CN114011457B - Preparation method of p-ethoxyphenol - Google Patents
Preparation method of p-ethoxyphenol Download PDFInfo
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- CN114011457B CN114011457B CN202111481940.3A CN202111481940A CN114011457B CN 114011457 B CN114011457 B CN 114011457B CN 202111481940 A CN202111481940 A CN 202111481940A CN 114011457 B CN114011457 B CN 114011457B
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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 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 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 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- 241000269350 Anura Species 0.000 claims abstract description 17
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 11
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 10
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 18
- 238000004108 freeze drying Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 230000007062 hydrolysis Effects 0.000 claims description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- 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
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-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
- 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
- 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
- 229910052782 aluminium Inorganic materials 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
- 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
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- 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
- 239000007864 aqueous solution Substances 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
- 239000002131 composite material Substances 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
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007789 sealing Methods 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
- 238000001354 calcination Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 238000001035 drying Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- MOEFFSWKSMRFRQ-UHFFFAOYSA-N 2-ethoxyphenol Chemical compound CCOC1=CC=CC=C1O MOEFFSWKSMRFRQ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 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
- 238000002791 soaking Methods 0.000 description 3
- 238000003786 synthesis reaction 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
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 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
- 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
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960005191 ferric oxide Drugs 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
- 239000002816 fuel 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
- 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
- -1 lanthanum cesium cobalt iron Chemical compound 0.000 description 1
- 238000011068 loading method Methods 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
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
- B01J29/82—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
Landscapes
- 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 synthesizing p-ethoxyphenol by continuously catalyzing hydroquinone and ethanol with high activity and high selectivity by adopting a SAPO molecular sieve doped with iron, cobalt, lanthanum and cesium as a catalyst. The process is environment-friendly, the reaction condition is mild, the p-ethoxyphenol can be continuously prepared, the catalyst can stably run for 3000 hours, and the activity is not obviously reduced.
Description
Technical field:
the invention relates to a preparation method of p-ethoxyphenol, in particular to a method for synthesizing p-ethoxyphenol by using a supported catalyst FeCoLacs/SAPO.
The background technology is as follows:
p-ethoxyphenol is an important chemical product, and is used as a polymerization inhibitor for synthesizing high molecular compounds, an anti-aging agent, a plasticizer, a fuel additive and the like in a large amount, and is also an intermediate for synthesizing fine chemical products such as medicines, pesticides, dyes, photographic sensitizers and the like.
At present, the preparation method of the p-ethoxyphenol mainly comprises the following three steps: (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 using hydroquinone and ethanol as raw materials through an electrolytic reaction, the electrolytic reaction preparation process has high energy consumption, is not suitable for industrial production, and has the problems of overhigh production cost and 85 percent of yield due to expensive materials such as electrodes and the like; (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 obtained raw materials, relatively stable process and suitability for large-scale industrial production. However, the process uses a liquid acid catalyst, and a series of operations such as alkali addition neutralization, filtration, extraction, reduced pressure distillation and the like are needed to be carried out in the subsequent reaction, so that the production flow is overlong.
The invention comprises the following steps:
the invention aims to provide a preparation method of a metal supported catalyst FeCoLaCs/SAPO, and the preparation method is applied to continuous production of catalytic synthesis of p-ethoxyphenol. The process has mild reaction condition, is environment-friendly, can continuously prepare p-ethoxyphenol, and has high reaction activity and good stability.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention firstly provides a preparation method of a supported lanthanum cesium cobalt iron composite metal oxide catalyst FeCoLaCs/SAPO, which comprises the following steps:
1) A certain amount of aluminum source is put into water for hydrolysis to obtain 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 standing and aging the solution for a period of time;
3) Then loading the aged solution into a crystallization kettle, and sealing for crystallization;
4) Cooling the crystallized mixture, and performing solid-liquid separation to obtain a solid product;
5) Freeze-drying the solid product to obtain a molecular sieve Fe-Co/SAPO;
6) Roasting a molecular sieve Fe-Co/SAPO;
7) And (3) immersing the baked molecular sieve Fe-Co/SAPO in an aqueous solution of a lanthanum source and a cesium source in an equivalent manner through ultrasonic, and then performing freeze drying and baking to obtain the catalyst.
In the preparation method of the catalyst, in the step 1), the Al source is one or more selected from pseudo-boehmite, aluminum nitrate and aluminum isopropoxide,
and (3) 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 that of water;
controlling the molar 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 to 2.0:3 to 8;
in the catalyst preparation method of the invention, 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 catalyst preparation method of the invention, in the step 4), the solid-liquid separation is realized by filtration.
In the catalyst preparation method of the invention, in the step 5), the freeze drying pressure is 10 Pa to 200Pa, 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 catalyst preparation method of the invention, 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,
the mole ratio of lanthanum, cesium, cobalt and iron is controlled 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, the pressure is 10 Pa to 200Pa, and the temperature is minus 20 ℃ to minus 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 ethoxyphenol:
the preferred steps are: filling the catalyst into a fixed bed, wherein the reaction raw materials are hydroquinone and ethanol mixed solution, and the mixed raw materials pass through the catalyst bed to obtain p-ethoxyphenol reaction liquid; separating and purifying the reaction liquid in a rectification mode to obtain pure p-ethoxyphenol;
in the invention, the mol ratio of hydroquinone to ethanol is 1:3 to 1:10, preferably 1:5 to 1:7;
in the invention, the reaction temperature is 200-260 ℃, the pressure is normal pressure, and the mass space velocity of hydroquinone relative to the catalyst is 0.1-0.5 h -1 。
In the invention, the reaction raw materials are all fed from the upper layer of the catalyst, and the bottom is discharged.
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, so that the structure of the molecular sieve is optimized, and catalytic active metals lanthanum and titanium are immersed in the framework, so that the p-ethoxyphenol can be synthesized by high-activity and high-selectivity catalytic hydroquinone and ethanol, 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: example 1 catalyst life test curve.
The specific embodiment is as follows:
for a better understanding of the present invention, reference will now be made to the following examples which are included to illustrate the general principles, features and advantages of the invention and are not to be construed as limiting the invention.
Example 1
The preparation method of the catalyst comprises the following steps:
placing pseudo-boehmite into water, hydrolyzing for 3 hours at 25 ℃, mixing the hydrolyzed solution with 30% of silica sol (alkaline nano silica sol), phosphoric acid, cobalt nitrate, ferric nitrate and triethylamine together with water, wherein the molar ratio of silicon, aluminum, phosphorus, cobalt, iron and triethylamine is 0.75:1:0.25:1.0: 1.0:7, standing and aging for 12 hours at 50 ℃, transferring the solution into a crystallization kettle, crystallizing for 72 hours at 210 ℃, filtering to obtain a solid, freeze-drying the solid, wherein the drying pressure is 20Pa, the temperature is-10 ℃, grinding the solid into powder after the drying is finished, roasting for 6 hours at 500 ℃, and the temperature rise is 2 ℃/min, and soaking the Fe-Co/SAPO obtained after roasting into a water solution of lanthanum nitrate and cesium nitrate for ultrasonic treatment, wherein the molar ratio of lanthanum, cesium, cobalt and iron is 1:0.5:1.0:1.0, performing ultrasonic freeze drying, wherein the drying pressure is 20Pa, the temperature is-20 ℃, roasting is performed after the drying is finished, the roasting temperature is 500 ℃, the roasting time is 6 hours, the temperature rise is 2 ℃/min, and the catalyst is obtained after the roasting is finished.
The reaction conditions for the synthesis of ethoxyphenol are as follows:
the mol ratio of hydroquinone to ethanol is 1:6, controlling the space velocity of hydroquinone to be 0.2h -1 The 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 analysis 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 2 hours at 25 ℃, mixing the hydrolyzed solution with 10% of silica sol (alkaline nano silica sol), phosphoric acid, cobalt chloride, ferric chloride and isopropylamine together with water, wherein the molar ratio of silicon, aluminum, phosphorus, cobalt, iron and isopropylamine is 0.2:1:0.2:0.5: 1.5:4, standing and aging for 20 hours at 25 ℃, transferring the solution into a crystallization kettle, crystallizing for 24 hours at 160 ℃, filtering to obtain a solid, freeze-drying the solid, wherein the drying pressure is 150Pa, the temperature is-5 ℃, grinding the solid into powder after the drying is finished, roasting for 10 hours at 400 ℃, and the temperature rise is 2 ℃/min, soaking the roasted Fe-Co/SAPO into a water solution of lanthanum sulfate and cesium nitrate for ultrasonic treatment, wherein the molar ratio of lanthanum sulfate, cesium nitrate, cobalt chloride and lanthanum, cesium, cobalt and iron in the ferric chloride is 1:0.2:0.5:1.5, freeze drying after ultrasonic treatment, wherein the drying pressure is 100Pa, the temperature is-5 ℃, roasting is carried out after the drying is finished, the roasting temperature is 450 ℃, the roasting time is 10 hours, the temperature rise is 5 ℃/min, and the catalyst is obtained after the roasting is finished.
The reaction conditions for the synthesis of ethoxyphenol are as follows:
the mol ratio of hydroquinone to ethanol is 1:5, controlling the space velocity of hydroquinone to be 0.1h -1 The 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 analysis results are shown in Table 1.
Example 3
Putting a certain amount of aluminum isopropoxide into water, hydrolyzing for 5 hours at 25 ℃, mixing the hydrolyzed solution with 20% of silica sol (alkaline nano silica sol), phosphoric acid, cobalt sulfate, ferric sulfate and tetraethylammonium hydroxide together with water, wherein the molar ratio of silicon, aluminum, phosphorus, cobalt, iron and tetraethylammonium hydroxide is 1.5:1:0.5:2.0: 0.5:6, standing and aging for 5 hours at 80 ℃, transferring the solution into a crystallization kettle, crystallizing for 120 hours at 260 ℃, filtering to obtain a solid, freeze-drying the solid, wherein the drying pressure is 100Pa, the temperature is-10 ℃, grinding the solid into powder after the drying is finished, roasting for 4 hours at 600 ℃, and the temperature rise is 1 ℃/min, soaking the Fe-Co/SAPO obtained after roasting into an aqueous solution of lanthanum nitrate and cesium sulfate for ultrasonic treatment, wherein the molar ratio of lanthanum nitrate and cesium sulfate to elements of lanthanum, cesium, cobalt and iron in cobalt sulfate and iron sulfate is 1:1:2.0: and 0.5, performing ultrasonic freeze drying, wherein the drying pressure is 100Pa, the temperature is-10 ℃, roasting is performed after the drying is finished, the roasting temperature is 600 ℃, the roasting time is 4 hours, the temperature rise is 1 ℃/min, and the catalyst is obtained after the roasting is finished.
The reaction conditions for the synthesis of ethoxyphenol are as follows:
the mol ratio of hydroquinone to ethanol is 1:7, controlling the space velocity of hydroquinone to be 0.5h -1 The 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 analysis results are shown in Table 1.
TABLE 1
| Examples | Conversion of hydroquinone% | P-ethoxyphenol Selectivity% | 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 is continuously used for 3000 hours, the conversion rate of hydroquinone is 94.6 percent and the yield of p-ethoxyphenol is 88.3 percent by sampling analysis, which indicates that the catalyst has higher activity for synthesizing p-ethoxyphenol from hydroquinone and ethanol and does not obviously decrease.
Claims (14)
1. A preparation method of a supported composite metal oxide catalyst FeCoLaCs/SAPO comprises the following steps:
1) A certain amount of aluminum source is put into water for hydrolysis to obtain 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 a molecular sieve Fe-Co/SAPO;
7) Immersing the roasted Fe-Co/SAPO in aqueous solution of a lanthanum source and a cesium source, and then freeze-drying and roasting to obtain the catalyst.
2. The method of claim 1, wherein in step 1), the aluminum source is selected from one or more of pseudo-boehmite, aluminum nitrate, aluminum isopropoxide; the hydrolysis time is 2-5h, and the hydrolysis temperature is 20-30 ℃.
3. The method of claim 1, wherein in step 2), the silicon source is a 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.
4. A method according to any one of claims 1 to 3 wherein the molar ratio of Si, al, P, co, fe to templating agent is from 0.1 to 1.5:1:0.1 to 0.5:0.1 to 2.0:0.1 to 2.0:3 to 8.
5. A process according to any one of claims 1 to 3, wherein the ageing temperature is 20 to 80 ℃ and the ageing time is 2 to 24 hours.
6. A process according to any one of claims 1 to 3, wherein in step 3) the crystallization temperature is 160 to 260 ℃ and the crystallization time is 24 to 120 hours.
7. A process according to any one of claims 1 to 3, wherein in step 5) the freeze-drying pressure is between 10 and 200Pa and the temperature is between-20 and-5 ℃.
8. A process according to any one of claims 1 to 3, wherein in step 6) the calcination temperature is 400 to 600 ℃ for a period of 4 to 10 hours.
9. The method of claim 1, 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.
10. The method of any one of claims 1-3, 9, wherein the molar ratio of lanthanum, cesium, cobalt, iron is 1:0.1-1:0.1-2.0:0.1-2.0.
11. The method according to claim 1, wherein in step 7), the freeze-drying pressure is 10 to 200Pa and the temperature is-20 to-5 ℃; the roasting temperature is 400-600 ℃ and the roasting time is 4-10 h.
12. A method for preparing p-ethoxyphenol, which is characterized in that hydroquinone and ethanol are adopted as raw materials, and the p-ethoxyphenol is prepared by reaction under the catalysis of a supported composite metal oxide catalyst FeCoLacs/SAPO prepared by the method according to any one of claims 1-11.
13. The method according to claim 12, wherein the molar ratio of hydroquinone to ethanol is 1: 3-1:10.
14. According to claim 12 or 13The 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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