CN109954499B - Phenol ortho-methylation catalyst and method for producing ortho-methylated phenol by using same - Google Patents
Phenol ortho-methylation catalyst and method for producing ortho-methylated phenol by using same Download PDFInfo
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- CN109954499B CN109954499B CN201910256493.8A CN201910256493A CN109954499B CN 109954499 B CN109954499 B CN 109954499B CN 201910256493 A CN201910256493 A CN 201910256493A CN 109954499 B CN109954499 B CN 109954499B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 150000002989 phenols Chemical class 0.000 title claims abstract description 55
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title abstract description 48
- 238000004519 manufacturing process Methods 0.000 title abstract description 22
- 238000007069 methylation reaction Methods 0.000 title abstract description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 164
- 229910052751 metal Inorganic materials 0.000 claims abstract description 86
- 239000002184 metal Substances 0.000 claims abstract description 86
- 239000011572 manganese Substances 0.000 claims abstract description 81
- 229910052742 iron Inorganic materials 0.000 claims abstract description 78
- 239000002131 composite material Substances 0.000 claims abstract description 74
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 71
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims abstract description 70
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 45
- 229910052684 Cerium Inorganic materials 0.000 claims description 44
- 229910052720 vanadium Inorganic materials 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 38
- 238000002360 preparation method Methods 0.000 claims description 24
- 239000011701 zinc Substances 0.000 claims description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- 229910052725 zinc Inorganic materials 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 22
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000011833 salt mixture Substances 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001785 cerium compounds Chemical class 0.000 claims description 3
- 229960001759 cerium oxalate Drugs 0.000 claims description 3
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 150000003682 vanadium compounds Chemical class 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 9
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 9
- 239000003153 chemical reaction reagent Substances 0.000 claims 6
- 125000003158 alcohol group Chemical group 0.000 claims 1
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000000935 solvent evaporation Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 77
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 35
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 35
- 239000002994 raw material Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- SKAXWKNRKROCKK-UHFFFAOYSA-N [V].[Ce] Chemical compound [V].[Ce] SKAXWKNRKROCKK-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- 238000011084 recovery Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- 238000002791 soaking Methods 0.000 description 7
- 238000005804 alkylation reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 150000003681 vanadium Chemical class 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- BPRYUXCVCCNUFE-UHFFFAOYSA-N 2,4,6-trimethylphenol Chemical compound CC1=CC(C)=C(O)C(C)=C1 BPRYUXCVCCNUFE-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- IDIMJXYDZXSZOS-UHFFFAOYSA-L [OH-].[OH-].[Ce+3].[Ce+3] Chemical compound [OH-].[OH-].[Ce+3].[Ce+3] IDIMJXYDZXSZOS-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229930014626 natural product Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a phenol ortho-methylation catalyst and a method for producing ortho-methylated phenol by using the same. Specifically, phenol-methanol-water is subjected to a reaction at a constant pressure of 250-300 ℃ in the presence of a metal N-doped iron/manganese/metal M composite oxide catalyst to produce orthomethylated phenol at a certain rate, and the orthomethylated phenol and/or 2, 6-dimethylphenol are separated to obtain purer orthocresol and/or 2, 6-dimethylphenol.
Description
Technical Field
The invention relates to a phenol ortho-methylation catalyst and a method for producing ortho-methylated phenol by using the same. Specifically, phenol-methanol-water is subjected to normal pressure at 250-300 ℃ in the presence of a metal N-doped iron/manganese/metal M composite oxide catalyst to produce ortho-methylated phenol through a reactor at a certain rate.
Background
Phenol orthomethylation is one of the important chemical reactions, and the products o-cresol and 2, 6-dimethylphenol are two important fine chemical intermediates. O-cresol is one of important intermediates of herbicides and pesticides, and is also one of raw materials for producing o-cresol formaldehyde resin, and the market demand is huge at present; 2, 6-dimethylphenol is a synthetic raw material of polyphenyl ether which is one of five general engineering plastics, and is also an important raw material of certain special antioxidants.
Ortho-methylated phenols were originally isolated from coal tar and petroleum cleavage products, but because of the complex composition of coal tar and petroleum cleavage products, it is difficult to obtain high purity ortho-methylated phenols, and natural product isolation has been gradually replaced by chemical synthesis. Among these, the most advanced chemical synthesis is the phenol-methanol vapor phase alkylation. The method is characterized in that phenol and methanol are synthesized into a crude phenol mixture with ortho-methylated phenol (yield > 90%) as a main component under the catalysis of metal composite oxide at the temperature of about 250-450 ℃, and then the crude phenol mixture is separated and purified to obtain high-purity o-cresol and/or 2, 6-dimethylphenol.
Different types of metal complex oxide catalysts have been developed for the production of ortho-methylated phenols.
The earliest catalyst used in the production of ortho-methylated phenol was Al 2 O 3 And its composite oxide, patent US2448942 discloses an Al 2 O 3 The phenol alkylation catalyst has low ortho-selectivity, and a large amount of meta-position and para-position methylated phenols are associated, so that the separation is difficult, and high-purity ortho-position methylated phenol cannot be obtained, so that the catalyst is not popularized in industrial production.
Later on, in order to overcome the weaknesses of the above-mentioned catalysts, the hot trend of developing phenol ortho-methylation catalysts was raised. The GE company discloses Mg/Mn composite oxide catalysts through patents such as US3974229, US4418224 and US4661638, and the like, can selectively synthesize ortho-methylated phenol and are applied to industrial production. However, the use of this catalyst still inevitably results in a certain proportion of para-methylated phenol during the production process. And the working temperature (450-550 ℃) of the catalyst is higher, so that raw material methanol is decomposed in a large amount in the production process, and the production cost is increased. Moreover, the service life of the catalyst is only 100 hours or more, and the catalyst needs to be frequently replaced in industrial production, so that the production mode is difficult to be said to be efficient.
With Fe 2 O 3 The disadvantages of the Mg/Mn composite oxide catalysts are overcome by the presence of the series of catalysts. Patent US3953529 discloses a Fe 2 O 3 Composite catalyst consisting of Fe 2 O 3 、SiO 2 And Cr (V) 2 O 3 The composition can effectively reduce the gas phase reaction temperature, and the o-methylated phenol is generated, and comprises anisole and 2,4, 6-trimethylphenol. Patent US3937669 discloses Fe 2 O 3 -V 2 O 5 The composite catalyst can lead the phenol methylation reaction to be carried out at a lower temperature (300-400 ℃), the generated products are mainly ortho-methylated phenol and trace para-methylated products, the service life of the catalyst is longer, and the catalyst can be continuously produced for at least 1000 hours. Patent CN1240654 discloses a Fe 2 O 3 A catalyst comprising Fe 2 O 3 、In 2 O 3 、Cr 2 O 3 、CaO、SiO 2 The composition has the phenol conversion rate reaching 99 percent, the ortho-position selectivity reaching 97 percent and the service life reaching more than 3000 hours. Patent CN101513614 discloses a preparation method of an environment-friendly Fe-based catalyst, which is a Fe/Mg/M composite oxide, and phenol and methanol can obtain good ortho-alkylation results under the action of the catalyst.
Careful analysis of Fe as described above 2 O 3 The catalyst is a patent, although the disclosed metal composite oxide catalyst obtains better ortho-methylation result and longer service life of the catalyst at a lower reaction temperature (250-400 ℃) in the process of preparing ortho-methylated phenol by gas phase alkylation of phenol and methanol. But with a high yield of o-cresol (yield>90%) is the goal, the lower reaction temperature often leads to lower conversion rate (40-60%) of raw material phenol, and the production efficiency is low; to enrich the yield of 2, 6-dimethylphenol (yield)>90%) is aimed at, and the higher production temperature (320-450 ℃) often leads to the decomposition of raw material methanol, increasing the production cost. Therefore, a metal composite oxide catalyst is needed, which not only can obtain higher phenol conversion rate when producing o-cresol, but also can reduce the reaction temperature when producing 2, 6-dimethylphenol, reduce the decomposition of raw material methanol and achieve the purpose of reducing the production cost.
Disclosure of Invention
The invention provides a phenol ortho-methylation catalyst and a method for producing ortho-methylated phenol by using the same. Specifically, phenol-methanol-water is subjected to normal pressure at 250-300 ℃ in the presence of a metal N-doped iron/manganese/metal M composite oxide catalyst to produce ortho-methylated phenol through a reactor at a certain rate, and the ortho-methylated phenol is separated to obtain purer ortho-cresol and/or 2, 6-dimethylphenol.
The ortho-methylated phenol includes an ortho-methylated phenol which is ortho-cresol and/or two ortho-methylated phenols which is 2, 6-dimethylphenol, which can be one of the phenols or a mixture of the two phenols.
The phenol and methanol are the starting materials for the production of ortho-methylated phenol. The molar ratio of phenol to methanol is not critical, but in order to ensure maximum conversion of phenol, the molar ratio of phenol to methanol added should be less than 1. The adding mode of the phenol and the methanol is not strict, and the phenol and the methanol can be added into the reactor respectively, or can be added into the reactor after the phenol and the methanol are mixed uniformly, preferably the phenol and the methanol are added into the reactor after the phenol and the methanol are mixed uniformly. The water is added into the reaction system to ensure the stable operation of the phenol-methanol gas phase for producing the ortho-methylated phenol, thereby prolonging the service life of the catalyst. The amount of water added is not critical, but should follow the following principle: too much water may inhibit the reaction, and too little water may increase the probability of side reactions.
The doped metal N is a mixture of metal vanadium (V) and cerium (Ce), the molar ratio is not strict, and in general, the molar ratio of vanadium to cerium is proper in a range of 50:1-1:50 (V: ce); when o-cresol is produced in a rich amount (yield > 90%), the molar ratio is preferably in the range of 1:1 to 1:30, more preferably 1:1 to 1:15; when 2, 6-dimethylphenol is produced in a high yield (yield > 90%), the molar ratio is preferably in the range of 50:1 to 2:1, more preferably 30:1 to 2:1.
In the iron/manganese/metal M composite oxide, the metal M is one of cobalt (Co), nickel (Ni), copper (Cu) and zinc (Zn), and the molar ratio of the iron, manganese and the metal M in the composite oxide has the following relation: fe: mn: M=1: x (0.5-x), the range of x varies depending on the number of ortho-substitutions. When the yield of the o-cresol is high (the yield is more than 90 percent), and the ortho-position substitution number is 1, x is preferably 0 to 0.2; when 2, 6-dimethylphenol is produced in a high yield (yield > 90%), the ortho-position substitution number is 2), x is preferably 0.3 to 0.5.
The preparation method of the metal N-doped iron/manganese/metal M composite oxide catalyst comprises the following steps:
I. preparing the iron/manganese/metal M composite oxide.
1. One of iron, manganese and metal cobalt, nickel, copper and zinc is dissolved in a solvent in proportion, one of the iron, manganese and metal cobalt, nickel, copper and zinc can be in the form of metal salts or oxides thereof, the metal salts can be one or more of sulfate, chloride, nitrate, acetate, oxalate and carbonate, and a certain inorganic acid is needed to be added in order to enable the metal salts or oxides to be dissolved in the solvent, and the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid. The valence state of the metal is not critical and may be a valence II, III, IV, V metal salt or oxide. The solvent may be water or water-miscible organic solvent, and the organic solvent may be polar organic solvent such as alcohols, amides, sulfones, etc.
2. The metal salt solution in step 1 is uniformly mixed and the metal salt mixture is separated from the solvent. The manner of mixing is not critical, and the purpose is to allow the dissolved metal salts to mix uniformly, which may be stirring, ultrasonic agitation or natural mixing, preferably stirring and/or ultrasonic agitation. The separation of the metal salt mixture from the solvent may be carried out by evaporation to remove the solvent, or by precipitation of the metal salt mixture by addition of an alkaline agent, preferably the latter. The alkaline agent is preferably ammonia and/or urea, and is not strictly added, as long as the added metal salt mixture is allowed to completely precipitate.
3. And (3) drying the metal salt mixture obtained in the step (2), and roasting at 400-800 ℃ for 4-24 hours under the air condition to obtain the iron/manganese/metal M composite oxide.
II. Preparing a metal N-doped iron/manganese/metal M composite oxide catalyst.
4. Vanadium and cerium are dissolved in the aqueous solution according to the required proportion, the vanadium and cerium can be metal salts and/or oxides thereof, the metal valence is not strict, the vanadium can be IV-valence and/or V-valence salts or oxides thereof, and the cerium can be III-valence or IV-valence salts and/or oxides thereof. The listed vanadium compounds include, but are not limited to, ammonium metavanadate, vanadium pentoxide, vanadyl oxalate, and the like; exemplary cerium compounds include, but are not limited to, cerium oxide, cerium nitrate, cerium hydroxide cerium hydroxide, cerium acetate, cerium carbonate, cerium oxalate and the like, cerium oxide and cerium nitrate are preferable. In order to completely dissolve the above-mentioned salts and/or oxides of vanadium and cerium in an aqueous solution, nitric acid and/or oxalic acid may be added in an amount as follows: the added nitric acid and/or the salt of vanadium and cerium are completely dissolved.
5. Immersing the iron/manganese/metal M composite oxide obtained in the step 3 into the solution obtained in the step 4, stirring for 2 hours, and then carrying out ultrasonic oscillation or standing for 4-24 hours.
6. The impregnation mixture obtained in step 5 was separated from the solution. The separation is not critical, and the solvent may be evaporated, or the metal may be completely precipitated by adding an alkaline agent, preferably an alkaline agent. The alkaline agent is preferably ammonia and/or urea, and the amount added is not critical, provided that the metal in the solution is completely precipitated.
7. Roasting the metal mixture separated in the step 6 for 4-24 hours at the temperature of 400-800 ℃ under the air condition to obtain the metal N-doped iron/manganese/metal M composite oxide catalyst.
The reaction pressure is normal pressure. The reaction pressure is too low and the vaporized feedstock cannot pass through the reactor at a steady rate; the reaction pressure is too high and the production cannot be operated in a safe manner.
The temperature of 250-300 ℃ is the reaction temperature for preparing ortho-methylated phenol. When the reaction temperature is between 250 ℃ and 280 ℃, the o-cresol is rich, and surprisingly, phenol still maintains high conversion rate (> 95%) although the reaction temperature is lower, and the o-cresol yield is more than 90%, the 2, 6-dimethylphenol yield is less than 10%, and no m-methylated phenol, p-methylated anisole and p-methylated anisole are generated; when the reaction temperature is increased to 280-300 ℃, the 2, 6-dimethylphenol is mainly produced in a rich way, and although the reaction temperature is lower than 300 ℃, the yield of the 2, 6-dimethylphenol can be ensured to be more than 90% by a proper catalyst and under proper reaction conditions, meanwhile, the conversion rate of the phenol is more than 95%, no m-methyl phenol, p-methyl phenol and anisole are produced, and the direct benefit of the reaction temperature lower than 300 ℃ is that the decomposition of raw material methanol is greatly reduced, so that the production cost is reduced. Although the reaction temperature is raised above 300 ℃ and the 2, 6-dimethylphenol is still produced in high yield, para-methylation reaction occurs at this time to produce trace amounts of 2,4, 6-trimethylphenol (< 1%).
The certain speed is the liquid hourly space velocity of the reaction, and for the reaction, the proper liquid hourly space velocity range is 0.1-5.0 h -1 Preferably 0.1 to 3.0 h -1 More preferably 0.2 to 1.0 h -1 。
The reactor is a reactor suitable for gas phase alkylation reaction, and can be a fixed bed reactor or a fluidized bed reactor. When a fixed bed reactor is used, the catalyst is fixed in the catalyst bed; when a fluidized bed reactor is used, the catalyst is in an ebullated bed.
The separation refers to the process of obtaining purer o-cresol and/or 2, 6-dimethylphenol through a plurality of stages of continuous rectifying towers. Suitable continuous rectification columns include phenol recovery columns, o-cresol columns, and 2, 6-dimethylphenol columns. The pure o-cresol and/or 2, 6-dimethylphenol can be obtained by continuously passing through the 3-level rectifying tower.
In summary, the present invention provides a phenol ortho-methylation catalyst and a method for producing ortho-methylated phenol using the same. By using the metal N-doped iron/manganese/metal M composite oxide catalyst provided by the invention, phenol has higher conversion rate (more than 95%) when o-cresol is rich at 250-280 ℃, the production efficiency is improved, 2, 6-dimethylphenol can be efficiently produced at a lower temperature of 280-300 ℃, the decomposition of methanol in the reaction process is reduced, and the production cost is reduced. In addition, no matter the o-cresol or 2, 6-dimethylphenol is produced, the products are not produced from m-methylated phenol, p-methylated phenol and anisole, and the more pure o-methylated phenol products reduce the rectifying towers required by separation and purification, thereby directly bringing about the reduction of investment and production cost.
The invention is generally described with respect to phenol ortho-methylation catalysts and methods for producing ortho-methylated phenols, and is further described in the following detailed description.
Detailed Description
Example 1
1. Preparation of vanadium-cerium doped iron/manganese/zinc composite oxide catalyst
40kg of Fe is weighed 2 O 3 ，14.35kg Mn(NO 3 ) 2 ·6H 2 O,16.2kg ZnO is placed in 150L water, 65kg concentrated nitric acid is weighed and added into the 150L water under continuous stirring, ammonia water is slowly added into the solution after metal oxide is completely dissolved, the solution is continuously stirred until metal in the solution is completely precipitated, then stirring is continued for 2h, and the solution is kept stand and aged for 12h. The precipitated precipitate was filtered and washed with water and dried at 130 ℃ for 2h. And (3) placing the dried precipitate in a roasting furnace to be roasted for 24 hours at the temperature of 450 ℃ to obtain the iron/manganese/zinc composite oxide. Weighing 31.85kg V 2 O 5 And 240.8kg CeO 2 Put in 150L of water, add nitric acid slowly with care, with constant stirring, until the oxide just dissolves. And (3) putting the iron/manganese/zinc composite oxide obtained by roasting into the dissolved vanadium and cerium solution, stirring for 2 hours, standing for 24 hours, fully soaking the iron/manganese/zinc composite oxide into the vanadium and cerium aqueous solution, removing water under reduced pressure, and roasting the mixture after the water removal at 450 ℃ for 24 hours to obtain the vanadium and cerium doped iron/manganese/zinc composite oxide catalyst. The molar ratio of the metals in the catalyst is Fe, mn, zn, ce=10, 1, 4, 28 and 7.
The obtained vanadium and cerium doped iron/manganese/zinc composite oxide catalyst is pressed into a cylinder with phi of 2mm multiplied by 2mm for standby.
2. Preparation of ortho-methylated phenols
The cylindrical catalyst prepared above was placed in a fixed bed reactor having a reaction tube bundle with an inner diameter of phi 25 mm. Raw materials of phenol, methanol and water are proportioned according to the mol ratio of 2:3:7, then pumped into a gasifier by a pump, gasified at 250 ℃ and then at a liquid hourly space velocity of 0.5h -1 Into the reactor, the reactor temperature was 250 ℃. Ortho-methylated phenol obtained after the reaction is subjected toThe phenol recovery tower and the o-cresol tower obtain 99.7% o-cresol.
The gas phase product obtained by the reaction was analyzed by gas chromatography, and the results are shown in the following table:
example 2
1. Preparation of vanadium-cerium doped iron/manganese/nickel composite oxide catalyst
Weigh 135kg FeCl 3 ·6H 2 O，39.6kg MnCl 2 ·4H 2 O，11.9kg NiCl 2 ·6H 2 And O, placing the mixture into a mixed solution of 100L of water and 50L of methanol, slowly adding ammonia water into the solution after the mixture is completely dissolved, continuously stirring the solution until the metal in the solution is completely precipitated, continuously stirring the solution for 2 hours, and standing and aging the solution for 12 hours. The precipitated precipitate was filtered and washed with water and dried at 130 ℃ for 2h. And (3) placing the dried precipitate in a roasting furnace to be roasted for 24 hours at 550 ℃ to obtain the iron/manganese/nickel composite oxide. Weigh 4.7kg NH 4 VO 3 And 4.4kg Ce (NO) 3 ) 3 ·6H 2 O was placed in 150L of water and oxalic acid was carefully added dropwise with constant stirring until the vanadium salt had just dissolved. And (3) putting the iron/manganese/nickel composite oxide obtained by roasting into the dissolved vanadium and cerium solution, stirring for 2 hours, carrying out ultrasonic oscillation for 12 hours, fully soaking the iron/manganese/nickel composite oxide into the vanadium and cerium aqueous solution, then removing water under reduced pressure, and roasting the mixture after removing water for 12 hours at 550 ℃ to obtain the vanadium-cerium doped iron/manganese/nickel composite oxide catalyst. The molar ratio of the metals in the catalyst is Fe, mn, ni, ce=50, 20, 5, 4 and 1.
And (3) spraying and granulating the obtained vanadium-cerium doped iron/manganese/nickel composite oxide catalyst into pellets with the diameter of 5mm for later use.
2. Preparation of ortho-methylated phenols
The spherical catalyst prepared above was put into a fluidized bed reactor. Raw materials of phenol, methanol and water are mixed according to a molar ratio of 1:3:5, and then pumped into a gasifier through a pump, gasified at 250 ℃ and then treated with liquidHourly space velocity of 2.3h -1 Into the reactor, the reactor temperature was 285 ℃. The ortho-methylated phenol obtained after the reaction passes through a phenol recovery tower, an ortho-cresol tower and a 2, 6-dimethylphenol tower to obtain 99.3 percent of ortho-cresol and 99.7 percent of 2, 6-dimethylphenol.
The gas phase product obtained by the reaction was analyzed by gas chromatography, and the results are shown in the following table:
example 3
1. Preparation of vanadium-cerium doped iron/manganese/cobalt composite oxide catalyst
Weigh 202kg Fe (NO) 3 ) 3 ·9H 2 O，35.9kg Mn(NO 3 ) 2 ·6H 2 O，36.4kg Co(NO 3 ) 2 ·6H 2 O is dissolved in 150L of water, ammonia water is slowly added into the solution after the solution is completely dissolved, stirring is continued until the metal in the solution is completely precipitated, stirring is continued for 2 hours, and the solution is kept stand and aged for 12 hours. The precipitated precipitate was filtered and washed with water and dried at 130 ℃ for 2h. And (3) placing the dried precipitate in a roasting furnace to be roasted for 24 hours at the temperature of 650 ℃ to obtain the iron/manganese/cobalt composite oxide. Weigh 49kg VOC 2 O 4 ·5H 2 O and 57.9kg Ce (NO) 3 ) 3 ·6H 2 O was placed in 150L of water and the added salt was dissolved with constant stirring. And (3) putting the iron/manganese/cobalt composite oxide obtained by roasting into the dissolved vanadium and cerium solution, stirring for 2 hours, carrying out ultrasonic oscillation for 12 hours, fully soaking the iron/manganese/cobalt composite oxide into the vanadium and cerium aqueous solution, then removing water under reduced pressure, and roasting the mixture after the water removal at 650 ℃ for 24 hours to obtain the vanadium and cerium doped iron/manganese/cobalt composite oxide catalyst. The molar ratio of the metals in the catalyst is Fe, mn, co, ce=60, 15, 24 and 16.
The obtained vanadium and cerium doped iron/manganese/cobalt composite oxide catalyst is pressed into a cylinder with phi of 2mm multiplied by 2mm for standby.
2. Preparation of ortho-methylated phenols
The cylindrical catalyst prepared above was placed in a fixed bed reactor having a reaction tube bundle with an inner diameter of phi 25 mm. Raw materials of phenol, methanol and water are mixed according to the mol ratio of 1:2:4, and then pumped into a gasifier through a pump, gasified at 250 ℃ and at the liquid hourly space velocity of 1h -1 Into the reactor, the reactor temperature was 290 ℃. The ortho-methylated phenol obtained after the reaction passes through a phenol recovery tower, an ortho-cresol tower and a 2, 6-dimethylphenol tower to obtain ortho-cresol with the purity of 99.5 percent and 2, 6-dimethylphenol with the purity of 99.6 percent.
The gas phase product obtained by the reaction was analyzed by gas chromatography, and the results are shown in the following table:
example 4
1. Preparation of vanadium-cerium doped iron/manganese/zinc composite oxide catalyst
40kg of Fe is weighed 2 O 3 ，14.35kg Mn(NO 3 ) 2 ·6H 2 O,16.2kg ZnO is placed in 150L water, 65kg concentrated nitric acid is weighed and added into the 150L water under continuous stirring, ammonia water is slowly added into the solution after metal oxide is completely dissolved, the solution is continuously stirred until metal in the solution is completely precipitated, then stirring is continued for 2h, and the solution is kept stand and aged for 12h. The precipitated precipitate was filtered and washed with water and dried at 130 ℃ for 2h. And (3) placing the dried precipitate in a roasting furnace to be roasted for 24 hours at the temperature of 450 ℃ to obtain the iron/manganese/zinc composite oxide. Weighing 30kg V 2 O 5 And 573kg CeO 2 In 300L of water, nitric acid was carefully added slowly with constant stirring until the oxide had just dissolved. And (3) putting the iron/manganese/zinc composite oxide obtained by roasting into the dissolved vanadium and cerium solution, stirring for 2 hours, standing for 24 hours, fully soaking the iron/manganese/zinc composite oxide into the vanadium and cerium aqueous solution, removing water under reduced pressure, and roasting the mixture after the water removal at 450 ℃ for 24 hours to obtain the vanadium and cerium doped iron/manganese/zinc composite oxide catalyst. The mol ratio of each metal in the catalyst is Fe, mn, zn, V:Ce= 30 : 3 : 12 : 10 : 200。
the obtained vanadium and cerium doped iron/manganese/zinc composite oxide catalyst is pressed into a cylinder with phi of 2mm multiplied by 2mm for standby.
2. Preparation of ortho-methylated phenols
The cylindrical catalyst prepared above was placed in a fixed bed reactor having a reaction tube bundle with an inner diameter of phi 25 mm. Raw materials of phenol, methanol and water are mixed according to the mol ratio of 2:3:8, and then pumped into a gasifier by a pump, gasified at 250 ℃ and then at a liquid hourly space velocity of 0.8h -1 Into the reactor, the reactor temperature was 265 ℃. The ortho-methylated phenol obtained after the reaction passes through a phenol recovery tower and an ortho-cresol tower to obtain 99.7 percent ortho-cresol.
The gas phase product obtained by the reaction was analyzed by gas chromatography, and the results are shown in the following table:
example 5
1. Preparation of vanadium-cerium doped iron/manganese/nickel composite oxide catalyst
Weigh 135kg FeCl 3 ·6H 2 O，39.6kg MnCl 2 ·4H 2 O，11.9kg NiCl 2 ·6H 2 And (3) placing O in 150L of water, slowly adding ammonia water into the solution after the O is completely dissolved, continuously stirring until the metal in the solution is completely precipitated, continuously stirring for 2 hours, and standing and aging the solution for 12 hours. The precipitated precipitate was filtered and washed with water and dried at 130 ℃ for 2h. And (3) placing the dried precipitate in a roasting furnace to be roasted for 24 hours at 550 ℃ to obtain the iron/manganese/nickel composite oxide. Weigh 19kg NH 4 VO 3 And 1.76kg Ce (NO) 3 ) 3 ·6H 2 O was placed in 150L of water and oxalic acid was carefully added dropwise with constant stirring until the vanadium salt had just dissolved. Placing the baked iron/manganese/nickel composite oxide into the above-mentioned dissolved vanadium and cerium solution, stirring for 2 hr, standing for 24 hr to make the iron/manganese composite oxide be fully soaked in the aqueous solution of vanadium and cerium, then decompressing to remove water, and removing waterThe mixture is roasted for 24 hours at 550 ℃ to obtain the vanadium and cerium doped iron/manganese/nickel composite oxide catalyst. The molar ratio of Fe to Mn to Ni to Ce=123 to 49.2 to 12.3 to 40 to 1 of the metals in the catalyst.
And (3) spraying and granulating the obtained vanadium-cerium doped iron/manganese/nickel composite oxide catalyst into pellets with the diameter of 5mm for later use.
2. Preparation of ortho-methylated phenols
The spherical catalyst prepared above was put into a fluidized bed reactor. Raw materials of phenol, methanol and water are mixed according to the mol ratio of 1:3:5, and then pumped into a gasifier by a pump, gasified at 250 ℃ and at a liquid hourly space velocity of 2.3h -1 Into the reactor, the reactor temperature was 300 ℃. The ortho-methylated phenol obtained after the reaction passes through a phenol recovery tower, an ortho-cresol tower and a 2, 6-dimethylphenol tower to obtain 99.3 percent of ortho-cresol and 99.7 percent of 2, 6-dimethylphenol.
The gas phase product obtained by the reaction was analyzed by gas chromatography, and the results are shown in the following table:
example 6
1. Preparation of vanadium-cerium doped iron/manganese/zinc composite oxide catalyst
40kg of Fe is weighed 2 O 3 ，14.35kg Mn(NO 3 ) 2 ·6H 2 O,16.2kg ZnO is placed in 150L water, 65kg concentrated nitric acid is weighed and added into the 150L water under continuous stirring, ammonia water is slowly added into the solution after metal oxide is completely dissolved, the solution is continuously stirred until metal in the solution is completely precipitated, then stirring is continued for 2h, and the solution is kept stand and aged for 12h. The precipitated precipitate was filtered and washed with water and dried at 130 ℃ for 2h. And (3) placing the dried precipitate in a roasting furnace to be roasted for 24 hours at 800 ℃ to obtain the iron/manganese/zinc composite oxide. Weigh 22.5kg NH 4 VO 3 And 1000kg Ce (NO) 3 ) 3 ·6H 2 O was placed in 500L of water and oxalic acid was carefully added dropwise with constant stirring until the vanadium salt had just dissolved.And (3) putting the iron/manganese/zinc composite oxide obtained by roasting into the dissolved vanadium and cerium solution, stirring for 2 hours, standing for 24 hours, fully soaking the iron/manganese/zinc composite oxide into the vanadium and cerium aqueous solution, removing water under reduced pressure, and roasting the mixture after removing water at 800 ℃ for 24 hours to obtain the vanadium and cerium doped iron/manganese/zinc composite oxide catalyst. The molar ratio of Fe to Mn to Zn to Ce=65 to 26 to 6.5 to 25 to 300.
The obtained vanadium and cerium doped iron/manganese/zinc composite oxide catalyst is pressed into a cylinder with phi of 2mm multiplied by 2mm for standby.
2. Preparation of ortho-methylated phenols
The cylindrical catalyst prepared above was placed in a fixed bed reactor having a reaction tube bundle with an inner diameter of phi 25 mm. Raw materials of phenol, methanol and water are mixed according to the mol ratio of 2:3:8, and then pumped into a gasifier by a pump, gasified at 250 ℃ and then at a liquid hourly space velocity of 0.8h -1 Into the reactor, the reactor temperature was 255 ℃. The ortho-methylated phenol obtained after the reaction passes through a phenol recovery tower and an ortho-cresol tower to obtain 99.7 percent ortho-cresol.
The gas phase product obtained by the reaction was analyzed by gas chromatography, and the results are shown in the following table:
example 7
1. Preparation of vanadium-cerium doped iron/manganese/copper composite oxide catalyst
Weighing 139kg FeSO 4 ·7H 2 O，38kg MnSO 4 ·H 2 O，6.25kg CuSO 4 ·5H 2 O is dissolved in 150L of water, ammonia water is slowly added into the solution after the solution is completely dissolved, stirring is continued until the metal in the solution is completely precipitated, stirring is continued for 2 hours, and the solution is kept stand and aged for 12 hours. The precipitated precipitate was filtered and washed with water and dried at 130 ℃ for 2h. And (3) placing the dried precipitate in a roasting furnace to be roasted for 24 hours at 750 ℃ to obtain the iron/manganese/copper composite metal oxide. Weigh 3kg VOC 2 O 4 ·5H 2 O and 0.13kg Ce (NO) 3 ) 3 ·6H 2 O was placed in 50L of water and the added salt was dissolved with constant stirring. And (3) putting the iron/manganese/copper composite metal oxide obtained by roasting into the dissolved vanadium and cerium solution, stirring for 2 hours, standing for 24 hours, fully soaking the iron/manganese/copper composite oxide into the vanadium and cerium aqueous solution, removing water under reduced pressure, and roasting the mixture after removing water for 24 hours at 750 ℃ to obtain the vanadium and cerium doped iron/manganese/copper composite oxide catalyst. The molar ratio of the metals in the catalyst is Fe to Mn to Cu to Ce=1640 to 738 to 82 to 40 to 1.
The obtained vanadium and cerium doped iron/manganese/copper composite oxide catalyst is pressed into a cylinder with phi of 2mm multiplied by 2mm for standby.
2. Preparation of ortho-methylated phenols
The cylindrical catalyst prepared above was placed in a fixed bed reactor having a reaction tube bundle with an inner diameter of phi 25 mm. Raw materials of phenol, methanol and water are mixed according to the mol ratio of 1:3:5, and then pumped into a gasifier by a pump, gasified at 250 ℃ and then at a liquid hourly space velocity of 3.7h -1 Into the reactor, the reactor temperature was 310 ℃. The ortho-methylated phenol obtained after the reaction passes through a phenol recovery tower, an ortho-cresol tower and a 2, 6-dimethylphenol tower to obtain 99.3 percent of ortho-cresol and 99.7 percent of 2, 6-dimethylphenol.
The gas phase product obtained by the reaction was analyzed by gas chromatography, and the results are shown in the following table:
example 8
1. Preparation of vanadium-cerium doped iron/manganese/nickel composite oxide catalyst
Weigh 135kg FeCl 3 ·6H 2 O，39.6kg MnCl 2 ·4H 2 O，11.9kg NiCl 2 ·6H 2 Placing O in 150L water, slowly adding ammonia water into the solution after complete dissolution, continuously stirring until metal in the solution is completely precipitated, continuously stirring for 2h, and collecting the solutionThe solution was left to stand and age for 12h. The precipitated precipitate was filtered and washed with water and dried at 130 ℃ for 2h. And (3) placing the dried precipitate in a roasting furnace to be roasted for 24 hours at 600 ℃ to obtain the iron/manganese/nickel composite oxide. Weigh 2.78kg NH 4 VO 3 And 0.52kg Ce (NO) 3 ) 3 ·6H 2 O was placed in 150L of water and oxalic acid was carefully added dropwise with constant stirring until the vanadium salt had just dissolved. And (3) putting the iron/manganese/nickel composite oxide obtained by roasting into the dissolved vanadium and cerium solution, stirring for 2 hours, standing for 24 hours, fully soaking the iron/manganese/nickel composite oxide into the vanadium and cerium aqueous solution, removing water under reduced pressure, and roasting the mixture after removing water at 600 ℃ for 24 hours to obtain the vanadium and cerium doped iron/manganese/nickel composite oxide catalyst. The molar ratio of the metals in the catalyst is Fe, mn, ni, ce=420, 168, 42, 20 and 1.
And (3) spraying and granulating the obtained vanadium-cerium doped iron/manganese/nickel composite oxide catalyst into pellets with the diameter of 5mm for later use.
2. Preparation of ortho-methylated phenols
The spherical catalyst prepared above was put into a fluidized bed reactor. Raw materials of phenol, methanol and water are mixed according to the mol ratio of 1:3:5, and then pumped into a gasifier by a pump, gasified at 250 ℃ and at a liquid hourly space velocity of 2.3h -1 Into the reactor, the reactor temperature was 330 ℃. The ortho-methylated phenol obtained after the reaction passes through a phenol recovery tower, an ortho-cresol tower and a 2, 6-dimethylphenol tower to obtain 99.3 percent of ortho-cresol and 99.7 percent of 2, 6-dimethylphenol.
The gas phase product obtained by the reaction was analyzed by gas chromatography, and the results are shown in the following table:
while the invention has been described in detail in the general context and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (12)
1. A preparation method of a metal N-doped iron/manganese/metal M composite oxide catalyst for producing ortho-methylated phenol is characterized by comprising the following steps of:
Fe : Mn : M = 1 : x : (0.5-x)；
the doped metal N consists of two metals of vanadium and cerium, wherein the molar ratio of the vanadium to the cerium is 50:1-1:50;
the metal M is one of cobalt, nickel, copper and zinc;
the preparation method of the catalyst comprises the following steps:
I. preparation of iron/manganese/Metal M composite oxides
(1) Dissolving iron, manganese and one of metal cobalt, nickel, copper and zinc in a solvent according to a proportion, wherein the iron, manganese and the one of metal cobalt, nickel, copper and zinc are in the form of metal salts or oxides thereof; the valence state of the metal is II, III, IV, V metal salt or oxide; the solvent is water or water-miscible organic solvent, and the organic solvent is alcohol, amide or sulfone polar organic solvent;
(2) Uniformly mixing the metal salt solution in the step (1), and separating the metal salt mixture from the solvent; the purpose of mixing is to uniformly mix the dissolved metal salts by stirring, ultrasonic vibration or natural mixing;
separating the metal salt mixture from the solvent by evaporating the solvent or precipitating the metal salt mixture by adding an alkaline reagent; the added alkaline reagent is ammonia water and/or urea, and the added alkaline reagent is added in an amount that the added metal salt mixture is completely precipitated;
(3) Drying the metal salt mixture obtained in the step (2), and roasting at 400-800 ℃ for 4-24 hours under the air condition to obtain an iron/manganese/metal M composite oxide;
II. Preparation of Metal N-doped iron/manganese/Metal M composite oxide catalysts
(4) Dissolving vanadium and cerium in a required proportion in an aqueous solution, wherein the vanadium and cerium are metal salts and/or oxides thereof, the vanadium in a metal valence state is IV and/or V salt or oxide thereof, and the cerium is III or IV salt and/or oxide thereof;
in order to completely dissolve the above-mentioned salts and/or oxides of vanadium and cerium in an aqueous solution, an amount of nitric acid and/or oxalic acid is added in the following manner: adding nitric acid and/or completely dissolving the salt of vanadium and cerium;
(5) Immersing the iron/manganese/metal M composite oxide obtained in the step (3) into the solution obtained in the step (4), stirring for 2 hours, and then carrying out ultrasonic oscillation or standing for 4-24 hours;
(6) Separating the impregnating mixture from the solution obtained in step (5); the separation mode adopts a solvent evaporation mode or adopts a mode of adding an alkaline reagent to completely precipitate the metal; the added alkaline reagent is ammonia water and/or urea, and the added alkaline reagent is added in an amount that the metal in the solution is completely precipitated;
(7) Roasting the metal mixture separated in the step (6) for 4-24 hours at the temperature of 400-800 ℃ under the air condition to obtain the metal N-doped iron/manganese/metal M composite oxide catalyst.
2. The preparation method according to claim 1, wherein the metal salt in the step (1) is one or more of sulfate, chloride, nitrate, acetate, oxalate and carbonate.
3. The method according to claim 2, wherein in the step (1), a certain amount of an inorganic acid is added to dissolve the metal salt or oxide in the solvent, and the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid.
4. The process according to claim 1, wherein the mixing in step (2) is performed by stirring and/or ultrasonic vibration.
5. The method of claim 1, wherein the vanadium compound in step (3) includes, but is not limited to, ammonium metavanadate, vanadium pentoxide, vanadyl oxalate; cerium compounds include, but are not limited to, cerium oxide, cerium nitrate, cerium hydroxide, cerium acetate, cerium carbonate, cerium oxalate, and cerium oxalate.
6. The method according to claim 5, wherein the cerium compound in the step (3) is cerium oxide or cerium nitrate.
7. The method according to claim 1, wherein x is in the range of 0 to 0.2 in the ratio of the complex oxide when o-cresol is rich.
8. The method according to claim 1, wherein x is in the range of 0.3 to 0.5 in the ratio of the composite oxide when 2, 6-dimethylphenol is enriched.
9. The method according to claim 1, wherein the molar ratio of vanadium to cerium is 1:1-1:30 when o-cresol is enriched.
10. The method according to claim 1, wherein the molar ratio of vanadium to cerium is 50:1-2:1 when 2, 6-dimethylphenol is enriched.
11. Use of the catalyst obtained by the preparation process according to any one of claims 1 to 10, characterized in that the phenol-methanol-water mixture is reacted at atmospheric pressure at a temperature of 250 ℃ to 300 ℃ in the presence of a metal N-doped iron/manganese/metal M composite oxidation catalyst to form ortho-methylated phenol.
12. The use according to claim 11, characterized in that the yield of o-cresol is >90% and the yield of 2, 6-dimethylphenol is <10% when the reaction temperature is between 250 ℃ and 280 ℃; no m, p-methylated phenol and anisole are generated; when the reaction temperature is increased to 280-300 ℃, the yield of 2, 6-dimethylphenol is more than 90%, and no m-methyl phenol, p-methyl phenol and anisole are generated.
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