CN115784850B - Method for preparing diethyl ether as byproduct in production of m-ethoxyphenol - Google Patents
Method for preparing diethyl ether as byproduct in production of m-ethoxyphenol Download PDFInfo
- Publication number
- CN115784850B CN115784850B CN202211586432.6A CN202211586432A CN115784850B CN 115784850 B CN115784850 B CN 115784850B CN 202211586432 A CN202211586432 A CN 202211586432A CN 115784850 B CN115784850 B CN 115784850B
- Authority
- CN
- China
- Prior art keywords
- dysprosium
- mass
- diethyl ether
- graphene
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 238000000034 method Methods 0.000 title claims abstract description 37
- VBIKLMJHBGFTPV-UHFFFAOYSA-N 3-ethoxyphenol Chemical compound CCOC1=CC=CC(O)=C1 VBIKLMJHBGFTPV-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000006227 byproduct Substances 0.000 title claims abstract description 10
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000003054 catalyst Substances 0.000 claims abstract description 78
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 40
- 239000002808 molecular sieve Substances 0.000 claims abstract description 40
- 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 40
- 229910052742 iron Inorganic materials 0.000 claims abstract description 36
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 31
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- NOTQUFQJAWMLCE-UHFFFAOYSA-N dysprosium(3+) trinitrate pentahydrate Chemical compound O.O.O.O.O.[Dy+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O NOTQUFQJAWMLCE-UHFFFAOYSA-N 0.000 claims description 12
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- DCKWZDOAGNMKMX-UHFFFAOYSA-N dysprosium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Dy+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DCKWZDOAGNMKMX-UHFFFAOYSA-N 0.000 claims description 5
- MAYVZUQEFSJDHA-UHFFFAOYSA-N 1,5-bis(methylsulfanyl)naphthalene Chemical compound C1=CC=C2C(SC)=CC=CC2=C1SC MAYVZUQEFSJDHA-UHFFFAOYSA-N 0.000 claims description 4
- XPEKDHWAGKXPST-UHFFFAOYSA-N dysprosium(3+);propan-2-olate Chemical compound [Dy+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] XPEKDHWAGKXPST-UHFFFAOYSA-N 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 34
- 238000004817 gas chromatography Methods 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- -1 m-hydroxyphenylethyl ether Chemical compound 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- MKGFYMKFBCWNCP-UHFFFAOYSA-N 1,3-diethoxybenzene Chemical group CCOC1=CC=CC(OCC)=C1 MKGFYMKFBCWNCP-UHFFFAOYSA-N 0.000 description 1
- DIBLUMFNEOKXMN-UHFFFAOYSA-N C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1(=CC=CC=C1)C Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1(=CC=CC=C1)C DIBLUMFNEOKXMN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Abstract
The invention relates to a method for preparing by-product diethyl ether in the production of m-ethoxyphenol, which comprises the steps of introducing diethyl ether and resorcinol into a composite catalyst of dysprosium type catalyst loaded by graphene and iron type catalyst loaded by USY molecular sieve, and reacting to prepare the m-ethoxyphenol. The method of the invention realizes the reuse of the diethyl ether byproduct waste, and simultaneously provides a novel synthesis process of the m-ethoxyphenol.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to a process for preparing m-ethoxyphenol by using diethyl ether and resorcinol which are byproducts in the production of m-ethoxyphenol.
Background
The m-ethoxyphenol is also called m-hydroxyphenylethyl ether, and the English name is m-hydroxyphenole, and is an important medical and dye intermediate. At present, resorcinol is mainly obtained by reacting resorcinol with an alkylating reagent, and ethanol is a relatively safe, clean and low-cost reagent compared with other alkylating reagents (diethyl sulfate, bromoethane and iodoethane), and is a mainstream direction of future development. Because the technology adopts weak acid and weak base catalyst, a part of ethanol generates diethyl ether under the catalysis of acid center. For the diethyl ether by-produced in the process, no effective utilization mode is available in industry, and the diethyl ether is generally directly burnt, so that great resource waste is caused.
