CN114011457A - Preparation method of p-ethoxyphenol - Google Patents
Preparation method of p-ethoxyphenol Download PDFInfo
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- CN114011457A CN114011457A CN202111481940.3A CN202111481940A CN114011457A CN 114011457 A CN114011457 A CN 114011457A CN 202111481940 A CN202111481940 A CN 202111481940A CN 114011457 A CN114011457 A CN 114011457A
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- LKVFCSWBKOVHAH-UHFFFAOYSA-N 4-Ethoxyphenol Chemical compound CCOC1=CC=C(O)C=C1 LKVFCSWBKOVHAH-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 18
- 241000269350 Anura Species 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 12
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 11
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002808 molecular sieve Substances 0.000 claims abstract description 8
- 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 8
- 239000000243 solution Substances 0.000 claims description 17
- 238000004108 freeze drying Methods 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 10
- 229910017061 Fe Co Inorganic materials 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical group O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 4
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 238000001035 drying Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 9
- 230000002194 synthesizing effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- MOEFFSWKSMRFRQ-UHFFFAOYSA-N 2-ethoxyphenol Chemical compound CCOC1=CC=CC=C1O MOEFFSWKSMRFRQ-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229940032950 ferric sulfate Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003747 fuel oil additive Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229960004838 phosphoric acid Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of p-ethoxyphenol, in particular to a method for continuously catalyzing hydroquinone and ethanol to synthesize the p-ethoxyphenol with high activity and high selectivity by using an SAPO molecular sieve doped with iron, cobalt, lanthanum and cesium as a catalyst. The process is green and environment-friendly, the reaction condition is mild, p-ethoxyphenol can be continuously prepared, the catalyst can stably run for 3000 hours, and the activity is not obviously reduced.
Description
The technical field is as follows:
the invention relates to a preparation method of p-ethoxyphenol, in particular to a method for synthesizing p-ethoxyphenol by catalyzing and synthesizing a supported catalyst FeCoLaCs/SAPO.
Background art:
p-ethoxyphenol is an important chemical product, is widely used as a polymerization inhibitor for synthesizing high molecular compounds, an anti-aging agent, a plasticizer, a fuel oil additive and the like, and is also an intermediate for synthesizing fine chemical products such as medicines, pesticides, dyes, photographic sensitizers and the like.
Currently, there are three main methods for preparing p-ethoxyphenol: (1) dehydrohalogenating hydroquinone and haloalkane in alkaline environment to obtain p-ethoxyphenol. In the method, halogen elements participate, so that the problem of corrosion to reaction equipment exists, the reaction conditions are harsh, and the later separation is difficult; (2) the p-ethoxyphenol is prepared by taking hydroquinone and ethanol as raw materials through an electrolytic reaction, the electrolytic reaction preparation process has high energy consumption and is not suitable for industrial production, the expensive materials such as electrodes and the like cause overhigh production cost, and the yield is only 85 percent; (3) under the catalysis of p-benzoquinone and concentrated sulfuric acid, hydroquinone and ethanol are synthesized into p-ethoxyphenol. Compared with the former two processes, the process has the advantages of easily available raw materials, relatively stable process and suitability for large-scale industrial production. However, the process uses a liquid acid catalyst, a series of operations such as alkali addition neutralization, filtration, extraction, reduced pressure distillation and the like are required in the subsequent reaction, and the production flow is too long.
The invention content is as follows:
the invention aims to provide a preparation method of a metal supported catalyst FeCoLaCs/SAPO, which is applied to the continuous production of the catalytic synthesis of p-ethoxyphenol. The process has mild reaction conditions, is environment-friendly, can continuously prepare the p-ethoxyphenol, and has high catalyst reaction activity and good stability.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention firstly provides a preparation method of a supported lanthanum, cesium, cobalt and iron composite metal oxide catalyst FeCoLaCs/SAPO, which comprises the following steps:
1) putting a certain amount of aluminum source into water for hydrolysis to obtain a hydrolysis solution;
2) mixing the hydrolysis solution, a silicon source, a phosphorus source, a cobalt source, an iron source and a template agent with water, and then standing and aging the solution for a period of time;
3) then the aged solution is put into a crystallization kettle and sealed for crystallization;
4) cooling the crystallized mixture, and then carrying out solid-liquid separation to obtain a solid product;
5) freeze-drying the solid product to obtain a molecular sieve Fe-Co/SAPO;
6) roasting the molecular sieve Fe-Co/SAPO;
7) soaking the roasted molecular sieve Fe-Co/SAPO in an aqueous solution of a lanthanum source and a cesium source in equal amount by using ultrasound, then freeze-drying and roasting to obtain the catalyst.
In the preparation method of the catalyst, in the step 1), the Al source is selected from one or more of pseudo-boehmite, aluminum nitrate and aluminum isopropoxide,
putting an Al source into water for hydrolysis, wherein the concentration of the Al source is 10-20%, the hydrolysis time is 2-5h, and the hydrolysis temperature is 20-30 ℃.
In the preparation method of the catalyst, in the step 2), the Si source is silica sol (alkaline nano silica sol), and the mass fraction of the silica sol is 10-30%;
the P source is one or more of phosphoric acid, trimethyl phosphate and triethyl phosphate;
the Co source is selected from one or more of cobalt chloride, cobalt sulfate and cobalt nitrate;
the Fe source is selected from one or more of ferric chloride, ferric sulfate and ferric nitrate;
the template agent is selected from one or more of triethylamine, isopropylamine or tetraethylammonium hydroxide;
the total mass of the Si source, the Al source, the P source, the Co source, the Fe source and the template agent is preferably 1/2-1/4 of water;
controlling the mol ratio of Si, Al, P, Co, Fe and the template agent to be 0.1-1.5: 1: 0.1-0.5: 0.1-2.0: 0.1-2.0: 3-8;
in the preparation method of the catalyst, in the step 2), the aging temperature is 20-80 ℃ and the aging time is 2-24 hours.
In the preparation method of the catalyst, in the step 3), the crystallization temperature is 160-260 ℃ and the crystallization time is 24-120 hours.
In the preparation method of the catalyst, in the step 4), solid-liquid separation is realized by filtering.
In the preparation method of the catalyst, in the step 5), the freeze drying pressure is 10-200 Pa, and the temperature is-20 to-5 ℃.
In the preparation method of the catalyst, in the step 6), the roasting temperature is 400-600 ℃, the time is 4-10 h, and the temperature rise is 1-5 ℃/min.
In the preparation method of the catalyst, in the step 7), the lanthanum source is one or more of lanthanum sulfate and lanthanum nitrate,
the cesium source is one or more of cesium sulfate and cesium nitrate,
controlling the mole ratio of the lanthanum, the cesium, the cobalt and the iron to be 1: 0.1-1: 0.1-2.0: 0.1-2.0, preferably 1: 0.2-0.6: 0.5-1.5: 0.5-1.5;
the freeze drying is carried out, wherein the pressure is 10-200 Pa, and the temperature is-20 to-5 ℃; the roasting temperature is 400-600 ℃, the time is 4-10 h, and the temperature rise is 1-5 ℃/min.
The catalyst prepared in the invention is used in a continuous reaction process for synthesizing the ethoxyphenol:
the preferred steps are: filling the catalyst into a fixed bed, wherein the reaction raw material is a mixed solution of hydroquinone and ethanol, and the mixed raw material passes through a catalyst bed layer to obtain a p-ethoxyphenol reaction solution; separating and purifying the reaction liquid in a rectification mode to obtain a pure p-ethoxyphenol product;
in the invention, the molar ratio of hydroquinone to ethanol is 1: 3-1: 10, preferably 1: 5-1: 7;
in the invention, the reaction temperature is 200-260 ℃, the pressure is normal pressure, and the mass space velocity of the hydroquinone relative to the catalyst is 0.1-0.5 h-1。
In the invention, reaction raw materials are fed from the upper layer of the catalyst and discharged from the bottom.
The invention has the beneficial effects that:
in the supported catalyst FeCoLaCs/SAPO adopted by the invention, iron and cobalt participate in a formed framework of the SAPO molecular sieve, the structure of the molecular sieve is optimized, and the catalytic active metals lanthanum and titanium are impregnated in the framework, so that hydroquinone and ethanol can be catalyzed to synthesize p-ethoxyphenol with high activity and high selectivity, the conversion rate of the hydroquinone can reach 95%, and the yield of the p-ethoxyphenol can reach more than 90%.
The catalyst of the invention has high activity and stability, can stably run for 3000 hours, and has no obvious reduction of activity.
Description of the drawings:
FIG. 1: life test curve of the catalyst of example 1.
The specific implementation mode is as follows:
for a better understanding of the present invention, the contents of the present invention are further illustrated below with reference to examples, which are provided to illustrate the basic principles, main features and advantages of the present invention, but the present invention is not limited by the following examples.
Example 1
The preparation method of the catalyst comprises the following steps:
putting pseudo-boehmite into water with the mass fraction of 15%, hydrolyzing for 3h at the temperature of 25 ℃, mixing the hydrolyzed solution with 30% silica sol (alkaline nano-silica sol), phosphoric acid, cobalt nitrate, ferric nitrate and triethylamine together with water, wherein the molar ratio of silicon to aluminum to phosphorus to cobalt to iron to triethylamine is 0.75: 1: 0.25: 1.0: 1.0: 7, standing and aging at 50 ℃ for 12h, transferring the solution to a crystallization kettle, crystallizing at 210 ℃ for 72h, filtering to obtain a solid, freeze-drying the solid at the drying pressure of 20Pa and the temperature of-10 ℃, grinding the solid into powder after drying, roasting at 500 ℃ for 6h at the temperature of 2 ℃/min, soaking the roasted Fe-Co/SAPO in an aqueous solution of lanthanum nitrate and cesium nitrate for ultrasound, wherein the molar ratio of lanthanum to cesium to cobalt to iron is 1: 0.5: 1.0: 1.0, carrying out ultrasonic and freeze drying at the drying pressure of 20Pa and the temperature of-20 ℃, roasting at the roasting temperature of 500 ℃ for 6h at the temperature rise of 2 ℃/min after drying, and obtaining the catalyst after roasting.
The reaction conditions for synthesizing the ethoxyphenol are as follows:
the molar ratio of hydroquinone to ethanol is 1: 6, controlling the airspeed of hydroquinone to be 0.2h-1The reaction temperature is 230 ℃;
after 12h of reaction, a sample of the reaction solution was taken and the product was analyzed by GC chromatography. The analytical results are shown in Table 1.
Example 2
The preparation method of the catalyst comprises the following steps:
putting aluminum nitrate into water, hydrolyzing for 2h at 25 ℃ with the mass fraction of 15%, mixing the hydrolysis solution with 10% silica sol (alkaline nano-silica sol), phosphoric acid, cobalt chloride, ferric chloride and isopropylamine together with water, wherein the mol ratio of silicon to aluminum to phosphorus to cobalt to iron to isopropylamine is 0.2: 1: 0.2: 0.5: 1.5: 4, standing and aging for 20h at 25 ℃, transferring the solution to a crystallization kettle, crystallizing for 24h at 160 ℃, filtering to obtain a solid, freeze-drying the solid at the drying pressure of 150Pa and the temperature of-5 ℃, grinding the solid into powder after drying, roasting at 400 ℃, heating at 2 ℃/min for 10h, dipping the roasted Fe-Co/SAPO in an aqueous solution of lanthanum sulfate and cesium nitrate, and performing ultrasonic treatment, wherein the molar ratio of lanthanum sulfate to cesium nitrate to lanthanum, cesium, cobalt and iron in cobalt chloride and iron chloride is 1: 0.2: 0.5: 1.5, carrying out ultrasonic and freeze drying at the drying pressure of 100Pa and the temperature of-5 ℃, roasting at the roasting temperature of 450 ℃ for 10h at the temperature rise of 5 ℃/min after drying, and obtaining the catalyst after roasting.
The reaction conditions for synthesizing the ethoxyphenol are as follows:
the molar ratio of hydroquinone to ethanol is 1:5, controlling the airspeed of hydroquinone to be 0.1h-1The reaction temperature is 250 ℃;
after 12h of reaction, a sample of the reaction solution was taken and the product was analyzed by GC chromatography. The analytical results are shown in Table 1.
Example 3
Putting a certain amount of aluminum isopropoxide into water, hydrolyzing for 5h at 25 ℃ with the mass fraction of 10%, mixing the hydrolysis solution with 20% silica sol (alkaline nano silica sol), phosphoric acid, cobalt sulfate, ferric sulfate and tetraethylammonium hydroxide together with water, wherein the molar ratio of silicon to aluminum to phosphorus to cobalt to iron to tetraethylammonium hydroxide is 1.5: 1: 0.5: 2.0: 0.5: 6, standing and aging for 5h at 80 ℃, transferring the solution to a crystallization kettle, crystallizing for 120h at 260 ℃, filtering to obtain a solid, freeze-drying the solid at the drying pressure of 100Pa and the temperature of-10 ℃, grinding the solid into powder after drying, roasting for 4h at 600 ℃, heating at 1 ℃/min, dipping the roasted Fe-Co/SAPO into an aqueous solution of lanthanum nitrate and cesium sulfate for ultrasound, wherein the molar ratio of the lanthanum nitrate to the cesium sulfate to the elements of lanthanum, cesium, cobalt and iron in the iron sulfate is 1: 1: 2.0: 0.5, carrying out ultrasonic treatment, then carrying out freeze drying under the drying pressure of 100Pa and at the temperature of-10 ℃, roasting after drying is finished, wherein the roasting temperature is 600 ℃, the roasting time is 4h, the temperature rise is 1 ℃/min, and obtaining the catalyst after roasting is finished.
The reaction conditions for synthesizing the ethoxyphenol are as follows:
the molar ratio of hydroquinone to ethanol is 1:7, controlling the airspeed of the hydroquinone to be 0.5h-1The reaction temperature is 210 ℃;
after 12h of reaction, a sample of the reaction solution was taken and the product was analyzed by GC chromatography. The analytical results are shown in Table 1.
TABLE 1
| Examples | Conversion of Hydroquinone% | Selectivity to ethoxyphenol% | Yield of p-ethoxyphenol% |
| Example 1 | 97.6 | 92.8 | 90.6 |
| Example 2 | 93.1 | 94.8 | 88.3 |
| Example 3 | 98.1 | 88.6 | 86.9 |
After the catalyst of example 1 was used continuously for 3000 hours, the conversion of hydroquinone was found to be 94.6% and the yield of p-ethoxyphenol was found to be 88.3% by sampling analysis, which indicates that the catalyst still has high activity for synthesizing p-ethoxyphenol from hydroquinone and ethanol, and no significant decrease was observed.
Claims (10)
1. A preparation method of a supported composite metal oxide catalyst FeCoLaCs/SAPO comprises the following steps:
1) putting a certain amount of aluminum source into water for hydrolysis to obtain a hydrolysis solution;
2) mixing the hydrolysis solution with a silicon source, a phosphorus source, a cobalt source, an iron source, a template agent and water, standing and aging for a period of time;
3) sealing and crystallizing the aged solution;
4) separating the crystallized mixture to obtain a solid product;
5) freeze-drying the solid product to obtain a molecular sieve Fe-Co/SAPO;
6) roasting the molecular sieve Fe-Co/SAPO;
7) and (3) soaking the roasted Fe-Co/SAPO in an aqueous solution of a lanthanum source and a cesium source, then freeze-drying and roasting to obtain the catalyst.
2. The method as claimed in claim 1, wherein in step 1), the aluminum source is selected from one or more of pseudo-boehmite, aluminum nitrate and aluminum isopropoxide; the hydrolysis time is 2-5h, and the hydrolysis temperature is 20-30 ℃.
3. The method according to claim 1 or 2, wherein in step 2), the silicon source is silica sol;
the phosphorus source is one or more of phosphoric acid, trimethyl phosphate and triethyl phosphate;
the cobalt source is selected from one or more of cobalt chloride, cobalt sulfate and cobalt nitrate;
the iron source is selected from one or more of ferric chloride, ferric sulfate and ferric nitrate;
the template agent is selected from one or more of triethylamine, isopropylamine or tetraethylammonium hydroxide;
preferably, the mol ratio of Si, Al, P, Co, Fe and the template agent is 0.1-1.5: 1: 0.1-0.5: 0.1-2.0: 0.1-2.0: 3-8;
preferably, the aging temperature is 20-80 ℃ and the aging time is 2-24 hours.
4. The method as claimed in any one of claims 1 to 3, wherein, in the step 3), the crystallization temperature is 160-260 ℃ and the crystallization time is 24-120 hours.
5. The method according to any one of claims 1 to 4, wherein in step 5), the freeze-drying pressure is 10 to 200Pa and the temperature is-20 to-5 ℃.
6. The method according to any one of claims 1 to 5, wherein in the step 6), the roasting temperature is 400 to 600 ℃ and the time is 4 to 10 hours.
7. The method of any one of claims 1-6, wherein in step 7), the lanthanum source is one or more of lanthanum sulfate and lanthanum nitrate, and the cesium source is one or more of cesium sulfate and cesium nitrate;
preferably, the molar ratio of lanthanum, cesium, cobalt and iron is 1: 0.1-1: 0.1-2.0: 0.1-2.0;
preferably, the freeze drying pressure is 10-200 Pa, and the temperature is-20 to-5 ℃; the roasting temperature is 400-600 ℃, and the roasting time is 4-10 h.
8. The preparation method of p-ethoxyphenol is characterized by adopting hydroquinone and ethanol as raw materials to react under the catalysis of a supported composite metal oxide catalyst FeCoLaCs/SAPO to prepare the p-ethoxyphenol.
9. The process of claim 8, wherein the molar ratio of hydroquinone to ethanol is 1: 3-1: 10.
10. According to claim 8 or claim 8The method is characterized in that the reaction temperature is 200-260 ℃, and the mass space velocity of hydroquinone relative to the catalyst is 0.1-0.5 h-1。
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