CN110841698B - Alkyl benzene hydroperoxide catalyst, preparation method and application thereof - Google Patents

Alkyl benzene hydroperoxide catalyst, preparation method and application thereof Download PDF

Info

Publication number
CN110841698B
CN110841698B CN201810952199.6A CN201810952199A CN110841698B CN 110841698 B CN110841698 B CN 110841698B CN 201810952199 A CN201810952199 A CN 201810952199A CN 110841698 B CN110841698 B CN 110841698B
Authority
CN
China
Prior art keywords
molecular sieve
catalyst
alkylbenzene
hydroperoxide
transition metal
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.)
Active
Application number
CN201810952199.6A
Other languages
Chinese (zh)
Other versions
CN110841698A (en
Inventor
王闻年
魏一伦
高焕新
谭永生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201810952199.6A priority Critical patent/CN110841698B/en
Publication of CN110841698A publication Critical patent/CN110841698A/en
Application granted granted Critical
Publication of CN110841698B publication Critical patent/CN110841698B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/143—X-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
    • B01J29/24—Iron group metals or copper
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention relates to an alkylbenzene hydroperoxide catalyst, a preparation method and application thereof. The catalyst comprises 85-96 wt% of a molecular sieve and 4-15 wt% of a transition metal oxide, relative to the total weight of the molecular sieve and the transition metal oxide; the molecular sieve is expressed by M. NaA; wherein M is selected from the group consisting of K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+、Ba2+At least one of the group consisting of; a is at least one selected from the group consisting of X zeolite, Y zeolite, zeolite Beta and mordenite; in the molecular sieve, the capacity χ of M is at least above 60%.