Therefore, how to use the by-product diethyl ether to generate larger economic value is a problem to be solved in the future.
Disclosure of Invention
The invention aims to provide a method for preparing diethyl ether by-product in the production of m-ethoxyphenol, which adopts a novel catalyst to catalyze resorcinol and diethyl ether to prepare m-ethoxyphenol. The process adopts a continuous fixed bed process, has good reactivity and selectivity, and can realize long-period stable operation.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing diethyl ether as byproduct in the production of m-ethoxyphenol is characterized in that resorcinol and diethyl ether are catalyzed to generate m-ethoxyphenol under the action of a catalyst, wherein the catalyst is a composite catalyst of dysprosium type supported by graphene and iron type supported by USY molecular sieve.
In a specific embodiment, the catalytic reaction of resorcinol with diethyl ether is carried out in a fixed bed; preferably, the resorcinol is added in an amount of 23-45% of the total mass of resorcinol and diethyl ether.
In a specific embodiment, the resorcinol and diethyl ether are reacted at a temperature of 250-350℃and a reaction pressure of 0.3-1.5bar (G).
In a specific embodiment, the resorcinol has a liquid hourly mass space velocity of from 0.4 to 2.4h -1 。
In a specific embodiment, the preparation method of the composite catalyst of the dysprosium type and USY molecular sieve supported iron type catalyst loaded by graphene comprises the following steps:
(1) Adding a dysprosium source into pure water, adding graphene, and uniformly stirring;
(2) Adding ammonia water into the solution in the step (1) to adjust the pH value to a target value, and then drying and calcining to obtain the dysprosium-type catalyst loaded by graphene;
(3) Dissolving an iron source in pure water, adding a USY molecular sieve, and uniformly stirring;
(4) Adding ammonia water into the solution in the step (3), regulating the pH value to a target value, and then drying and calcining to obtain an iron-type catalyst loaded by the USY molecular sieve;
(5) And (3) mixing the dysprosium type catalyst loaded by the graphene prepared in the step (2) and the iron type catalyst loaded by the USY molecular sieve prepared in the step (4) according to a certain proportion to obtain the composite catalyst.
In a specific embodiment, in the step (1), the dysprosium source is selected from one or more of dysprosium nitrate pentahydrate, dysprosium nitrate hexahydrate, dysprosium chloride or dysprosium isopropoxide, and the mass of the water is 8-20 times the mass of the dysprosium source; preferably, the addition amount of the graphene is 10-20 times of the mass of the dysprosium source.
In a specific embodiment, in the step (2), ammonia water is added to adjust the pH value to 6.5-8.5; preferably, the drying temperature is 110-130 ℃ and the drying time is 8-24 hours; more preferably, the calcination is carried out in an air atmosphere at a calcination temperature of 450-600 ℃ for a calcination time of 6-15 hours.
In a specific embodiment, in step (3), the iron source is selected from one or more of ferric nitrate nonahydrate, ferric trichloride anhydrous and ferric trichloride hexahydrate; the mass of the water is 10-30 times of that of the iron source; preferably, the USY molecular sieve is added in an amount of 15-25 times the iron source.
In a specific embodiment, in the step (4), ammonia is added to adjust the pH to 5.5-7.5; preferably, the drying temperature is 110-130 ℃ and the drying time is 8-24 hours; more preferably, the calcination is carried out in an air atmosphere at a calcination temperature of 400-550 ℃ for a calcination time of 5-12 hours.
In a specific embodiment, in step (5), the mass of the dysprosium type catalyst supported by graphene is 0.1 to 10 times the mass of the iron type catalyst supported by USY molecular sieve.
Compared with the prior art, the invention has the beneficial effects that:
1) The method of the invention realizes the reutilization of diethyl ether in the production of the m-ethoxyphenol, and simultaneously provides a novel synthesis process of the m-ethoxyphenol.
