demand of hydrogen peroxide is increasing day by day, and the synthesis process of hydrogen peroxide is widely researched in order to meet the huge market demand. The existing hydrogen peroxide preparation methods include anthraquinone method and direct hydrogen-oxygen synthesis method. The principle of anthraquinone method for industrially producing hydrogen peroxide is that alkyl anthraquinone is dissolved into working solution, hydrogenation reaction is carried out under the catalytic action of a catalyst taking nickel or palladium as an active component to generate alkyl anthraquinone, then the working solution containing the alkyl anthraquinone is oxidized to generate hydrogen peroxide and the alkyl anthraquinone, and then the working solution is extracted to obtain hydrogen peroxide solution and the working solution. The principle of the direct hydrogen-oxygen combination method is that a reaction medium and a catalyst are added into a high-pressure reactor, a mixed gas of hydrogen, oxygen and nitrogen in a certain proportion is introduced under the condition of continuous stirring, and the hydrogen peroxide can be generated through reaction at a certain temperature and under a certain pressure. The direct hydrogen-oxygen synthesis method has the defects of low product content and harsh conditions, and uses the mixed gas of hydrogen and oxygen, so the mixed gas has high risk, and the anthraquinone method is often selected industrially to prepare the hydrogen peroxide.
The principle of anthraquinone method for industrially producing hydrogen peroxide is that alkyl anthraquinone is dissolved into working solution, hydrogenation reaction is carried out under the catalytic action of a catalyst taking nickel or palladium as an active component to generate alkyl anthraquinone, then the working solution containing the alkyl anthraquinone is oxidized to generate hydrogen peroxide and the alkyl anthraquinone, and then the working solution is extracted to obtain hydrogen peroxide solution and the working solution. The anthraquinone process produces hydrogen peroxide carrier namely alkyl anthraquinone and tetrahydro alkyl anthraquinone, but because alkyl anthraquinone is continuously and cyclically hydrogenated and oxidized in the process of preparing hydrogen peroxide by anthraquinone process, various accompanying side reactions are inevitable to produce some anthraquinone derivatives, substances which can not react to produce hydrogen peroxide are produced, and these substances are called degradation products collectively. The degradation of the alkylanthraquinone is divided into hydrogenation degradation and oxidation degradation, wherein the hydrogenation degradation comprises deep hydrogenation and carbonyl hydrogenolysis of anthraquinone aromatic rings, and the oxidation degradation is that the hydrogenated anthraquinone is subjected to oxidation reaction to generate anthraquinone epoxy compounds or acid anhydride substances. When the degradation product is accumulated to a certain concentration, the content of effective alkylanthraquinone in the working solution is reduced, the reaction efficiency is reduced, the loss is increased, and meanwhile, the degradation of the alkylanthraquinone influences the property of the working solution, so that the density of the working solution is increased, the viscosity is increased, the operation load is increased, the energy consumption is increased, and the reaction can be stopped seriously. Therefore, the degradation and regeneration of organic matters such as anthraquinone and the like in the process of preparing hydrogen peroxide by the anthraquinone method are important factors influencing the production. The invention provides a method for improving the stability of a molecular sieve framework by using a modified Y-shaped molecular sieve as a regenerant, which has an ideal regeneration effect, and can improve the stability and activity of the molecular sieve framework by modifying the Y-shaped molecular sieve by using a binder.
Patent CN 101554996A proposes a preparation method of hydrogen peroxide working solution regenerant, which adopts calcium oxide as an active component, and the component proportion is as follows: 1% -99% of calcium oxide, and the balance of alkaline oxide, preferably 50% -70% of calcium oxide, and the balance of alkaline oxide. The method has the advantages of high calcium oxide content, no bonding with alkaline oxides, direct mixing, low strength, instability, easy dispersion in working solution, blockage of production devices and production stop.
Patent 105174229B proposes a composite active regenerant for hydrogen peroxide working solution by anthraquinone process and a preparation method thereof, comprising a two-layer or three-layer structure, wherein the two-layer structure comprises 50-95% of active alumina on the outer surface layer, the rest is calcium oxide, 50% of calcium oxide on the core layer, 50% of silicon dioxide, and the three-layer structure comprises 50-99% of active alumina on the outermost layer, 0-2.5% of alkali metal oxide, the rest is calcium oxide, 50-99% of calcium oxide on the centripetal layer, 0-2.5% of alkali metal oxide, the rest is silicon dioxide, 50-99% of silicon oxide on the core layer, and the rest is calcium oxide. The hydrogen peroxide working solution regenerant prepared by the method comprises a multilayer structure, a core structure does not contain a binder, the structure is unstable, and in addition, the multilayer structure ensures that the regeneration effect is not thorough, limits the regeneration amount of the working solution, and increases the alkalinity of the working solution due to long-term use of the regenerant.
Patent CN 105152137B proposes a hydrogen peroxide working solution regenerant in hydrogen peroxide preparation process by anthraquinone method and a preparation method thereof, wherein the regenerant comprises: 10-80% of alumina powder, 10-80% of magnesium oxide powder, 1-112% of sesbania powder, gamma-type aluminum oxide and cubic magnesium oxide powder. The aluminum oxide is used as a regenerant, the regeneration effect is not ideal, a large amount of anthraquinone degradation products still exist after treatment, the service life of the regenerant is short, the regenerant needs to be replaced, and the waste of the regenerant is caused.
Disclosure of Invention
Based on the above problems, the present invention aims to provide a modified Y-type molecular sieve regenerant, which is obtained by modifying a Y-type molecular sieve with a binder and an auxiliary agent, so that micropores of the Y-type molecular sieve are more uniform, and the Y-type molecular sieve regenerant has a larger cavity and a three-dimensional twelve-membered ring channel system. The modified Y-type molecular sieve regenerant can enable various organic molecules to enter a supercage and to perform catalytic reaction. The modified Y-type molecular sieve can increase the effective anthraquinone content of hydrogen peroxide working solution by 10-17% under the condition of lower regeneration temperature.
The modified Y-type molecular sieve regenerant is composed of a Y-type molecular sieve, a binder and an auxiliary agent, wherein the auxiliary agent is water or graphite powder.
Preferably, the Y-type molecular sieve is a USY-type molecular sieve or an HY-type molecular sieve.
Preferably, the binder is at least one of kaolin, methyl cellulose, silica sol, sesbania powder, alumina powder and nitric acid solution.
More preferably, the binder in the regenerant accounts for 5% -30% of the weight of the Y-type molecular sieve.
More preferably, the auxiliary agent in the regenerant accounts for 3-40% of the weight of the Y-type molecular sieve.
The invention also provides a preparation method of the modified Y-type molecular sieve regenerant, which comprises the following steps:
weighing raw materials in proportion;
step (2), adding the weighed raw materials into a kneader to be fully kneaded for 0.5-2h, and then rotating an extrusion strip machine to be molded;
and (3) drying the prepared strip-shaped molecular sieve at the temperature of 80-140 ℃ for 1-8h, and then roasting at the temperature of 550-650 ℃ for 3-12h.
The invention also provides an application method of the modified Y-type molecular sieve regenerant in regeneration of hydrogen peroxide working solution, wherein the hydrogen peroxide working solution is the working solution in a hydrogen peroxide preparation process by an anthraquinone method, the specific application method is that the regenerant is added into the working solution, and the addition amount of the regenerant is 1-10g/100mL.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the Y-type molecular sieve is modified, so that the prepared modified Y-type molecular sieve regenerant can obviously improve the regeneration effect of the working solution, and has the advantages of high static water balance adsorption capacity, difficult pulverization of the regenerant, stable performance, long service life and high recovery rate.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
Step 1, weighing 85wt% of USY type molecular sieve according to the mass ratio, wherein 5wt% of sesbania powder is used as a binder, and 10wt% of water is used as an auxiliary agent.
And 2, adding all the materials into a kneader, fully kneading for 1h, and then rotating a strip extruder for molding.
And 3, drying the prepared strip-shaped molecular sieve at the temperature of 120 ℃ for 2h, and roasting at the temperature of 550 ℃ for 5h to obtain the regenerant.
Weighing 3g of the regenerant, adding the regenerant into 200ml of hydrogen peroxide working solution, sealing, placing in a water bath constant temperature oscillator, adjusting the temperature of the water bath to 50 ℃, adjusting the oscillation frequency to 150rpm, regenerating for 4 hours, taking out the Erlenmeyer flask after regeneration is finished, cooling to room temperature, and taking the regenerated working solution for quantitative analysis.
Example 2
Step 1, weighing 85wt% of USY type molecular sieve according to the proportion, wherein 5wt% of sesbania powder is used as a binder, and 10wt% of water is used as an auxiliary agent.
And 2, adding all the materials into a kneader, fully kneading for 1h, and then rotating a strip extruder for molding.
And 3, drying the prepared strip-shaped molecular sieve at the temperature of 120 ℃ for 2h, and roasting at the temperature of 600 ℃ for 5h.
The hydrogen peroxide working solution was regenerated using the prepared regenerant according to the method of example 1, and the regenerated working solution was quantitatively analyzed.
Example 3
Step 1, weighing 85wt% of USY type molecular sieve according to the proportion, wherein 5wt% of sesbania powder is used as a binder, and 10wt% of water is used as an auxiliary agent.
And 2, adding all the materials into a kneader, fully kneading for 1h, and then rotating a strip extruder for molding.
And step 3, drying the prepared strip-shaped molecular sieve at the temperature of 120 ℃ for 2h, and roasting at the temperature of 650 ℃ for 5h.
The hydrogen peroxide working solution was regenerated using the prepared regenerant according to the method of example 1, and the regenerated working solution was quantitatively analyzed.
Example 4
Step 1, weighing 85wt% of USY type molecular sieve according to the proportion, wherein 5wt% of sesbania powder is used as a binder, and 10wt% of water is used as an auxiliary agent.
And 2, adding all the materials into a kneader, fully kneading for 1h, and then rotating a strip extruder for molding.
And 3, drying the prepared strip-shaped molecular sieve at the temperature of 120 ℃ for 2h, and roasting at the temperature of 550 ℃ for 4h.
The hydrogen peroxide working solution was regenerated using the prepared regenerant according to the method of example 1, and the regenerated working solution was quantitatively analyzed.
Example 5
The regenerant obtained by regenerating the hydrogen peroxide working fluid in example 1 was recovered, and the regenerated working fluid was subjected to quantitative analysis by regenerating the hydrogen peroxide working fluid with the recovered regenerant according to the procedure in example 1.
Example 6
Step 1, weighing 85wt% of USY type molecular sieve, 5wt% of sesbania powder as a binder, and 10wt% of graphite powder as an auxiliary agent according to the proportion.
And 2, adding all the materials into a kneader, fully kneading for 1h, and then rotating a strip extruder for molding.
And 3, drying the prepared strip-shaped molecular sieve at the temperature of 120 ℃ for 2h, and roasting at the temperature of 600 ℃ for 5h.
The hydrogen peroxide working solution was regenerated using the prepared regenerant according to the method of example 1, and the regenerated working solution was quantitatively analyzed.
Comparative example 1
And (3) sealing 200ml of hydrogen peroxide working solution without adding any regenerant, placing the hydrogen peroxide working solution into a water bath constant temperature oscillator, adjusting the water bath temperature to 50 ℃, adjusting the oscillation frequency to 150rpm, regenerating for 4 hours, taking out the Erlenmeyer flask after regeneration is finished, cooling to room temperature, and taking the regenerated working solution for quantitative analysis.
The working solutions of examples 1 to 6 and comparative example 1 after regeneration were subjected to quantitative analysis, and the results of the detection were recorded as shown in Table 1.
TABLE 1
The experimental results show that the regenerant can meet the regeneration of the working solution for preparing hydrogen peroxide by an anthraquinone process, the regeneration effect is obvious, and the embodiment and the corresponding results show that the percentage content of the regenerant is increased, the regeneration effect can be improved, the regenerant can be repeatedly used, and the stability is high.
The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to help understand the method and the core concept of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.
Claims (2)
1. An application method of a modified Y-type molecular sieve regenerant for regenerating hydrogen peroxide working solution is characterized in that,
the hydrogen peroxide working solution is the working solution in the hydrogen peroxide preparation process by the anthraquinone method, 3g of regenerant is weighed and added into 200ml of hydrogen peroxide working solution, the hydrogen peroxide working solution is sealed and then placed in a water bath constant temperature oscillator, the water bath temperature is adjusted to 50 ℃, the oscillation frequency is 150rpm, and regeneration is carried out for 4 hours;
the regenerant was composed of 85wt% USY type molecular sieve, 5wt% sesbania powder, 10wt% water.
2. The application method of the modified Y-type molecular sieve regenerant in regenerating hydrogen peroxide working solution according to claim 1 is characterized in that the preparation method of the regenerant comprises the following steps:
weighing raw materials in proportion;
adding the weighed raw materials into a kneader to be fully kneaded for 1h, and then rotating an extrusion strip machine to be molded;
and (3) drying the prepared strip-shaped molecular sieve at the temperature of 120 ℃ for 2 hours, and then roasting at the temperature of 600 ℃ for 5 hours.
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| CN101612585A (en) * | 2009-07-29 | 2009-12-30 | 中国石油化工集团公司 | A kind of gasoline reforming catalyst and its production and application |
| CN103157507B (en) * | 2011-12-15 | 2015-05-13 | 中国石油天然气股份有限公司 | Heavy oil catalytic cracking catalyst and preparation method thereof |
| CN103159227B (en) * | 2011-12-15 | 2015-05-13 | 中国石油天然气股份有限公司 | Magnesium modified ultrastable rare earth Y-type molecular sieve and preparation method thereof |
| CN102600890A (en) * | 2012-03-13 | 2012-07-25 | 杭州绿洲能源科技有限公司 | Gas-phase catalyst for regenerating diesel through catalytic cracking of waste oil and preparation method thereof |
| CN104418307B (en) * | 2013-08-22 | 2016-06-22 | 中国石油化工股份有限公司 | A kind of hydrogen dioxide solution production by anthraquinone process multistage hydrogenation process |
| CN103879969B (en) * | 2014-03-12 | 2016-01-13 | 广西新晶科技有限公司 | The anthraquinone preparation method preparing hydrogen peroxide regenerator |
| CN105174229B (en) * | 2015-08-28 | 2017-05-10 | 陕西开达化工有限责任公司 | Composite activated regenerant for hydrogen peroxide working fluid of anthraquinone process and preparation method thereof |
| CN105152137B (en) * | 2015-09-28 | 2018-03-09 | 湘潭大学 | A kind of anthraquinone recycling agent for hydrogen peroxide solution prepared in hydrogen peroxide process and preparation method thereof |
| CN111001401B (en) * | 2019-10-28 | 2022-11-29 | 浙江恒逸石化研究院有限公司 | Method for preparing anthraquinone degradation product regenerant by using waste argil as raw material, anthraquinone degradation product regenerant and application thereof |
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