Description

Alkyl benzene hydroperoxide catalyst, preparation method and application thereof
Technical Field
The invention relates to an alkylbenzene hydroperoxide catalyst, a preparation method and application thereof.
Background
Alkylbenzene hydroperoxides, including cumene hydroperoxide, diisopropylbenzene hydroperoxide, sec-butylbenzene hydroperoxide and the like, are produced by the oxidation of cumene, diisopropylbenzene, sec-butylbenzene and the like with oxygen, and generally require a basic catalyst. For example, documents BP727498 and US3953521 disclose a process for the preparation of DHP by continuous oxidation of diisopropylbenzene with alkaline extraction. In this process, it is required to maintain the pH of the oxidation system at 8 to 11. US4237319 discloses that the oxidation of m-diisopropylbenzene to m-diisopropylbenzene hydroperoxide is carried out under basic conditions. US6350921 reports a process for the continuous preparation of diisopropylbenzene hydroperoxide using 4% and 8% NaOH solution as catalyst. CN102151584A uses an alkaline polyimidazole, polyquaternary ammonium or polyquaternary phosphorus ionic liquid as a catalyst to perform catalytic oxidation on alkyl aromatic hydrocarbon. And CN103242211A is the catalytic oxidation of the mixture of cumene and sec-butylbenzene by using ammonia water as catalyst promoter.
In the alkaline catalyst adopted in the prior art, alkaline liquid containing a large amount of water, such as sodium hydroxide solution, ammonia water and the like, not only the problem of oil-water separation exists, but also a large amount of alkaline wastewater is generated, and the problem of recycling of alkaline liquor also exists. On the other hand, the basic ionic liquid has a problem in cost and a problem in separation.
Disclosure of Invention
The present inventors have assiduously studied on the basis of the prior art and found that at least one of the aforementioned problems can be solved by using a molecular sieve containing alkali metal ions other than sodium ions and alkaline earth metal ions as a carrier and supporting a transition metal oxide as a catalyst and controlling the M metal ion capacity of the molecular sieve, and thus completed the present invention.
Specifically, the invention relates to an alkylbenzene hydroperoxide catalyst, which comprises 85-96 wt% of a molecular sieve and 4-15 wt% of a transition metal oxide, wherein the weight of the molecular sieve and the transition metal oxide is relative to the total weight of the molecular sieve and the transition metal oxide;
the molecular sieve is expressed by M. NaA; wherein M is selected from the group consisting of K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+、Ba2+At least one of the group consisting of; a is at least one selected from the group consisting of X zeolite, Y zeolite, zeolite Beta and mordenite;
in the molecular sieve, the capacity χ of M is at least above 60%;
wherein,
Figure BDA0001771804750000021
according to one aspect of the invention, the catalyst comprises 88 to 94 wt% of the molecular sieve and 6 to 12 wt% of the transition metal oxide, preferably 90 to 92 wt% of the molecular sieve and 8 to 10 wt% of the transition metal oxide, relative to the total weight of the molecular sieve and the transition metal oxide.
According to an aspect of the present invention, the transition metal is at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, preferably at least one selected from the group consisting of Ti, Co, Ni and Cu.
According to one aspect of the invention, the molecular sieve has a capacity χ of M of at least above 60%, preferably at least above 70%, more preferably at least above 80%, more preferably at least above 90%, most preferably 100%. For example, the capacity χ of M may be 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%. .
The invention also relates to a preparation method of the alkylbenzene hydroperoxide catalyst. The method comprises the following steps:
a) contacting a sodium type molecular sieve NaA with a salt solution containing metal M to obtain a molecular sieve M. NaA;
b) contacting a molecular sieve M & NaA with a salt solution containing a transition metal to obtain the alkylbenzene hydroperoxide catalyst;
wherein M is selected from the group consisting of K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+、Ba2+At least one of the group consisting of; a is at least one selected from the group consisting of X zeolite, Y zeolite, zeolite Beta and mordenite;
in the molecular sieve, the capacity χ of M is at least above 60%;
wherein,
Figure BDA0001771804750000022
according to one aspect of the invention, in the step a), the sodium type molecular sieve NaA is contacted with a salt solution containing metal M for ion exchange, the solid-to-liquid ratio is 1: 1-1: 50, the contact temperature is 0-180 ℃, and the contact time is 0.5-12 hours. Optionally, filtering, washing, drying and roasting to obtain the molecular sieve M. NaA after ion exchange. Wherein the drying and firing may be performed in any manner conventionally known in the art. Specifically, for example, the drying temperature is 40 to 250 ℃, preferably 60 to 150 ℃, and the drying time is 8 to 30 hours, preferably 10 to 20 hours. The drying may be carried out under normal pressure or under reduced pressure. For example, the calcination temperature is generally 300 to 800 ℃, preferably 400 to 650 ℃, and the calcination time is generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen. In order to make the molecular sieve M.Na+In A, relative to M and Na+At least above 60% by weight, this step may be repeated a number of times, for example 2-3 times.