2) The method develops a high-efficiency composite catalyst, and the conversion rate of resorcinol is up to 81% and the highest selectivity of m-ethoxyphenol can be up to 92% by using a continuous fixed bed process.
Detailed Description
The following examples will further illustrate the method provided by the present invention for a better understanding of the technical solution of the present invention, but the present invention is not limited to the examples listed but should also include any other known modifications within the scope of the claims of the present invention.
A method for preparing by-product diethyl ether from m-ethoxyphenol adopts a novel catalyst to catalyze toluene diphenol and diethyl ether to generate m-ethoxyphenol.
The novel catalyst is a composite catalyst of a dysprosium type catalyst loaded by graphene and an iron type catalyst loaded by USY molecular sieve. The preparation process of the composite catalyst of the dysprosium type catalyst loaded by graphene and the iron type catalyst loaded by USY molecular sieve comprises the following steps:
(1) Adding a certain amount of dysprosium source into the pure water;
(2) Adding a certain amount of graphene into the solution, and uniformly stirring;
(3) Adding ammonia water into the solution in the step (2), and regulating the pH value to a certain value;
(4) Drying the solution of step (3) at a temperature for a period of time;
(5) Roasting the dried sample in the step (4) in an air atmosphere to obtain a dysprosium-type catalyst loaded by graphene;
(6) Dissolving a certain iron source in pure water;
(7) Adding a certain amount of USY molecular sieve into the solution in the step (6), and uniformly stirring;
(8) Adding ammonia water into the solution obtained in the step (7), and regulating the pH value to a certain value;
(9) Drying the solution in the step (8) for a period of time at a certain temperature;
(10) And (3) roasting the dried sample in the step (9) in an air atmosphere to obtain the USY molecular sieve supported iron catalyst.
(11) And mixing the dysprosium catalyst loaded by graphene and the iron catalyst loaded by the USY molecular sieve according to a certain proportion to obtain the final composite catalyst.
Wherein in the step (1), the dysprosium source is one or more of dysprosium nitrate pentahydrate (also referred to as dysprosium nitrate pentahydrate in the present invention), dysprosium nitrate hexahydrate, dysprosium chloride and dysprosium isopropoxide, and the mass of water is 8-20 times, for example 8-fold, 9-fold, 10-fold, 11-fold, 12-fold, 13-fold, 14-fold, 15-fold, 16-fold, 17-fold, 18-fold, 19-fold, 20-fold, etc., of the mass of the dysprosium source.
In the step (2), the addition amount of the graphene is 10-20 times, such as 10 times, 11 times, 12 times, 13 times, 14 times, 15 times, 16 times, 17 times, 18 times, 19 times, 20 times, and the like, of the mass of the dysprosium source.
In the step (3), ammonia is added to adjust the pH to 6.5 to 8.5, for example, to 6.5, 7, 7.5, 8, 8.5, etc., wherein the concentration of ammonia is not particularly limited, and the ammonia may be adjusted to a target pH, for example, 15% by mass.
In the step (4), the drying temperature is 110-130 ℃, including but not limited to 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, and the drying time is 8-24 hours, including but not limited to 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours.
In the step (5), the roasting temperature is 450-600 ℃, such as 450 ℃,500 ℃,550 ℃, 600 ℃ and the like, and the roasting time is 6-15h, such as 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h and the like.
In the step (6), the iron source is one or more of ferric nitrate nonahydrate (also referred to as ferric nitrate nonahydrate in the invention), anhydrous ferric trichloride and ferric trichloride hexahydrate; the mass of water is 10 to 30 times, for example, 8 times, 9 times, 10 times, 11 times, 12 times, 13 times, 14 times, 15 times, 16 times, 17 times, 18 times, 19 times, 20 times, 21 times, 22 times, 23 times, 24 times, 25 times, 26 times, 27 times, 28 times, 29 times, 30 times, or the like, the mass of the iron source.
In the step (7), the USY molecular sieve is added 15 to 25 times, for example 15 times, 16 times, 17 times, 18 times, 19 times, 20 times, 21 times, 22 times, 23 times, 24 times, 25 times, etc., of the iron source.
