CN110841698A - Alkyl benzene hydroperoxide catalyst, preparation method and application thereof - Google Patents
Alkyl benzene hydroperoxide catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN110841698A CN110841698A CN201810952199.6A CN201810952199A CN110841698A CN 110841698 A CN110841698 A CN 110841698A CN 201810952199 A CN201810952199 A CN 201810952199A CN 110841698 A CN110841698 A CN 110841698A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyst
- alkylbenzene
- hydroperoxide
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 150000004996 alkyl benzenes Chemical class 0.000 title claims description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 70
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 69
- -1 alkylbenzene hydroperoxide Chemical class 0.000 claims abstract description 41
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 27
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 22
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010457 zeolite Substances 0.000 claims abstract description 15
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 14
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 47
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 239000001301 oxygen Substances 0.000 claims description 29
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 claims description 23
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- LGXAANYJEHLUEM-UHFFFAOYSA-N 1,2,3-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1C(C)C LGXAANYJEHLUEM-UHFFFAOYSA-N 0.000 claims description 2
- WWRCMNKATXZARA-UHFFFAOYSA-N 1-Isopropyl-2-methylbenzene Chemical compound CC(C)C1=CC=CC=C1C WWRCMNKATXZARA-UHFFFAOYSA-N 0.000 claims description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N p-methylisopropylbenzene Natural products CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 description 34
- 238000005406 washing Methods 0.000 description 33
- 230000003647 oxidation Effects 0.000 description 26
- 238000007254 oxidation reaction Methods 0.000 description 26
- 239000007788 liquid Substances 0.000 description 24
- 238000001354 calcination Methods 0.000 description 22
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- 238000001914 filtration Methods 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000003999 initiator Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 150000002978 peroxides Chemical class 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
- KHADDDTZDWSVIZ-UHFFFAOYSA-N butan-2-ylbenzene;hydrogen peroxide Chemical compound OO.CCC(C)C1=CC=CC=C1 KHADDDTZDWSVIZ-UHFFFAOYSA-N 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 238000004876 x-ray fluorescence Methods 0.000 description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 241000219793 Trifolium Species 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SBUBPFHJZHQNNT-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene hydrogen peroxide Chemical compound OO.OO.CC(C)C1=CC=CC=C1C(C)C SBUBPFHJZHQNNT-UHFFFAOYSA-N 0.000 description 1
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 1
- ADNTWSHRSHPGHG-UHFFFAOYSA-N 1,3-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC(C(C)C)=C1 ADNTWSHRSHPGHG-UHFFFAOYSA-N 0.000 description 1
- KGSZJJXPYRHHSY-UHFFFAOYSA-N 1,6-di(propan-2-yl)-7-oxabicyclo[4.1.0]hepta-2,4-diene Chemical compound C1=CC=CC2(C(C)C)C1(C(C)C)O2 KGSZJJXPYRHHSY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011830 basic ionic liquid Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical group [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
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%;
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%;
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 cost is low, the environment is friendly, and the industrial prospect is wide.
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,
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):
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 ]
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 molecular sieve using 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 the Nabeta molecular sieve, the molecular sieve,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 ]
Of catalystsPreparation: 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 was added to an aqueous solution containing copper nitrate and nickel acetate, wherein the content of copper nitrate was 4% by weight based on the amount of copper oxide supported and the content of nickel acetate was 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: 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%.
Formation 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 cobalt chloride content was 2% by weight based on the supported amount of cobalt oxide and the titanium chloride content was 8% by weight based on the supported amount of titanium oxide, and the mixture was stirred at 25 ℃ to react 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 solution reaches 72.0%, and the selectivity of 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
TABLE 2
Claims (11)
1. An alkylbenzene hydroperoxide 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;
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%;
2. the alkylbenzene hydroperoxide catalyst according to claim 1, wherein the catalyst comprises 88-94 wt% of molecular sieve and 6-12 wt% of transition metal oxide, preferably 90-92 wt% of molecular sieve and 8-10 wt% of transition metal oxide, relative to the total weight of molecular sieve and transition metal oxide.
3. Alkylbenzene hydroperoxide catalyst according to claim 1, characterised in that the transition metal is selected from at least one of the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn, preferably from at least one of the group consisting of Ti, Co, Ni and Cu.
4. Alkylbenzene hydroperoxide catalyst according to claim 1, characterised in that the molecular sieve has a capacity χ of M of at least above 70%, more preferably at least above 80%, more preferably at least above 90%, most preferably 100%.
5. A method for preparing an alkylbenzene hydroperoxide catalyst, comprising the steps of:
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%;
6. the method for preparing an alkylbenzene hydroperoxide catalyst according to claim 5, wherein 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.
7. Process for the preparation of an alkylbenzene hydroperoxide catalyst according to claim 5 characterised in that the molecular sieve M. NaA has a capacity χ of M of at least 70%, more preferably at least 80%, more preferably at least 90%, most preferably 100%.
8. 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 4 or prepared by the process for preparing the catalyst of any one of claims 5 to 7 under effective reaction conditions to synthesize alkylbenzene hydroperoxide.
9. The process for the production of alkylbenzene hydroperoxide according to claim 8, wherein the effective reaction conditions comprise: 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.
10. The process for producing alkylbenzene hydroperoxide according to claim 8, wherein the catalyst is added in an amount of 0.001 to 1 times by weight based on the weight of alkylbenzene.
11. The process for producing alkylbenzene hydroperoxide according to claim 8, wherein the alkylbenzene comprises cumene, diisopropylbenzene, triisopropylbenzene, sec-butylbenzene or methylisopropylbenzene.
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 true CN110841698A (en) | 2020-02-28 |
CN110841698B 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)
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 |
-
2018
- 2018-08-21 CN CN201810952199.6A patent/CN110841698B/en active Active
Patent Citations (4)
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)
Title |
---|
S. VETRIVEL ET AL.: ""Co and Mn impregnated MCM-41: their applications to vapour phase oxidation of isopropylbenzene"", 《JOURNAL OF MOLECULAR CATALYSIS A:CHEMICAL》 * |
张美英等: ""改性HMS分子筛在多相催化反应中的应用"", 《石油学报(石油加工)》 * |
薛常海等: ""碱土金属氧化物催化氧化异丙苯反应研究"", 《石油学报(石油加工)》 * |
Also Published As
Publication number | Publication date |
---|---|
CN110841698B (en) | 2022-07-08 |
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 | |
US9713804B2 (en) | Catalyst composition for the dehydrogenation of alkanes | |
DK155920B (en) | CATALYST AND METHOD OF PRODUCING THEREOF | |
CN104549349B (en) | MAL and the catalyst of methacrylic acid | |
US20160354764A1 (en) | Method for Preparing Ferrite Metal Oxide Catalyst | |
US20170073284A1 (en) | Improved catalyst for dehydrogenating hydrocarbons | |
CN107999118A (en) | A kind of aromatic hydrocarbons and synthesis gas alkylation catalyst and preparation method and application | |
CN110841698B (en) | Alkyl benzene hydroperoxide catalyst, preparation method and application thereof | |
CN110845382B (en) | Process for preparing alkylbenzene hydroperoxide | |
CN100443177C (en) | Ethyl benzene oxidizing-dehydrogenation catalyst | |
CN105732255B (en) | Selective hydrogenation method for alkyne | |
CN104549353B (en) | MAL and the catalyst of methacrylic acid and its preparation method | |
US10543478B2 (en) | Catalyst for oxidative dehydrogenation and method of preparing the same | |
US4386226A (en) | Process for the ortho-alkylation of phenols | |
CN110975884B (en) | Preparation method of transition metal-containing catalyst for preparing benzaldehyde by selectively oxidizing toluene | |
US10052620B2 (en) | Catalyst for oxidation reactions, a method for its preparation and the use thereof | |
Hara et al. | Epoxidation of cyclic enones with hydrogen peroxide catalysed by alkylcarboxylate-intercalated Ni–Zn mixed basic salts | |
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 | |
CN100496728C (en) | Catalyst for preparing cyclohexene by selective benzene hydrogenation, its preparing method and use | |
KR101785181B1 (en) | Catalyst for acrylonitrile production and method for producing acrylonitrile | |
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 |
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 |