According to one aspect of the invention, the molecular sieve M · NaA has a capacity χ of M of at least above 60%, preferably at least above 70%, more preferably at least above 80%, more preferably at least above 90%, most preferably 100%. For example, the capacity χ of M may be 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%.
According to one aspect of the invention, the molecular sieve M. NaA after ion exchange in the step b) is contacted with a salt solution containing transition metal at the temperature of 0-90 ℃ for 0.5-12 hours. Optionally, drying and roasting to obtain the catalyst. Wherein the drying and firing may be performed in any manner conventionally known in the art. Specifically, for example, the drying temperature is 40 to 250 ℃, preferably 60 to 150 ℃, and the drying time is 8 to 30 hours, preferably 10 to 20 hours. The drying may be carried out under normal pressure or under reduced pressure. For example, the calcination temperature is generally 300 to 800 ℃, preferably 400 to 650 ℃, and the calcination time is generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as air or oxygen.
According to an aspect of the present invention, the transition metal is at least one selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, preferably at least one selected from the group consisting of Ti, Co, Ni and Cu.
According to one aspect of the invention, the alkylbenzene hydroperoxide catalyst may be in any physical form, such as a powder, granules or a moulded article, such as a tablet, a bar, a clover; preferably in the form of tablet, strip, or clover. These physical forms can be obtained in any manner conventionally known in the art and are not particularly limited.
The invention also relates to a process for producing alkylbenzene hydroperoxide. The process comprises the step of contacting alkylbenzene and an oxygen-containing gas with the alkylbenzene hydroperoxide catalyst or an alkylbenzene hydroperoxide catalyst prepared according to the process for preparing the alkylbenzene hydroperoxide catalyst under effective reaction conditions to synthesize alkylbenzene hydroperoxide.
According to one aspect of the invention, the effective reaction conditions include: the reaction temperature is 80-120 ℃, the reaction pressure is 0.1-0.4 MPa, and the dosage of the oxygen-containing gas is 0.01-2.00 ml of oxygen/(min. g of alkylbenzene) calculated by oxygen; preferably, the reaction temperature is 90-110 ℃, the reaction pressure is 0.1-0.3 MPa, and the dosage of the oxygen-containing gas is 0.04-1.80 mL of oxygen/(min. g of alkylbenzene) calculated by the oxygen.
According to one aspect of the invention, the catalyst is added in an amount of 0.001 to 1 times the weight of the alkylbenzene.
According to one aspect of the invention, the alkylbenzene comprises cumene, diisopropylbenzene, triisopropylbenzene, sec-butylbenzene or methyl isopropylbenzene.
In accordance with one aspect of the invention, to accelerate the reaction, an initiator may be added. The initiator may be diisopropylbenzene monohydroperoxide, diisopropylbenzene dihydroperoxide, dicumyl peroxide, azobisisobutyronitrile and cumene peroxide. The amount of the initiator is generally 1-15% of the weight of the alkylbenzene raw material.
The invention has the technical effects that:
according to the invention, the alkylbenzene hydroperoxide catalyst is in a solid form, such as a strip shape, a spherical shape, a sheet shape and other molding shapes, is convenient to separate after reaction and recycle, and reduces the production cost.
According to the invention, the oxidation speed of alkylbenzene and the selectivity of alkylbenzene hydroperoxide products are greatly improved, compared with the method using the traditional sodium hydroxide solution catalyst, the oxidation speed of alkylbenzene can be improved by 50-300%, and the selectivity of alkylbenzene hydroperoxide can be improved by 3-8%.
According to the present invention, since a liquid-based alkaline catalyst is not used, no alkaline liquid waste water is produced; meanwhile, an organic base catalyst is not used, so that the method is low in cost, environment-friendly and wide in industrial prospect.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the appended claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
When the specification concludes with claims with the heading "known to those skilled in the art", "prior art", or the like, to derive materials, substances, methods, procedures, devices, or components, etc., it is intended that the subject matter derived from the heading encompass those conventionally used in the art at the time of filing this application, but also include those that are not currently in use, but would become known in the art to be suitable for a similar purpose.
It should be expressly understood that two or more of the aspects (or embodiments) disclosed in the context of this specification can be combined with each other as desired, and that such combined aspects (e.g., methods or systems) are incorporated in and constitute a part of this original disclosure, while remaining within the scope of the present invention.
Unless otherwise expressly indicated, all percentages, parts, ratios, etc. mentioned in this specification are by weight unless otherwise not in accordance with the conventional knowledge of those skilled in the art.
The invention is further illustrated by the following specific examples. It should be noted that, in the following examples and comparative examples, the ion capacity χ in the molecular sieve after ion exchange was determined according to the formula (1):