In the step (8), ammonia is added to adjust the pH to 5.5 to 7.5, for example, to 5.5, 6, 6.5, 7, 7.5, etc., wherein the concentration of ammonia is not particularly limited, and the ammonia may be adjusted to a target pH, for example, 15% by mass.
In the step (9), the drying temperature is 110-130 ℃, including but not limited to 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, and the drying time is 8-24 hours, including but not limited to 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours.
In the step (10), the baking temperature is 400-550 ℃, for example, 450 ℃,500 ℃,550 ℃, etc., and the baking time is 5-12 hours, for example, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, etc.
In the step (11), the mass of the dysprosium type catalyst supported by the graphene is 0.1-10 times, for example 0.1 times, 0.5 times, 1 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, and the like, of the mass of the iron type catalyst supported by the USY molecular sieve.
In the present invention, the reaction of resorcinol with diethyl ether may be carried out in a fluidized bed or a fixed bed, preferably using a continuous fixed bed process.
Wherein the resorcinol is added in an amount of 23-45% of the total mass of resorcinol and diethyl ether, including, for example, but not limited to, 23%, 25%, 30%, 35%, 40%, 45%.
The resorcinol and diethyl ether have a reaction temperature of 250-350 ℃, including, for example, but not limited to, 250 ℃, 280 ℃, 300 ℃, 325 ℃, 350 ℃; the reaction pressure is 0.3-1.5bar (G), including for example but not limited to 0.3bar (G), 0.5bar (G), 0.8bar (G), 1.0bar (G), 1.1bar (G), 1.2bar (G), 1.3bar (G), 1.4bar (G), 1.5bar (G); the liquid hourly mass space velocity of the resorcinol is 0.4-2.4h -1 For example, include but are not limited to 0.4h -1 、0.6h -1 、0.8h -1 、1.0h -1 、1.2h -1 、1.4h -1 、1.6h -1 、1.8h -1 、2.0h -1 、2.2h -1 、2.4h -1 。
The following examples are presented to further illustrate the invention, but are not to be construed as limiting in any way.
The diethyl ether in the following examples directly adopts outsourced diethyl ether reagent to replace diethyl ether which is by-produced in the production of m-ethoxyphenol, and those skilled in the art can understand that the reaction solution containing the by-produced diethyl ether in the production of m-ethoxyphenol can obtain diethyl ether by rectification, the purity of the diethyl ether can reach 99%, and the impurities are the same as the reagent.
Gas chromatography: the composition of resorcinol-diethyl ether reaction liquid was analyzed by gas chromatography under the following operating conditions: the use of Shimadzu GC-2030 gas chromatography, DB-5MS UI (20 m 0.25mm 0.25 μm) column chromatography, acetonitrile as the dilution solvent. The temperature of the vaporization chamber is 300 ℃, the flow rate of the column is 1.00mL/min, and the sample injection amount is 0.2 mu L. Chromatographic column temperature programming: the temperature is firstly increased to 100 ℃ at the temperature rising rate of 2 ℃/min at 40 ℃ and finally to 300 ℃ at the temperature rising rate of 10 ℃/min.
The reactor used in the examples: the reaction adopts a stainless steel fixed bed reactor, the inner diameter of a reaction tube is 19mm, and two ends of a catalyst are filled with alpha-Al with the diameter of phi 3mm 2 O 3 Porcelain ball.
The sources of the raw materials used are as follows:
example 1
The preparation method of the catalyst comprises the following steps:
(1) 10g of dysprosium nitrate pentahydrate was dissolved in pure water, the mass of water being 10 times the mass of dysprosium nitrate pentahydrate.
(2) Adding graphene into the solution, wherein the adding amount of the graphene is 19 times of the mass of dysprosium nitrate pentahydrate, and uniformly stirring;
(3) Adding 15% ammonia water to the solution obtained in the step (2), and adjusting the pH to 6.8;
(4) Drying the solution in the step (3) at 110 ℃ for 22 hours;
(5) Roasting the dried sample in the step (4) in an air atmosphere at 500 ℃ for 8 hours to obtain a dysprosium-type catalyst loaded by graphene;
(6) 10g of ferric nitrate nonahydrate is dissolved in pure water, and the mass of the water is 20 times that of the ferric nitrate nonahydrate;
(7) Adding USY molecular sieve into the solution in the step (6), wherein the adding amount of the USY molecular sieve is 22 times of the mass of ferric nitrate nonahydrate, and stirring uniformly;
(8) Adding 15% ammonia water to the solution obtained in the step (7), and adjusting the pH to 7.2;
(9) Drying the solution in the step (8) for 9 hours at 130 ℃;
(10) And (3) roasting the dried sample in the step (9) in an air atmosphere at 550 ℃ for 6 hours to obtain the USY molecular sieve supported iron catalyst.
(11) The dysprosium type catalyst loaded by graphene and the iron type catalyst loaded by USY molecular sieve are mixed according to the ratio of 0.3:1 to obtain the final composite catalyst.
The reaction conditions of resorcinol and diethyl ether were as follows:
the resorcinol and diethyl ether are reacted using a continuous fixed bed process. The addition amount of resorcinol is 35% of the total mass of resorcinol and diethyl ether. The reaction temperature of resorcinol and diethyl ether was 270 ℃. The reaction pressure was 1.3bar (G). The liquid hourly mass space velocity of resorcinol is 0.6h -1 。
The reaction was stabilized and the sample was taken and analyzed by gas chromatography, and the specific results of examples are shown in Table 1.
Example 2
The preparation method of the catalyst comprises the following steps:
(1) 10g of dysprosium chloride was dissolved in pure water, the mass of which was 13 times the mass of dysprosium nitrate pentahydrate.
(2) Adding a certain amount of graphene into the solution, wherein the adding amount of the graphene is 12 times of the mass of dysprosium nitrate pentahydrate, and uniformly stirring;
(3) Adding 15% ammonia water to the solution obtained in the step (2), and adjusting the pH to 8.3;
(4) Drying the solution in the step (3) at 120 ℃ for 18 hours;
(5) Roasting the dried sample in the step (4) in an air atmosphere at 460 ℃ for 10 hours to obtain a dysprosium-type catalyst loaded by graphene;
(6) 10g of anhydrous ferric trichloride is dissolved in pure water, and the mass of water is 15 times of that of the anhydrous ferric trichloride;
(7) Adding a certain amount of USY molecular sieve into the solution in the step (6), wherein the adding amount of the USY molecular sieve is 16 times of the mass of the anhydrous ferric trichloride, and stirring uniformly;
(8) Adding 15% ammonia water to the solution obtained in the step (7), and adjusting the pH to 7.0;
(9) Drying the solution in the step (8) at 120 ℃ for 19h;
(10) And (3) roasting the dried sample in the step (9) in an air atmosphere at 510 ℃ for 10 hours to obtain the USY molecular sieve supported iron catalyst.
(11) And mixing the dysprosium catalyst loaded by graphene and the iron catalyst loaded by the USY molecular sieve according to the mass ratio of 2.2:1 to obtain the final composite catalyst.
The reaction conditions of resorcinol and diethyl ether were as follows:
the resorcinol and diethyl ether are reacted using a continuous fixed bed process. The addition amount of resorcinol was 42% of the total mass of resorcinol and diethyl ether. The reaction temperature of resorcinol and diethyl ether was 290 ℃. The reaction pressure was 1.1bar (G). The liquid hourly mass space velocity of resorcinol is 1.2h -1 。
The reaction was stabilized and the sample was taken and analyzed by gas chromatography, and the specific results of examples are shown in Table 1.
Example 3
The preparation method of the catalyst comprises the following steps:
(1) 10g of dysprosium nitrate hexahydrate was dissolved in pure water, the mass of water being 19 times the mass of dysprosium nitrate pentahydrate.
(2) Adding a certain amount of graphene into the solution, wherein the adding amount of the graphene is 15 times of the mass of the dysprosium nitrate hexahydrate, and uniformly stirring;
(3) Adding 15% ammonia water to the solution obtained in the step (2), and adjusting the pH to 7.2;
(4) Drying the solution in the step (3) at 120 ℃ for 16 hours;
(5) Roasting the dried sample in the step (4) under an air atmosphere for 12 hours at 590 ℃ to obtain a dysprosium-type catalyst loaded by graphene;
(6) 10g of ferric nitrate nonahydrate is dissolved in pure water, and the mass of the water is 24 times that of the ferric nitrate nonahydrate;
(7) Adding a certain amount of USY molecular sieve into the solution in the step (6), wherein the adding amount of the USY molecular sieve is 18 times of the mass of ferric nitrate nonahydrate, and stirring uniformly;
(8) Adding 15% ammonia water to the solution obtained in the step (7), and adjusting the pH to 6.7;
(9) Drying the solution in the step (8) for 14 hours at 120 ℃;
(10) And (3) roasting the dried sample in the step (9) in an air atmosphere at 460 ℃ for 8 hours to obtain the USY molecular sieve supported iron catalyst.
(11) And mixing the dysprosium catalyst loaded by graphene and the iron catalyst loaded by the USY molecular sieve in a mass ratio of 5:1 to obtain the final composite catalyst.
The reaction conditions of resorcinol and diethyl ether were as follows:
the resorcinol and diethyl ether are reacted using a continuous fixed bed process. The addition amount of resorcinol is 28% of the total mass of resorcinol and diethyl ether. The reaction temperature of resorcinol and diethyl ether was 340 ℃. The reaction pressure was 0.5bar (G). The liquid hourly mass space velocity of resorcinol is 2h -1 。
The reaction was stabilized and the sample was taken and analyzed by gas chromatography, and the specific results of examples are shown in Table 1.
Example 4
The preparation method of the catalyst comprises the following steps:
(1) 10g of dysprosium isopropoxide was dissolved in pure water, the mass of which was 16 times the mass of dysprosium nitrate pentahydrate.
(2) Adding a certain amount of graphene into the solution, wherein the adding amount of the graphene is 17 times of the mass of dysprosium nitrate pentahydrate, and uniformly stirring;
(3) Adding 15% ammonia water to the solution obtained in the step (2), and adjusting the pH to 7.6;
(4) Drying the solution in the step (3) at 130 ℃ for 12 hours;
(5) Roasting the dried sample in the step (4) in an air atmosphere at 530 ℃ for 15 hours to obtain a dysprosium-type catalyst loaded by graphene;
(6) 10g of ferric trichloride hexahydrate was dissolved in pure water, the mass of water being 29 times that of ferric trichloride hexahydrate;
(7) Adding a certain amount of USY molecular sieve into the solution in the step (6), wherein the adding amount of the USY molecular sieve is 24 times of the mass of the ferric trichloride hexahydrate, and stirring uniformly;
(8) Adding 15% ammonia water to the solution obtained in the step (7), and adjusting the pH to 5.8;
(9) Drying the solution in the step (8) at 110 ℃ for 21h;
(10) And (3) roasting the dried sample in the step (9) in an air atmosphere at 420 ℃ for 11 hours to obtain the USY molecular sieve supported iron catalyst.
(11) And mixing the dysprosium catalyst loaded by graphene and the iron catalyst loaded by the USY molecular sieve in a mass ratio of 8:1 to obtain the final composite catalyst.
The reaction conditions of resorcinol and diethyl ether were as follows:
the resorcinol and diethyl ether are reacted using a continuous fixed bed process. The addition amount of resorcinol is 31% of the total mass of resorcinol and diethyl ether. The reaction temperature of resorcinol and diethyl ether was 310 ℃. The reaction pressure was 0.7bar (G). The liquid hourly mass space velocity of resorcinol is 1.6h -1 。
The reaction was stabilized and the sample was taken and analyzed by gas chromatography, and the specific results of examples are shown in Table 1.
Comparative example 1
The difference from example 1 is that: the catalyst only uses dysprosium type catalyst loaded by graphene.
Comparative example 2
The difference from example 1 is that: the catalyst used was only an iron type catalyst supported on USY molecular sieve.
Table 1 conversion and selectivity for each example
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (17)
1. A method for producing diethyl ether by-product by using m-ethoxyphenol is characterized in that resorcinol and diethyl ether are catalyzed to generate m-ethoxyphenol under the action of a catalyst, wherein the catalyst is a composite catalyst of dysprosium type catalyst loaded by graphene and iron type catalyst loaded by USY molecular sieve;
the mass of the dysprosium type catalyst loaded by the graphene is 0.1-10 times of that of the iron type catalyst loaded by the USY molecular sieve.
2. The method according to claim 1, wherein the catalytic reaction of resorcinol with diethyl ether is carried out in a fixed bed.
3. The method according to claim 2, wherein the resorcinol is added in an amount of 23-45% of the total mass of resorcinol and diethyl ether.
4. The process according to claim 1 or 2, wherein the resorcinol and diethyl ether are reacted at a temperature of 250-350 ℃ and a reaction pressure of 0.3-1.5bar (G).
5. A process according to any one of claims 1 to 3, wherein the resorcinol has a liquid hourly space velocity of from 0.4 to 2.4h -1 。
6. A method according to any one of claims 1 to 3, wherein the preparation method of the composite catalyst of the dysprosium type and USY molecular sieve supported iron type catalyst supported by graphene comprises the following steps:
(1) Adding a dysprosium source into pure water, adding graphene, and uniformly stirring;
(2) Adding ammonia water into the solution in the step (1) to adjust the pH value to a target value, and then drying and calcining to obtain the dysprosium-type catalyst loaded by graphene;
(3) Dissolving an iron source in pure water, adding a USY molecular sieve, and uniformly stirring;
(4) Adding ammonia water into the solution in the step (3), regulating the pH value to a target value, and then drying and calcining to obtain an iron-type catalyst loaded by the USY molecular sieve;
(5) And (3) mixing the dysprosium type catalyst loaded by the graphene prepared in the step (2) and the iron type catalyst loaded by the USY molecular sieve prepared in the step (4) according to a certain proportion to obtain the composite catalyst.
7. The method of claim 6, wherein in step (1), the dysprosium source is selected from one or more of dysprosium nitrate pentahydrate, dysprosium nitrate hexahydrate, dysprosium chloride, or dysprosium isopropoxide, and the mass of water is 8-20 times the mass of the dysprosium source.
8. The method of claim 7, wherein the graphene is added in an amount of 10-20 times the mass of the dysprosium source.
9. The method according to claim 7 or 8, wherein in the step (2), ammonia water is added to adjust the pH to 6.5 to 8.5.
10. The method according to claim 9, wherein in the step (2), the drying temperature is 110 to 130 ℃ and the drying time is 8 to 24 hours.
11. The method according to claim 10, wherein in the step (2), the calcination is performed under an air atmosphere at a calcination temperature of 450 to 600 ℃ for a calcination time of 6 to 15 hours.
12. The method of claim 6, wherein in step (3), the iron source is selected from one or more of ferric nitrate nonahydrate, ferric trichloride anhydrous, and ferric trichloride hexahydrate; the mass of the water is 10-30 times of that of the iron source.
13. The method of claim 12, wherein USY molecular sieve is added in an amount of 15-25 times the iron source.
14. The method according to claim 6 or 12, wherein in the step (4), ammonia is added to adjust the pH to 5.5 to 7.5.
15. The method of claim 14, wherein the drying temperature is 110-130 ℃ and the drying time is 8-24 hours.
16. The method according to claim 15, wherein the calcination is carried out in an air atmosphere at a calcination temperature of 400-550 ℃ for a calcination time of 5-12 hours.
17. The method according to claim 6, wherein in the step (5), the mass of the dysprosium type catalyst supported on graphene is 0.1 to 10 times the mass of the iron type catalyst supported on USY molecular sieve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211586432.6A CN115784850B (en) | 2022-12-09 | 2022-12-09 | Method for preparing diethyl ether as byproduct in production of m-ethoxyphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211586432.6A CN115784850B (en) | 2022-12-09 | 2022-12-09 | Method for preparing diethyl ether as byproduct in production of m-ethoxyphenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115784850A CN115784850A (en) | 2023-03-14 |
| CN115784850B true CN115784850B (en) | 2024-02-27 |
Family
ID=85419198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211586432.6A Active CN115784850B (en) | 2022-12-09 | 2022-12-09 | Method for preparing diethyl ether as byproduct in production of m-ethoxyphenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115784850B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114349611A (en) * | 2022-01-04 | 2022-04-15 | 万华化学集团股份有限公司 | Preparation method of m-ethoxyphenol |
-
2022
- 2022-12-09 CN CN202211586432.6A patent/CN115784850B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114349611A (en) * | 2022-01-04 | 2022-04-15 | 万华化学集团股份有限公司 | Preparation method of m-ethoxyphenol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115784850A (en) | 2023-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| BRPI0614960A2 (en) | fluidized bed catalyst for gas phase reactions, processes for its production, and for catalytically oxidizing hydrogen chloride, and use of catalyst | |
| CN111992241A (en) | Catalyst for synthesizing hexamethylene diamine key intermediate and preparation method and application thereof | |
| CN115784850B (en) | Method for preparing diethyl ether as byproduct in production of m-ethoxyphenol | |
| JP2019526588A (en) | Method for producing 1,3-cyclohexanedimethanol | |
| CN109422657B (en) | Method for separating methylamine mixed gas and co-producing formamide compound | |
| CN108786922B (en) | Preparation method of nickel and palladium modified nano silicon dioxide for coupling reaction | |
| CN104557468B (en) | Method for phenol hydroxylation | |
| CN112739674B (en) | Method for producing chloromethane by multistage reaction | |
| US2502678A (en) | Method for preparing acrylonitrile by vapor phase catalytic reaction of acetylene and hydrogen cyanide | |
| JPS6193154A (en) | Manufacture of methylmercaptane | |
| CN107311839B (en) | The fluoro- chlorine exchange system of gas phase for seven fluorine cyclopentene method | |
| CN115999607A (en) | Preparation method and application of hydrogen chloride catalytic oxidation catalyst | |
| CN113304747B (en) | Catalyst for preparing 2-methylpyridine, preparation method and method for preparing 2-methylpyridine by using same | |
| CN112210055B (en) | Polymer with hollow core-shell structure and preparation method thereof | |
| KR100851725B1 (en) | Method for producing a palladium-containing hydrogenation catalyst | |
| CN102781894B (en) | Process for producing methyl chloride and sulfur dioxide | |
| JPH03246269A (en) | Method for increasing yield of acetonitrile | |
| JPH07275711A (en) | Nickel-supported catalyst for modifying hydrocarbon and production thereof | |
| CN111847477A (en) | Preparation method and application of HZSM-5/HMS composite molecular sieve | |
| CN115819192B (en) | Preparation method of m-methoxyphenol | |
| Tian et al. | Deciphering structural evolution of adsorbed˙ OH species on Zr-oxo nodes of UiO-66 to modulate methane hydroxylation | |
| CN115672394A (en) | Preparation method of Cs/Eu-AFN molecular sieve catalyst and preparation method of 1,2-di-n-propoxybenzene | |
| CN109248699A (en) | The method of cyclohexane oxidation KA oil | |
| JP2819572B2 (en) | Crystalline aluminophosphate and method for producing the same | |
| CN115650322A (en) | Method for preparing nitrosyl ruthenium nitrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |