CN116217348B - Preparation method of 1, 2-di-n-propoxybenzene - Google Patents
Preparation method of 1, 2-di-n-propoxybenzene Download PDFInfo
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- CN116217348B CN116217348B CN202111478062.XA CN202111478062A CN116217348B CN 116217348 B CN116217348 B CN 116217348B CN 202111478062 A CN202111478062 A CN 202111478062A CN 116217348 B CN116217348 B CN 116217348B
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- lanthanum
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- XUIKECLBCZBUCM-UHFFFAOYSA-N 1,2-dipropoxybenzene Chemical compound CCCOC1=CC=CC=C1OCCC XUIKECLBCZBUCM-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052779 Neodymium Inorganic materials 0.000 claims description 28
- 229910052746 lanthanum Inorganic materials 0.000 claims description 28
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 28
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- -1 lanthanum neodymium titanium Chemical compound 0.000 claims description 4
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 4
- BYDYILQCRDXHLB-UHFFFAOYSA-N 3,5-dimethylpyridine-2-carbaldehyde Chemical compound CC1=CN=C(C=O)C(C)=C1 BYDYILQCRDXHLB-UHFFFAOYSA-N 0.000 claims description 3
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 3
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 3
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 3
- 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 3
- RHVPCSSKNPYQDU-UHFFFAOYSA-H neodymium(3+);trisulfate;hydrate Chemical compound O.[Nd+3].[Nd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RHVPCSSKNPYQDU-UHFFFAOYSA-H 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 10
- 239000003814 drug Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229940079593 drug Drugs 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- KWTSXDURSIMDCE-QMMMGPOBSA-N (S)-amphetamine Chemical compound C[C@H](N)CC1=CC=CC=C1 KWTSXDURSIMDCE-QMMMGPOBSA-N 0.000 description 1
- 244000223014 Syzygium aromaticum Species 0.000 description 1
- 235000016639 Syzygium aromaticum Nutrition 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229940025084 amphetamine Drugs 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process 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
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011049 filling Methods 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
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 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
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000021 stimulant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1804—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with rare earths or actinides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a novel preparation process of 1, 2-di-n-propoxybenzene, which takes catechol and n-propanol as raw materials, adopts a novel superfine La aNdbTicPO4 catalyst, and has the product yield as high as 85.1 percent. Compared with the traditional process, the process has the advantages of simple reaction steps, mild conditions, low-cost and easily-obtained raw materials and no pollution to the environment. And the catalyst has stable performance and has no obvious change in activity after continuous operation for 1000 hours.
Description
Technical Field
The invention relates to a preparation method of 1, 2-di-n-propoxybenzene, in particular to a preparation method of a novel superfine La aNdbTicPO4 catalyst, which is applied to a reaction system for catalyzing catechol and n-propanol to synthesize 1, 2-di-n-propoxybenzene.
Background
1, 2-Di-n-propoxybenzene is an important pharmaceutical, agrochemical intermediate. In the field of medicine, the method can be used for synthesizing amphetamine stimulants, aryl benzamide weight-losing medicines and anti-inflammatory active medicines. In the field of pesticide chemistry, the synthesis of egg inhibitors or poisons such as dioxybenzene and clove compounds is an extremely important raw material in pest control drugs.
At present, the preparation process of 1, 2-di-n-propoxybenzene is prepared by dehalogenating catechol and halogenated alkane in alkaline solvent. The halogen participates in the method, so that the corrosion problem on reaction equipment exists, and the halogenated alkane serving as a raw material has toxicity and is destructive to the ecological environment. In addition, the yield of the target product 1, 2-di-n-propoxybenzene in the reaction process is only 80% at maximum, and the subsequent processes of reflux, neutralization, cooling and the like are also needed for obtaining a pure product, so that the production flow is long and the cost is high.
Disclosure of Invention
The invention aims to provide a novel process for preparing 1, 2-di-n-propoxybenzene, which is specifically prepared by taking catechol and n-propanol as raw materials under the action of a lanthanum neodymium titanium composite catalyst. The process has the advantages of simple reaction steps, mild conditions, low-cost and easily-obtained raw materials, no pollution to the environment and good catalyst 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 lanthanum neodymium titanium catalyst, which comprises the following steps:
1) Dissolving a lanthanum source and a neodymium source in pure water, adding an auxiliary agent, and stirring and mixing uniformly at a low temperature;
2) Dropwise adding ammonia water into the solution;
3) Dropwise adding a titanium source into the system;
4) Slowly dripping phosphoric acid into the system until the system is neutral;
5) Heating to a certain temperature and keeping constant for a period of time;
6) Standing for aging after heating, and filtering the aged solution;
7) The filtered solid product was freeze-dried and calcined to give the catalyst, designated La aNdbTicPO4.
In the catalyst preparation method, in the step 1), the auxiliary agent is at least one selected from glycol, ethanol, glycerol, sodium chloride and acetate, and the addition amount is preferably 30-40% of the water mass;
The lanthanum source is selected from one or more of lanthanum sulfate, lanthanum carbonate, lanthanum acetate and lanthanum nitrate;
The neodymium source is selected from one or more of neodymium sulfate, neodymium acetate and neodymium nitrate;
wherein the mole ratio of lanthanum to neodymium is 1:0.1 to 10;
The ratio of the total mass of the lanthanum source and the neodymium source to the pure water is preferably 1:3 to 10;
the low temperature is in the range of-20 to-10 ℃.
In the step 2), the concentration of the ammonia water is preferably 25 to 28wt%, wherein the molar ratio of the total mole amount of lanthanum and neodymium to the mole amount of ammonia is 1: 6-18;
in the step 3), the titanium source is selected from one or more of tetrabutyl titanate, tetraisopropyl titanate and ethyl titanate;
wherein the mole ratio of the total mole of lanthanum and neodymium to titanium is 1:0.1 to 1;
in the step 4), the concentration of phosphoric acid is preferably 85%, and the adding amount is the amount until the system is neutral;
In the step 5), the certain temperature is 70-100 ℃, and the constant time is kept for 1-20 hours;
In the step 6), the aging time is 24-120 hours;
In the step 7), the freeze-drying conditions are as follows: the pressure is 1-20 Pa, the temperature is-20 to-5 ℃ and the time is 48-120 h; the roasting conditions are as follows: the temperature is 350-650 ℃ and the time is 3-10 h.
The invention also relates to the application of the catalyst La aNdbTicPO4:
the catalyst prepared by the invention is used in a reaction process for synthesizing 1, 2-di-n-propoxybenzene, and the preferable steps are as follows:
Filling the catalyst into a fixed bed, controlling a certain space velocity and temperature, and introducing a catechol and n-propanol mixed solution;
In the reaction process of the invention, the molar ratio of catechol to n-propanol is 1: 3-1:12, controlling the catechol airspeed to be 0.05-0.25 h -1, and controlling the reaction temperature to be 200-260 ℃;
the reaction liquid is rectified to obtain the pure 1, 2-di-n-propoxybenzene.
The invention has the beneficial effects that:
The novel superfine La aNdbTicPO4 catalyst is synthesized, has large specific surface area and high catalytic activity, is applied to a reaction system for catalytic synthesis of 1, 2-di-n-propoxybenzene for the first time, has the catechol conversion rate of up to 98.6 percent, and has the 1, 2-di-n-propoxybenzene yield of more than 85 percent; and the catalyst has stable performance and has no obvious change in activity after continuous operation for 1000 hours.
Detailed Description
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:
dissolving lanthanum carbonate and neodymium acetate in pure water (wherein the molar ratio of lanthanum to neodymium is 1:0.2, the mass of pure water is 3 times of the total mass of a lanthanum source and a neodymium source), adding ethylene glycol (the mass ratio of ethylene glycol to water is 30%), and stirring at-10 ℃; dropwise adding 25% ammonia water into the solution (wherein the molar ratio of the total amount of lanthanum and neodymium to ammonia is 1:6), and dropwise adding ethyl titanate into the system (wherein the molar ratio of the total amount of lanthanum and neodymium to titanium is 1:0.5); slowly dripping 85% phosphoric acid into the system until the system is neutral; heating the system to 70 ℃ for 18 hours, standing and aging for 120 hours, filtering, and freeze-drying for 48 hours, wherein the drying pressure is 15Pa, and the temperature is-6 ℃; finally roasting for 10 hours at 350 ℃ to obtain the catalyst.
The reaction conditions were as follows:
the molar ratio of catechol to n-propanol is 1:12, controlling the catechol space velocity to be 0.05h -1 and the reaction temperature to be 200 ℃.
After 12 hours of reaction, a sample of the reaction solution was taken and analyzed, and the analysis results are shown in Table 1.
Example 2
The preparation method of the catalyst comprises the following steps:
Dissolving lanthanum sulfate and neodymium sulfate in pure water (wherein the molar ratio of lanthanum to neodymium is 1:10, the mass of pure water is 10 times of the total mass of a lanthanum source and a neodymium source), adding ethylene glycol (the mass ratio of ethylene glycol to water is 40%), and keeping stirring at-20 ℃; dropwise adding 28% ammonia water into the solution (wherein the molar ratio of the total amount of lanthanum and neodymium to ammonia is 1:8); then dripping tetraisopropyl titanate into the system (wherein the molar ratio of the total of lanthanum and neodymium to titanium is 1:0.2); slowly dripping 85% phosphoric acid into the system until the system is neutral; heating the system to 100 ℃ for 5 hours, standing and aging for 24 hours, filtering, and freeze-drying for 120 hours, wherein the drying pressure is 2Pa, and the temperature is-10 ℃; and finally roasting for 3 hours at 650 ℃ to obtain the catalyst.
The reaction conditions were as follows:
The molar ratio of catechol to n-propanol is 1:6, controlling the catechol space velocity to be 0.25h -1 and the reaction temperature to be 260 ℃.
After 12 hours of reaction, a sample of the reaction solution was taken and analyzed, and the analysis results are shown in Table 1.
Example 3
The preparation method of the catalyst comprises the following steps:
Dissolving lanthanum acetate and neodymium nitrate in pure water (wherein the molar ratio of lanthanum to neodymium is 1:1, the mass of pure water is 6 times of the total mass of a lanthanum source and a neodymium source), adding ethylene glycol (the mass ratio of ethylene glycol to water is 32%), and stirring at-14 ℃; dropwise adding 26% ammonia water into the solution (wherein the molar ratio of the total amount of lanthanum and neodymium to ammonia is 1:16); then dripping tetrabutyl titanate into the system (wherein the molar ratio of the total amount of lanthanum and neodymium to titanium is 1:0.9); slowly dripping 85% phosphoric acid into the system until the system is neutral; heating the system to 80 ℃ for 12 hours, standing and aging for 96 hours, filtering, and freeze-drying for 72 hours, wherein the drying pressure is 10Pa, and the temperature is-14 ℃; finally roasting for 8 hours at 550 ℃ to obtain the catalyst.
The reaction conditions were as follows:
The molar ratio of catechol to n-propanol is 1:3, controlling the catechol space velocity to be 0.15h -1 and the reaction temperature to be 220 ℃.
After 12 hours of reaction, a sample of the reaction solution was taken and analyzed, and the analysis results are shown in Table 1.
Example 4
The preparation method of the catalyst comprises the following steps:
Dissolving lanthanum nitrate hexahydrate and neodymium nitrate in pure water (wherein the molar ratio of lanthanum to neodymium is 1:0.5, the mass of pure water is 5 times of the total mass of a lanthanum source and a neodymium source), adding ethylene glycol (the mass ratio of ethylene glycol to water is 36%), and stirring at-16 ℃; dropwise adding 27% ammonia water into the solution, wherein the molar ratio of the total amount of lanthanum and neodymium to ammonia is 1:12; then dripping ethyl titanate into the system (wherein the molar ratio of the total of lanthanum and neodymium to titanium is 1:0.4); slowly dripping 85% phosphoric acid into the system until the system is neutral; heating the system to 90 ℃ for 8 hours, standing and aging for 72 hours, filtering, and freeze-drying for 96 hours, wherein the drying pressure is 5Pa, and the temperature is-18 ℃; finally roasting for 5 hours at 600 ℃ to obtain the catalyst.
The reaction conditions were as follows:
The molar ratio of catechol to n-propanol is 1:9, controlling the catechol space velocity to be 0.2h -1 and the reaction temperature to be 240 ℃.
After 12 hours of reaction, a sample of the reaction solution was taken and analyzed, and the analysis results are shown in Table 1.
Table 1 example sample analysis results
| Examples | Catechol conversion% | 1, 2-Di-n-propoxybenzene Selectivity% | 1, 2-Di-n-propoxybenzene yield% |
| 1 | 90.3 | 89.9 | 81.2 |
| 2 | 98.6 | 81.2 | 80.1 |
| 3 | 93.6 | 89.3 | 83.6 |
| 4 | 95.2 | 89.4 | 85.1 |
After the catalyst of example 4 was continuously used for 1000 hours, the conversion rate of catechol was 94.6% and the yield of 1, 2-di-n-propoxybenzene was 84.3% as measured by sampling analysis, which indicated that the catalyst still had higher activity for synthesizing 1, 2-di-n-propoxybenzene from catechol and n-propanol, and no significant decrease was observed.
Claims (7)
1. A preparation method of 1, 2-di-n-propoxybenzene is characterized in that catechol and n-propanol are used as raw materials to react under the action of lanthanum neodymium titanium composite catalyst to prepare 1, 2-di-n-propoxybenzene;
The preparation method of the catalyst comprises the following steps:
1) Dissolving a lanthanum source and a neodymium source in pure water, adding an auxiliary agent, and stirring and mixing uniformly at the temperature of minus 20 ℃ to minus 10 ℃; wherein the mole ratio of lanthanum to neodymium is 1:0.1 to 10 percent of auxiliary agent selected from at least one of glycol, ethanol, glycerol, sodium chloride and acetate, and the addition amount is 30 to 40 percent of the water mass;
2) Slowly adding ammonia water into the solution; the molar ratio of the total mole of lanthanum and neodymium to ammonia is 1: 6-18;
3) Slowly adding a titanium source into the system; the mole ratio of the total mole of lanthanum and neodymium to titanium is 1:0.1 to 1;
4) Slowly adding phosphoric acid until the system is neutral;
5) Heating to 70-100 ℃ and keeping constant for a period of time;
6) Standing for aging after heating, and filtering the aged solution;
7) And freeze-drying and roasting the filtered solid product to obtain the catalyst.
2. The method of claim 1, wherein the molar ratio of catechol to n-propanol is 1: 3-1:12, catechol airspeed is 0.05-0.25 h -1, and the reaction temperature is 200-260 ℃.
3. The method of claim 1, wherein in step 1), the lanthanum source is selected from one or more of lanthanum sulfate, lanthanum carbonate, lanthanum acetate, lanthanum nitrate;
The neodymium source is selected from one or more of neodymium sulfate, neodymium acetate and neodymium nitrate;
The mass ratio of the total mass of the lanthanum source and the neodymium source to the pure water is 1:3 to 10.
4. The method of claim 1, wherein in step 3), the titanium source is selected from one or more of tetra-n-butyl titanate, tetra-isopropyl titanate, and ethyl titanate.
5. The method according to claim 1, wherein in step 5), the constant time is maintained for 1 to 20 hours.
6. The process according to claim 1, wherein in step 6), the aging time is 24 to 120 hours.
7. The method of claim 1, wherein in step 7), the freeze-drying conditions are: the pressure is 1-20 Pa, the temperature is-20 to-5 ℃ and the time is 48-120 h; the roasting conditions are as follows: the temperature is 350-650 ℃ and the time is 3-10 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111478062.XA CN116217348B (en) | 2021-12-06 | 2021-12-06 | Preparation method of 1, 2-di-n-propoxybenzene |
Applications Claiming Priority (1)
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