wherein,
Figure BDA0001771804750000051
in the formula, the gram-atom equivalent of metal in the molecular sieve phase can be determined by an X-ray fluorescence (XRF) method. XRF test conditions were: a Rigaku ZSX 100e type XRF instrument is adopted, a rhodium target is used as an excitation source, the maximum power is 3600W, the tube voltage is 60KV, and the tube current is 120 mA.
The content of alkylbenzene hydroperoxide was calculated as alkylbenzene hydroperoxide (RHP) and titrated with a standardized concentration of sodium thiosulfate solution. The RHP concentration was determined according to equation (2):
Figure BDA0001771804750000052
wherein M (RHP) is the molecular weight of alkylbenzene hydroperoxide, V (Na)2S2O3) Volume of sodium thiosulfate solution used, c (Na)2S2O3) Is the molar concentration of the sodium thiosulfate solution, and m is the mass of the oxidizing solution used for titration.
The selectivity of alkylbenzene hydroperoxide was calculated as the total amount of alkylbenzene monohydroperoxide (RHP) and alkylbenzene Dihydroperoxide (DHP) minus the amount of peroxide added to the initiator divided by the conversion of alkylbenzene.
[ example 1 ] A method for producing a polycarbonate
Preparation of the catalyst: 10.0g of NaX molecular sieve was added to 50g of an aqueous solution containing 10g of potassium nitrate, and the reaction was stirred at 90 ℃ for 2 hours. Filtering, washing with deionized water, drying at 110 deg.C, and calcining at 200 deg.C for 4 hr to obtain K ion exchanged X-type molecular sieve+NaX. Taking the above K+5.0g of NaX molecular sieve was added to an aqueous solution containing nickel nitrate in an amount of 8% by weight based on the amount of nickel oxide supported, and the reaction was stirred at 25 ℃ for 12 hours. Drying at 110 deg.C for 12 hr, and calcining at 400 deg.C for 4 hr to obtain the catalyst. The catalyst comprises the following components: 8 wt% NiO/92 wt% K+·NaX。K+In NaX molecular sieves, K+The capacity of (2) was 69%.
Formation of alkylbenzene hydroperoxide: 100.0g of diisopropylbenzene is taken, 10.0g of diisopropylbenzene hydroperoxide is added as an initiator, and the mixture is stirred until the mixture is uniformly mixed. Then 1.0g of the catalyst is added, 0.84 ml of oxygen/(min. g of diisopropylbenzene) is introduced, and the reaction is carried out for 12 hours at the temperature of 90 ℃, thus obtaining the diisopropylbenzene hydroperoxide mixed solution. After the reaction is finished, filtering, washing the catalyst with 10.0g of diisopropylbenzene for three times, mixing the washing liquid with the oxidation liquid, and washing and drying the catalyst by acetone to recycle. The concentration of peroxide in the final oxidation liquid reaches 72.5%, and the selectivity of diisopropylbenzene hydroperoxide reaches 65.1%.
[ example 2 ]
Preparation of the catalyst: 10.0g of NaY molecular sieve was added to 100g of an aqueous solution containing 15g of magnesium nitrate in a closed reaction vessel, and the mixture was stirred at 120 ℃ for 4 hours. Filtering, washing with deionized water, drying at 110 deg.C, and calcining at 200 deg.C for 4 hr to obtain Mg ion exchanged Y-type componentSub-sieve with Mg2+NaY. Taking the above Mg2+5.0g of NaY molecular sieve was added to an aqueous solution containing nickel nitrate in an amount of 8% by weight based on the amount of nickel oxide supported, and the reaction was stirred at 25 ℃ for 12 hours. Drying at 110 deg.C for 12 hr, and calcining at 400 deg.C for 4 hr to obtain the catalyst. The catalyst comprises the following components: 8 wt% NiO/92 wt% Mg2+·NaY。Mg2+In NaY molecular sieves, Mg2+The capacity of (2) was 62%.
Formation of alkylbenzene hydroperoxide: 100.0g of cumene was taken, 10.0g of cumene hydroperoxide was added as an initiator, and stirred until mixed uniformly. Then 1.0g of the catalyst is added, 0.84 ml of oxygen/(min. g of cumene) is introduced, and the mixture reacts for 12 hours at the temperature of 90 ℃ to obtain the cumene hydroperoxide mixed solution. After the reaction, filtering, washing the catalyst with 10.0g cumene for three times, mixing the washing liquid with the above oxidation liquid, washing the catalyst with acetone, and drying for recycling. The peroxide concentration in the final oxidation liquid reaches 74.2 percent, and the selectivity of cumene hydroperoxide reaches 71.6 percent.
[ example 3 ]
Preparation of the catalyst: 10.0g of Nabeta molecular sieve was added to 200g of an aqueous solution containing 20g of calcium chloride, and the reaction was stirred at 90 ℃ for 4 hours. Filtering, washing with deionized water, drying at 110 deg.C, and calcining at 200 deg.C for 4 hr to obtain Ca ion exchanged Beta molecular sieve2+Nabeta. Taking the above Ca2+5.0g of Nabeta molecular sieve was added to an aqueous solution containing copper nitrate in an amount of 10% by weight based on the amount of copper oxide supported, and the reaction was stirred at 25 ℃ for 12 hours. Drying at 110 deg.C for 12 hr, and calcining at 400 deg.C for 4 hr to obtain the catalyst. The catalyst comprises the following components: 10 wt.% CuO/90 wt.% Ca2+·NaBeta。Ca2+In Nabeta molecular sieves, Ca2+The capacity of (2) was 86%.
Formation of alkylbenzene hydroperoxide: 100.0g of sec-butylbenzene was taken, 10.0g of azobisisobutyronitrile was added as an initiator, and stirred until mixed uniformly. Then 0.5g of the catalyst is added, 0.84 ml of oxygen/(min. g of sec-butylbenzene) is introduced, and the reaction is carried out for 15 hours at 90 ℃ to obtain the sec-butylbenzene hydroperoxide mixed solution. After the reaction is finished, filtering, washing the catalyst for three times by using 10.0g of sec-butylbenzene, mixing the washing liquid with the oxidation liquid, and washing and drying the catalyst by using acetone so as to recycle the catalyst. The concentration of the peroxide in the final oxidation solution reaches 71.3 percent, and the selectivity of the sec-butylbenzene hydroperoxide reaches 60.9 percent.
[ example 4 ]
Preparation of the catalyst: 10.0g of sodium mordenite was added to 50g of an aqueous solution containing 5g of cesium acetate, and the reaction was stirred at 90 ℃ for 2 hours. Filtering, washing with deionized water, drying at 110 deg.C, and calcining at 200 deg.C for 4 hr to obtain cesium ion exchanged mordenite with Cs2+NaMor. Taking the above Cs2+5.0g of NaMor molecular sieve was added to an aqueous solution containing copper nitrate in an amount of 10% by weight based on the amount of copper oxide supported, and the reaction was stirred at 25 ℃ for 12 hours. Drying at 110 deg.C for 12 hr, and calcining at 400 deg.C for 4 hr to obtain the catalyst. The catalyst comprises the following components: 10 wt% CuO/90 wt% Cs2+·NaMor。Cs2 +In NaMor molecular sieves, Cs2+The capacity of (2) was 61%.
Formation of alkylbenzene hydroperoxide: 100.0g of cumene was taken, 10.0g of azobisisobutyronitrile was added as an initiator, and stirred until mixed uniformly. Then 0.5g of the catalyst is added, 0.84 ml of oxygen/(min. g of cumene) is introduced, and the mixture reacts for 12 hours at the temperature of 90 ℃ to obtain the cumene hydroperoxide mixed solution. After the reaction, filtering, washing the catalyst with 10.0g cumene for three times, mixing the washing liquid with the above oxidation liquid, washing the catalyst with acetone, and drying for recycling. The peroxide concentration in the final oxidation liquid reaches 69.8%, and the selectivity of cumene hydroperoxide reaches 82.5%.
[ example 5 ]
Preparation of the catalyst: 10.0g of NaY molecular sieve was added to 50g of an aqueous solution containing 10g of potassium nitrate and 5g of magnesium nitrate, and the reaction was stirred at 90 ℃ for 2 hours. Filtering, washing with deionized water, drying at 110 deg.C, and calcining at 200 deg.C for 4 hr to obtain Y molecular sieve with K ion and Mg ion exchanged by K+Mg2+NaY. Taking the above K+Mg2+5.0g of NaY molecular sieve,adding the mixture into an aqueous solution containing copper nitrate and nickel acetate, wherein the content of the copper nitrate is 4 weight percent of the loading amount of copper oxide, and the content of the nickel acetate is 8 weight percent of the loading amount of nickel oxide, and stirring and reacting for 12 hours at 25 ℃. Drying at 110 deg.C for 12 hr, and calcining at 400 deg.C for 4 hr to obtain the catalyst. The catalyst comprises the following components: 4 wt% CuO-8 wt% NiO/88 wt% K+Mg2+·NaY。K+Mg2+In NaY molecular sieves, K+56% of Mg2+The capacity of (2) is 32%.
Production of alkylbenzene hydroperoxide: 100.0g of diisopropylbenzene is taken, 10.0g of azobisisobutyronitrile is added as an initiator, and the mixture is stirred until the mixture is uniformly mixed. Then 0.5g of the catalyst is added, 0.84 ml of oxygen/(min. g of diisopropylbenzene) is introduced, and the reaction is carried out for 16 hours at the temperature of 90 ℃, thus obtaining the diisopropylbenzene hydroperoxide mixed solution. After the reaction is finished, filtering, washing the catalyst with 10.0g of diisopropylbenzene for three times, mixing the washing liquid with the oxidation liquid, and washing and drying the catalyst by acetone to recycle. The peroxide concentration in the final oxidation liquid reaches 69.3%, and the selectivity of cumene hydroperoxide reaches 74.2%.
[ example 6 ]
Preparation of the catalyst: 10.0g of NaY molecular sieve was added to 50g of an aqueous solution containing 7.5g of potassium chloride and 5.0g of calcium chloride, and the reaction was stirred at 90 ℃ for 2 hours. Filtering, washing with deionized water, drying at 110 deg.C, and calcining at 200 deg.C for 4 hr to obtain Y molecular sieve with K ion and Ca ion exchanged+Ca2+NaY. Taking the above K+Ca2+5.0g of NaY molecular sieve was added to an aqueous solution containing cobalt chloride and titanium chloride, wherein the content of cobalt chloride was 2% by weight based on the supported amount of cobalt oxide and the content of titanium chloride was 8% by weight based on the supported amount of titanium oxide, and the reaction was stirred at 25 ℃ for 12 hours. Drying at 110 deg.C for 12 hr, and calcining at 400 deg.C for 4 hr to obtain the catalyst. The catalyst comprises the following components: 2 wt% CoO-8 wt% TiO290% by weight of K+Ca2+·NaY。K+Ca2 +In NaY molecular sieves, K+Capacity of (2) 56%, Ca2+The capacity of (2) is 24%.
Formation of alkylbenzene hydroperoxide: 100.0g of diisopropylbenzene is taken, 10.0g of diisopropylbenzene hydroperoxide is added as an initiator, and the mixture is stirred until the mixture is uniformly mixed. Then 0.1g of the catalyst is added, 0.84 ml of oxygen/(min. g of diisopropylbenzene) is introduced, and the reaction is carried out for 10 hours at the temperature of 90 ℃, thus obtaining the diisopropylbenzene hydroperoxide mixed solution. After the reaction is finished, filtering, washing the catalyst with 10.0g of diisopropylbenzene for three times, mixing the washing liquid with the oxidation liquid, and washing and drying the catalyst by acetone to recycle. The concentration of peroxide in the final oxidation solution reaches 70.0%, and the selectivity of diisopropylbenzene hydroperoxide reaches 79.5%.
[ example 7 ]
Preparation of the catalyst: 10.0g of NaBeta molecular sieve was added to 100g of an aqueous solution containing 10g of potassium chloride and 5g of calcium chloride, and the reaction was stirred at 90 ℃ for 2 hours. Filtering, washing with deionized water, drying at 110 deg.C, and calcining at 200 deg.C for 4 hr to obtain Y molecular sieve with K ion and Ca ion exchanged+Ca2+Nabeta. Taking the above K+Ca2+5.0g of Nabeta molecular sieve was added to an aqueous solution containing cobalt chloride and nickel nitrate, wherein the content of cobalt chloride was 4% by weight based on the amount of cobalt oxide supported and the content of nickel nitrate was 6% by weight based on the amount of nickel oxide supported, and the reaction was stirred at 25 ℃ for 12 hours. Drying at 110 deg.C for 12 hr, and calcining at 400 deg.C for 4 hr to obtain the catalyst. The catalyst comprises the following components: 4 wt% CoO-6 wt% NiO/90 wt% K+Ca2+·NaBeta。K+Ca2+In Nabeta molecular sieves, K+80% of Ca2+The capacity of (2) is 15%.
Formation of alkylbenzene hydroperoxide: 100.0g of diisopropylbenzene is taken, 10.0g of diisopropylbenzene hydroperoxide is added as an initiator, and the mixture is stirred until the mixture is uniformly mixed. Then 0.1g of the catalyst is added, 1.68 ml of oxygen/(min. g of diisopropylbenzene) is introduced, and the reaction is carried out for 8 hours at the temperature of 90 ℃, thus obtaining the diisopropylbenzene hydroperoxide mixed solution. After the reaction is finished, filtering, washing the catalyst with 10.0g of diisopropylbenzene for three times, mixing the washing liquid with the oxidation liquid, and washing and drying the catalyst by acetone to recycle. The concentration of peroxide in the final oxidation liquid reaches 65.9 percent, and the selectivity of the diisopropylbenzene hydroperoxide reaches 81.0 percent.
[ example 8 ]
Preparation of the catalyst: 10.0g of NaX molecular sieve was added to 100g of an aqueous solution containing 15g of magnesium nitrate and 5g of calcium chloride, and the reaction was stirred at 90 ℃ for 2 hours. Filtering, washing with deionized water, drying at 110 deg.C, and calcining at 200 deg.C for 4 hr to obtain X molecular sieve exchanged with Mg ions and Ca ions2+Ca2+NaX. Taking the above Mg2+Ca2+5.0g of NaX molecular sieve was added to an aqueous solution containing cobalt chloride and nickel nitrate, wherein the content of cobalt chloride was 4% by weight based on the amount of cobalt oxide supported and the content of nickel nitrate was 6% by weight based on the amount of nickel oxide supported, and the reaction was stirred at 25 ℃ for 12 hours. Drying at 110 deg.C for 12 hr, and calcining at 400 deg.C for 4 hr to obtain the catalyst. The catalyst comprises the following components: 4 wt% CoO-6 wt% NiO/Mg2+Ca2+·NaX。Mg2+Ca2+In NaX molecular sieves, Mg2+Capacity of (2) 56%, Ca2+The capacity of (2) is%.
Formation of alkylbenzene hydroperoxide: 100.0g of diisopropylbenzene is taken, 10.0g of diisopropylbenzene hydroperoxide is added as an initiator, and the mixture is stirred until the mixture is uniformly mixed. Then 0.1g of the catalyst is added, 1.68 ml of oxygen/(min. g of diisopropylbenzene) is introduced, and the reaction is carried out for 10 hours at the temperature of 90 ℃, thus obtaining the diisopropylbenzene hydroperoxide mixed solution. After the reaction is finished, filtering, washing the catalyst with 10.0g of diisopropylbenzene for three times, mixing the washing liquid with the oxidation liquid, and washing and drying the catalyst by acetone to recycle. The concentration of peroxide in the final oxidation liquid reaches 72.0%, and the selectivity of the diisopropylbenzene hydroperoxide reaches 87.6%.
Comparative example 1
The catalyst of the present invention is not used.
100.0g of diisopropylbenzene is taken, 10.0g of diisopropylbenzene hydroperoxide is added as an initiator, and the mixture is stirred until the mixture is uniformly mixed. Introducing 0.84 ml of oxygen/(min. g of diisopropylbenzene), and reacting for 36 hours at 90 ℃ to obtain a diisopropylbenzene oxide mixed solution. After the reaction was completed, the peroxide content was analyzed, and the results are shown in Table 2. The peroxide concentration in the final oxidation solution was 54.8% and the selectivity to diisopropylbenzene hydroperoxide was 48.0%. The reaction takes long time and the product selectivity is low.
Comparative example 2
A base catalyst of the prior art is used.
100.0g of diisopropylbenzene is taken, 10.0g of diisopropylbenzene hydroperoxide is added as an initiator, and the mixture is stirred until the mixture is uniformly mixed. Then, 10.0g of 1 wt% aqueous sodium hydroxide solution was added thereto, and 1.68 ml of oxygen/(min. g of diisopropylbenzene) was introduced thereinto to react at 90 ℃ for 48 hours, thereby obtaining a mixture of a diisopropylbenzene hydroperoxide mixture and an aqueous sodium hydroxide solution, which was allowed to stand for 24 hours and then separated. The resulting diisopropylbenzene hydroperoxide content is shown in Table 2. The peroxide concentration in the final oxidation solution was 65.0% and the selectivity to diisopropylbenzene hydroperoxide was 54.2%. Not only the reaction takes long time, but also the product selectivity is not high.
Comparative example 3
The same as [ example 1 ] except that the ion capacity was 30%.
Comparative example 4
Similarly [ example 5 ], except that the ion capacity of potassium ions was 30% and the exchange capacity of magnesium ions was 20%.
TABLE 1
Figure BDA0001771804750000111
TABLE 2
Figure BDA0001771804750000112

Claims (14)

1. Use of a catalyst comprising 85 to 96 wt% of a molecular sieve and 4 to 15 wt% of a transition metal oxide, relative to the total weight of the molecular sieve and the transition metal oxide, for the preparation of an alkylbenzene hydroperoxide;
the molecular sieve is represented by m.naa; wherein M is selected from the group consisting of K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+、Ba2+At least one of the group consisting of; a is at least one selected from the group consisting of X zeolite, Y zeolite, zeolite Beta and mordenite;
in the molecular sieve, the capacity of M is over 60 percent;
Figure DEST_PATH_IMAGE001
2. use according to claim 1, characterized in that the catalyst comprises 88 to 94% by weight of molecular sieve and 6 to 12% by weight of transition metal oxide, relative to the total weight of molecular sieve and transition metal oxide.
3. Use according to claim 2, characterized in that the catalyst comprises 90 to 92 wt% of molecular sieve and 8 to 10 wt% of transition metal oxide, relative to the total weight of molecular sieve and transition metal oxide.
4. Use according to claim 1, wherein the transition metal is selected from at least one of the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.
5. Use according to claim 4, wherein the transition metal is selected from at least one of the group consisting of Ti, Co, Ni and Cu.
6. Use according to claim 1, characterized in that in the molecular sieve, the capacity of M is above 70%.
7. Use according to claim 6, characterized in that in the molecular sieve, the capacity of M is above 80%.
8. Use according to claim 7, characterized in that in the molecular sieve, the capacity of M is above 90%.
9. Use according to claim 1, characterized in that the preparation process of the catalyst comprises the steps of:
a) contacting sodium type molecular sieve NaA with a salt solution containing metal M to obtain a molecular sieve M.NaA;
b) contacting a molecular sieve m.naa with a salt solution containing a transition metal to obtain the alkylbenzene hydroperoxide catalyst;
wherein M is selected from the group consisting of K+、Rb+、Cs+、Mg2+、Ca2+、Sr2+、Ba2+At least one of the group consisting of; a is at least one selected from the group consisting of X zeolite, Y zeolite, zeolite Beta and mordenite;
in the molecular sieve, the capacity of M is over 60 percent;
Figure 221593DEST_PATH_IMAGE001
10. a process for producing alkylbenzene hydroperoxide comprising the step of contacting alkylbenzene and an oxygen-containing gas with the catalyst of any one of claims 1 to 9 under effective reaction conditions to synthesize alkylbenzene hydroperoxide.
11. The process for the production of alkylbenzene hydroperoxides as claimed in claim 10, wherein said effective reaction conditions include: the reaction temperature is 80-120 ℃, the reaction pressure is 0.1-0.4 MPa, and the dosage of the oxygen-containing gas is 0.01-2.00 ml of oxygen/(min. g of alkylbenzene) calculated by oxygen.
12. The process for the production of alkylbenzene hydroperoxide according to claim 11, wherein the effective reaction conditions comprise: the reaction temperature is 90-110 ℃, the reaction pressure is 0.1-0.3 MPa, and the dosage of the oxygen-containing gas is 0.04-1.80 ml of oxygen/(min. g of alkylbenzene) calculated by the oxygen.
13. The process for producing alkylbenzene hydroperoxide according to claim 10, wherein the catalyst is added in an amount of 0.001-1 times by weight based on the weight of alkylbenzene.
14. The process for producing alkylbenzene hydroperoxide according to claim 10, wherein the alkylbenzene comprises cumene, diisopropylbenzene, triisopropylbenzene, sec-butylbenzene or methylisopropylbenzene.
CN201810952199.6A 2018-08-21 2018-08-21 Alkyl benzene hydroperoxide catalyst, preparation method and application thereof Active CN110841698B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810952199.6A CN110841698B (en) 2018-08-21 2018-08-21 Alkyl benzene hydroperoxide catalyst, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810952199.6A CN110841698B (en) 2018-08-21 2018-08-21 Alkyl benzene hydroperoxide catalyst, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110841698A CN110841698A (en) 2020-02-28
CN110841698B true CN110841698B (en) 2022-07-08

Family

ID=69595702

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810952199.6A Active CN110841698B (en) 2018-08-21 2018-08-21 Alkyl benzene hydroperoxide catalyst, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110841698B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4152293A (en) * 1977-04-05 1979-05-01 The Goodyear Tire & Rubber Company Redox catalyst oxidant, catalyst and polymerization therewith
CN101235007A (en) * 2007-01-29 2008-08-06 湖南大学 Method for preparing isopropyl benzene hydrogen peroxide by catalytically oxidizing isopropyl benzene
CN101346362A (en) * 2005-12-30 2009-01-14 科学与工业研究委员会 Molecular oxygen catalysis epoxidation vinyl benzene used for exchanging zeolite with metallic ion
CN102941116A (en) * 2012-11-13 2013-02-27 中国石油化工股份有限公司 Cumene hydroperoxide catalyst prepared by cumene oxidizing reaction and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4152293A (en) * 1977-04-05 1979-05-01 The Goodyear Tire & Rubber Company Redox catalyst oxidant, catalyst and polymerization therewith
CN101346362A (en) * 2005-12-30 2009-01-14 科学与工业研究委员会 Molecular oxygen catalysis epoxidation vinyl benzene used for exchanging zeolite with metallic ion
CN101235007A (en) * 2007-01-29 2008-08-06 湖南大学 Method for preparing isopropyl benzene hydrogen peroxide by catalytically oxidizing isopropyl benzene
CN102941116A (en) * 2012-11-13 2013-02-27 中国石油化工股份有限公司 Cumene hydroperoxide catalyst prepared by cumene oxidizing reaction and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Co and Mn impregnated MCM-41: their applications to vapour phase oxidation of isopropylbenzene";S. Vetrivel et al.;《JOURNAL OF MOLECULAR CATALYSIS A:CHEMICAL》;20041209(第227期);第269-278页 *
"改性HMS分子筛在多相催化反应中的应用";张美英等;《石油学报(石油加工)》;20050830;第21卷(第4期);第22-30页 *
"碱土金属氧化物催化氧化异丙苯反应研究";薛常海等;《石油学报(石油加工)》;20020630;第18卷(第3期);第30-35页 *

Also Published As

Publication number Publication date
CN110841698A (en) 2020-02-28

Similar Documents

Publication Publication Date Title
CN101815578B (en) Method of preparing multicomponent bismuth molybdate catalysts comprising four metal components and method of preparing 1,3-butadiene using the catalysts
US20130165729A1 (en) Zinc and/or manganese aluminate catalyst useful for alkane dehdyrogenation
KR101514848B1 (en) Catalyst for synthesizing acrylonitrile and process for producing acrylonitrile
CN104718023A (en) Catalyst composition for the dehydrogenation of alkanes
CN107771101B (en) Preparation method of ferrite metal oxide catalyst
CN104549349B (en) MAL and the catalyst of methacrylic acid
US20170073284A1 (en) Improved catalyst for dehydrogenating hydrocarbons
CN110841698B (en) Alkyl benzene hydroperoxide catalyst, preparation method and application thereof
CN110845382B (en) Process for preparing alkylbenzene hydroperoxide
CN104549353B (en) MAL and the catalyst of methacrylic acid and its preparation method
US4386226A (en) Process for the ortho-alkylation of phenols
EP3272417A1 (en) Catalyst for oxidative dehydrogenation reaction, and preparation method therefor
CN110975884A (en) Preparation method of transition metal-containing catalyst for preparing benzaldehyde by selectively oxidizing toluene
FR3003773A1 (en) CATALYST FOR SYNTHESIS OF METHYL MERCAPTAN AND PROCESS FOR PRODUCTION OF METHYL MERCAPTAN FROM SYNTHESIS GAS AND HYDROGEN SULFIDE
CN104284721B (en) Oxidation catalyst for producing butadiene and preparation method thereof
CN105271126A (en) Iodate preparation method
US20190031527A1 (en) Process For The Manufacture Of Lithium Metal Oxide Cathode Materials
CN100496728C (en) Catalyst for preparing cyclohexene by selective benzene hydrogenation, its preparing method and use
PL87738B1 (en) Synthesis of maleic anhydride[us3904653a]
CN101723858B (en) Method for preparing benzenesulfonic acid
US8603939B2 (en) Amide compound production catalyst, and process for production of amide compound
CN111655369A (en) Method for preparing metal complex catalyst and metal complex catalyst prepared thereby
CN112823883B (en) Alpha, alpha-dimethyl benzyl alcohol hydrogenolysis catalyst and preparation method and application thereof
CN108314609A (en) A kind of synthetic method of butylated hydroxy anisole
CN106423254B (en) By the catalyst of acetic acid and benzene synthesizing ethyl benzene

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant