CN117843459A - Method for preparing guaiacol from catechol - Google Patents
Method for preparing guaiacol from catechol Download PDFInfo
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- CN117843459A CN117843459A CN202211230108.0A CN202211230108A CN117843459A CN 117843459 A CN117843459 A CN 117843459A CN 202211230108 A CN202211230108 A CN 202211230108A CN 117843459 A CN117843459 A CN 117843459A
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- alumina
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 title claims abstract description 142
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 51
- 229960001867 guaiacol Drugs 0.000 title claims abstract description 29
- 238000007069 methylation reaction Methods 0.000 claims abstract description 151
- 230000011987 methylation Effects 0.000 claims abstract description 135
- 239000003054 catalyst Substances 0.000 claims abstract description 122
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 80
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 239000012022 methylating agents Substances 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000007086 side reaction Methods 0.000 abstract description 7
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 19
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 16
- 229910052719 titanium Inorganic materials 0.000 description 16
- 239000010936 titanium Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 12
- 238000007654 immersion Methods 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 229910052726 zirconium Inorganic materials 0.000 description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- -1 alkali metal salts Chemical class 0.000 description 4
- 238000002715 modification method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 2
- PGSWEKYNAOWQDF-UHFFFAOYSA-N 3-methylcatechol Chemical compound CC1=CC=CC(O)=C1O PGSWEKYNAOWQDF-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- RYHGQTREHREIBC-UHFFFAOYSA-N 3,4-dimethylbenzene-1,2-diol Chemical compound CC1=CC=C(O)C(O)=C1C RYHGQTREHREIBC-UHFFFAOYSA-N 0.000 description 1
- ZBCATMYQYDCTIZ-UHFFFAOYSA-N 4-methylcatechol Chemical compound CC1=CC=C(O)C(O)=C1 ZBCATMYQYDCTIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 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
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing guaiacol from catechol, which comprises the following steps: (1) In the presence of hydrogen, catechol and a first methylation reagent are mixed and then enter a reactor to contact and react with a first methylation catalyst; (2) And (3) mixing the reaction product of the step (1) with a second methylation reagent, carrying out contact reaction with a second methylation catalyst, and separating to obtain guaiacol. The invention solves the problem of low catechol conversion rate in the single-bed catalyst design in the prior art by utilizing the acid gradient difference of the double-bed catalyst and the sectional feeding process, and improves the catechol conversion rate while inhibiting the C-methylation side reaction.
Description
Technical Field
The invention belongs to the field of guaiacol production, and particularly relates to a method for preparing guaiacol with high selectivity by catechol.
Background
Guaiacol is an important fine chemical intermediate and is a synthetic raw material of perfume vanillin with the largest global sales. The annual demand of the world is currently up to 2 tens of thousands of tons. Guaiacol has two main synthetic methods, namely ortho-nitrochlorobenzene and catechol methylation. Because the catechol process is relatively cleaner, there is a trend to fully replace the o-nitrochlorobenzene process.
The reaction for synthesizing guaiacol by catechol methylation is generally completed in a fixed bed reactor under the action of an acidic solid acid catalyst, and the reaction temperature is generally about 270 ℃. Because of the higher reaction temperature, the target product guaiacol can be generated and the benzene ring C-methylation side reaction can be generated to generate byproducts such as methyl catechol and the like, such as 4-methyl catechol, 3-methyl catechol, dimethyl catechol and the like.
It is now common practice to modify the acidity of the acid catalyst in order to reduce the C-methylation side reactions by inhibiting the acidity. CN101081805a discloses the use of TiO 2 、BaCO 3 And alkaline oxides such as CaO and the like modify the acidic active center, so that the selectivity of guaiacol is improved; CN109651095a discloses the use of alkali metal salts and alkaline earth metal salts to modify the acid catalyst to inhibit C-methylation side reactions. Meanwhile, although the alkaline auxiliary agent modification can inhibit the C-methylation side reaction, the catechol methylation activity is reduced, and the reaction conversion rate is reduced.
Therefore, it is necessary to develop a method for preparing guaiacol by methylation of catechol, and to increase the conversion rate of catechol as much as possible while ensuring selectivity.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a method for preparing guaiacol from catechol. The method solves the problem of low catechol conversion rate in the single-bed catalyst design in the prior art, and ensures the catechol conversion rate while inhibiting the C-methylation side reaction.
The invention provides a method for preparing guaiacol from catechol. The method comprises the following steps:
(1) In the presence of hydrogen, catechol and a first methylation reagent are mixed and then enter a reactor to contact and react with a first methylation catalyst;
(2) And (3) mixing the reaction product of the step (1) with a second methylation reagent, carrying out contact reaction with a second methylation catalyst, and separating to obtain guaiacol.
According to the invention, the reactor in step (1) is a fixed bed reactor.
According to the invention, the first methylating agent in step (1) and the second methylating agent in step (2) may be the same or different.
According to the invention, the first methylating agent in step (1) and/or the second methylating agent in step (2) comprises at least one of methanol, dimethyl carbonate, dimethyl ether, dimethyl sulfate; at least one of methanol and dimethyl carbonate is preferable.
According to the invention, the first methylation catalyst in step (1) is a modified alumina catalyst. Preferably, at least one of Mg, ti, zr elements is used as a modifying metal element to modify alumina.
According to the present invention, preferably, the first methylation catalyst in step (1) is a co-modified alumina catalyst of the P element and the modified metal element.
According to the invention, further, the composition of the first methylation catalyst in step (1) comprises:
based on the mass of the catalyst, the catalyst is used as a reference,
the mass content of the alumina is 90-97% in terms of oxide;
the mass content of the modified metal element is 2-5% based on oxide;
calculated by oxide, the P element is calculated by P 2 O 5 The mass content is 1-5%.
According to the invention, the second methylation catalyst in step (2) is a modified alumina catalyst. The modified alumina catalyst is preferably one of Mg, ti and Zr elements as modified metal elements for modifying alumina. Further, the second methylation catalyst does not contain a P element.
According to the invention, further, the composition of the second methylation catalyst in step (2) comprises:
based on the mass of the catalyst, the catalyst is used as a reference,
the mass content of the alumina is 96-99% based on oxide;
the mass content of the modified metal element is 1-4% based on the oxide.
According to the invention, the content of the modifying metal element in the second methylation catalyst is lower than the content of the modifying metal element in the first methylation catalyst, preferably by 1 to 3 percentage points, calculated as oxide.
According to the present invention, the modification method of the first methylation catalyst and/or the second methylation catalyst is preferably an impregnation method; further, the method specifically comprises the following steps: modifying the alumina powder by an impregnation method; the impregnating solution is a solution containing modified metal elements; and then drying, roasting and steam treatment are carried out to obtain the catalyst.
According to the modification method of the first methylation catalyst and/or the second methylation catalyst, the water vapor treatment can be a mode that an object to be treated is placed in a water vapor environment for standing. The water vapor treatment temperature is 200-800 ℃, preferably 300-500 ℃; the treatment time is 0.5 to 24 hours, preferably 2 to 10 hours. Preferably, the water vapor treatment may be followed by drying, wherein the drying condition is 90-120 ℃ and the treatment time is 2-10 hours.
According to the invention, the drying condition in the modification method of the first methylation catalyst and/or the second methylation catalyst is 90-120 ℃, and the treatment time is 2-10 hours; the roasting condition is 350-550 ℃ and the treatment time is 2-10 h.
According to the modification method of the first methylation catalyst of the present invention, the modified product may be treated in phosphoric acid after impregnating the modified metal. The treatment mode can be a mode of static soaking in solution. The temperature of the phosphoric acid treatment is 0-90 ℃, preferably 25-50 ℃; the treatment time is 0.5 to 24 hours, preferably 1 to 5 hours. The phosphoric acid is dilute phosphoric acid; the mass concentration of the dilute phosphoric acid is 0.1-20%, preferably 0.5-5%. The phosphoric acid treatment may be followed by calcination and drying. The drying condition is 90-120 ℃ and the treatment time is 2-10 h; the roasting condition is 350-550 ℃ and the treatment time is 2-10 h.
According to the method for preparing guaiacol by catechol, the separation device in the step (2) is a gas-liquid separation tank; further, the gaseous product releases hydrogen from the top of the separation tank; the liquid phase product enters a subsequent separation unit for further separation.
According to the present invention, in the method for preparing guaiacol from catechol, the reaction conditions in the step (1) are as follows: the reaction temperature is 100-250 ℃, and the feeding mass airspeed is 0.5-1.0 h -1 The reaction pressure is 1-2 MPa. The feed space velocity refers to the mass space velocity of catechol.
According to the method for preparing guaiacol by catechol, the reactions of the step (1) and the step (2) are carried out in the presence of hydrogen; the hydrogen is fed simultaneously with catechol; preferably, the molar ratio of hydrogen to catechol is between 1 and 15mol/mol.
According to the invention, in the process for preparing guaiacol from catechol, the molar ratio of the first methylating agent to catechol in step (1) is between 1 and 10mol/mol, preferably between 2 and 4mol/mol.
According to the present invention, in the method for preparing guaiacol from catechol, the reaction conditions in the step (2) are as follows: the reaction temperature is 200-300 ℃, and the space velocity of the feeding mass is 0.5-1.0 h -1 The reaction pressure is 1-2 MPa. The reaction product of step (1) is used as a feed for the reaction of step (2); the feed mass space velocity of step (2) refers to the mass space velocity of the reaction product of step (1) as feed.
According to the present invention, in the method for producing guaiacol from catechol, the molar ratio of the second methylating agent to catechol in the step (2) is 0.5 to 6mol/mol, preferably 4 to 6mol/mol.
According to the invention, the reaction temperature of step (1) is preferably lower than the reaction temperature of step (2), preferably 60 to 120 ℃.
According to the invention, the molar ratio of the first methylating agent to catechol in step (1) is preferably lower than the molar ratio of the second methylating agent to catechol in step (2), preferably between 1 and 3mol/mol lower.
Compared with the prior art, the invention mainly has the following beneficial effects:
in the method, the methylation reagent is combined for staged feeding through the grading design of the catalysts and the difference of the acid gradients of the two catalysts. The method can inhibit C-methylation side reaction and improve catechol conversion rate.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The raw materials used in the examples and comparative examples of the present invention were commercially available in the purity of analytical grade (AR).
Example 1
1) Preparation of a first methylation catalyst:
100g of alumina is taken, magnesium nitrate is immersed by an isovolumetric immersion method, and after the completion, the alumina is dried for 5 hours at 120 ℃, and then baked for 5 hours at 550 ℃ to obtain magnesium modified alumina.
And (3) placing the magnesium modified alumina in a 1% dilute phosphoric acid solution, treating for 1h at 50 ℃, drying for 5h at 120 ℃ after the treatment, and roasting for 5h at 550 ℃ to obtain the composite modified alumina. And (3) taking the composite modified alumina, treating the composite modified alumina for 2 hours at the water vapor condition of 500 ℃, and drying the composite modified alumina at the temperature of 120 ℃ for 5 hours after the treatment is finished to obtain the first methylation catalyst.
The first methylation catalyst composition is: 96% Al 2 O 3 3% MgO,1% P 2 O 5 。
2) Preparation of a second methylation catalyst:
100g of alumina is taken, magnesium nitrate is immersed by an isovolumetric immersion method, and after the completion, the alumina is dried for 5 hours at 120 ℃, and then baked for 5 hours at 550 ℃ to obtain magnesium modified alumina. The modified alumina is treated for 2 hours under the condition of 500 ℃ water vapor, and is dried for 5 hours at 120 ℃ after the treatment is finished, so as to obtain the second methylation catalyst.
The second methylation catalyst composition is: 98.5% of Al 2 O 3 1.5% MgO.
3) The first and second methylation catalysts are used for O-methylation of catechol
(1) In the presence of hydrogen, catechol and a first methylation reagent are mixed and then enter a reactor to contact and react with a first methylation catalyst;
(2) And (3) mixing the reaction product obtained in the step (1) with a second methylation catalyst, performing contact reaction with the second methylation catalyst, and separating to obtain guaiacol.
The reaction conditions of the step (1) are as follows:
the reaction temperature is 200 ℃, the reaction pressure is 2MPa, the first methylation reagent is methanol, the mol ratio of the first methylation reagent to catechol is 4mol/mol, and the feed weight airspeed is 1h -1 The molar ratio of hydrogen to catechol was 4mol/mol.
The reaction conditions of the step (2) are as follows:
the reaction temperature is 280 ℃, the reaction pressure is 2MPa, the second methylation reagent is methanol, the mol ratio of the second methylation reagent to catechol is 6mol/mol, and the feed weight airspeed is 1h -1 . The reaction results are shown in Table 1.
Example 2
1) Preparation of a first methylation catalyst:
100g of alumina is taken, tetraethyl titanate is immersed by an isovolumetric immersion method, and after completion, the alumina is dried for 5 hours at 120 ℃, and then baked for 5 hours at 550 ℃ to obtain titanium modified alumina. And (3) taking the titanium modified alumina, treating the titanium modified alumina in a 5% dilute phosphoric acid solution for 5 hours at 25 ℃, drying the titanium modified alumina for 5 hours at 120 ℃ after the titanium modified alumina is finished, and roasting the titanium modified alumina for 5 hours at 550 ℃ to obtain the composite modified alumina. And (3) taking the composite modified alumina, treating the composite modified alumina for 10 hours under the water vapor condition of 300 ℃, and drying the composite modified alumina for 5 hours at 120 ℃ after the treatment is finished to obtain the first methylation catalyst.
The first methylation catalyst composition is 90% Al 2 O 3 5% TiO 2 5% of P 2 O 5 。
2) Preparation of a second methylation catalyst:
100g of alumina is taken, tetraethyl titanate is immersed by an isovolumetric immersion method, and after completion, the alumina is dried for 5 hours at 120 ℃, and then baked for 5 hours at 550 ℃ to obtain titanium modified alumina. The modified alumina is treated for 10 hours under the water vapor condition of 300 ℃, and after the treatment is finished, the second methylation catalyst is obtained after drying for 5 hours at 120 ℃.
The second methylation catalyst composition was 96.25% Al 2 O 3 3.75% TiO 2 。
3) The first and second methylation catalysts are used for O-methylation of catechol
(1) In the presence of hydrogen, catechol and a first methylation reagent are mixed and then enter a reactor to contact and react with a first methylation catalyst;
(2) And (3) mixing the reaction product obtained in the step (1) with a second methylation catalyst, performing contact reaction with the second methylation catalyst, and separating to obtain guaiacol.
The reaction conditions of the step (1) are as follows:
the reaction temperature is 150 ℃, the reaction pressure is 1MPa, the first methylation reagent is dimethyl carbonate, the mole ratio of the first methylation reagent to catechol is 3mol/mol, and the feed weight airspeed is 0.5h -1 The molar ratio of hydrogen to catechol was 6mol/mol.
The reaction conditions of the step (2) are as follows:
the reaction temperature is 250 ℃, the reaction pressure is 1MPa, the second methylation reagent is dimethyl carbonate, the mol ratio of the second methylation reagent to catechol is 4mol/mol, and the feeding weight airspeed is 0.5h -1 . The reaction results are shown in Table 1.
Example 3
1) Preparation of a first methylation catalyst:
100g of alumina is taken, zirconium nitrate is immersed by an isovolumetric immersion method, and after the completion, the alumina is dried for 5 hours at 120 ℃, and then baked for 5 hours at 550 ℃ to obtain zirconium modified alumina. And (3) taking the zirconium-modified alumina, treating the zirconium-modified alumina in a 2% dilute phosphoric acid solution for 5 hours at 40 ℃, drying the zirconium-modified alumina for 5 hours at 120 ℃ after the zirconium-modified alumina is finished, and roasting the zirconium-modified alumina for 5 hours at 550 ℃ to obtain the composite-modified alumina. And (3) taking the composite modified alumina, treating the composite modified alumina for 10 hours under the water vapor condition of 300 ℃, and drying the composite modified alumina for 5 hours at 120 ℃ after the treatment is finished to obtain the first methylation catalyst.
The first methylation catalyst composition is: 94% Al 2 O 3 ，4％ZrO 2 ，2％P 2 O 5 。
2) Preparation of a second methylation catalyst:
100g of alumina is taken, zirconium nitrate is immersed by an isovolumetric immersion method, and after the completion, the alumina is dried for 5 hours at 120 ℃, and then baked for 5 hours at 550 ℃ to obtain zirconium modified alumina. The modified alumina is treated for 10 hours under the water vapor condition of 300 ℃, and after the treatment is finished, the second methylation catalyst is obtained after drying for 5 hours at 120 ℃.
The second methylation catalyst composition is 98% Al 2 O 3 ，2％ZrO 2 。
3) The first and second methylation catalysts are used for O-methylation of catechol
(1) In the presence of hydrogen, catechol and a first methylation reagent are mixed and then enter a reactor to contact and react with a first methylation catalyst;
(2) And (3) mixing the reaction product obtained in the step (1) with a second methylation catalyst, performing contact reaction with the second methylation catalyst, and separating to obtain guaiacol.
The reaction conditions of the step (1) are as follows:
the reaction temperature is 200 ℃, the reaction pressure is 2MPa, the first methylation reagent is dimethyl carbonate, the mole ratio of the first methylation reagent to catechol is 2mol/mol, and the feeding weight is highThe weight space velocity is 0.5h -1 The molar ratio of hydrogen to catechol was 6mol/mol.
The reaction conditions of the step (2) are as follows:
the reaction temperature is 280 ℃, the reaction pressure is 2MPa, the second methylation reagent is dimethyl carbonate, the mol ratio of the second methylation reagent to catechol is 5mol/mol, and the feeding weight airspeed is 0.5h -1 . The reaction results are shown in Table 1.
Example 4
1) Preparation of a first methylation catalyst:
100g of aluminum oxide is taken, magnesium nitrate and tetraethyl titanate are immersed by an isovolumetric immersion method, and after the completion, the aluminum oxide is dried for 5 hours at 120 ℃, and then baked for 5 hours at 550 ℃ to obtain the magnesium-titanium modified aluminum oxide.
And (3) taking the magnesium and titanium modified alumina, placing the magnesium and titanium modified alumina into a 4% dilute phosphoric acid solution, treating the magnesium and titanium modified alumina for 4 hours at 30 ℃, drying the magnesium and titanium modified alumina for 5 hours at 120 ℃ after the treatment, and roasting the magnesium and titanium modified alumina for 5 hours at 550 ℃ to obtain the composite modified alumina.
And (3) taking the composite modified alumina, treating the composite modified alumina for 5 hours at the water vapor condition of 500 ℃, and drying the composite modified alumina for 5 hours at the temperature of 120 ℃ after the treatment is finished to obtain the first methylation catalyst.
The first methylation catalyst composition is: 92% of Al 2 O 3 1% MgO,3% TiO 2 4% of P 2 O 5 。
2) Preparation of a second methylation catalyst:
100g of aluminum oxide is taken, magnesium nitrate and tetraethyl titanate are immersed by an isovolumetric immersion method, and after the completion, the aluminum oxide is dried for 5 hours at 120 ℃, and then baked for 5 hours at 550 ℃ to obtain the magnesium-titanium modified aluminum oxide. And (3) treating the modified alumina for 5 hours at the water vapor condition of 500 ℃, and drying at 120 ℃ for 5 hours after the treatment is finished to obtain the second methylation catalyst.
The second methylation catalyst composition is: 97.75% Al 2 O 3 0.75% MgO,1.5% TiO 2 。
3) The first and second methylation catalysts are used for O-methylation of catechol
(1) In the presence of hydrogen, catechol and a first methylation reagent are mixed and then enter a reactor to contact and react with a first methylation catalyst;
(2) And (3) mixing the reaction product obtained in the step (1) with a second methylation catalyst, performing contact reaction with the second methylation catalyst, and separating to obtain guaiacol.
The reaction conditions of the step (1) are as follows:
the reaction temperature is 150 ℃, the reaction pressure is 1MPa, the first methylation reagent is dimethyl carbonate, the mole ratio of the first methylation reagent to catechol is 4mol/mol, and the feed weight airspeed is 1h -1 The molar ratio of hydrogen to catechol was 4mol/mol.
The reaction conditions of the step (2) are as follows:
the reaction temperature is 270 ℃, the reaction pressure is 1MPa, the second methylation reagent is dimethyl carbonate, the mol ratio of the second methylation reagent to catechol is 6mol/mol, and the weight space velocity of the feed is 1h -1 . The reactivity is shown in Table 1.
Example 5
1) Preparation of a first methylation catalyst:
100g of alumina is taken, zirconium nitrate and tetraethyl titanate are immersed by an isovolumetric immersion method, and after the completion, the alumina is dried for 5 hours at 120 ℃, and then baked for 5 hours at 550 ℃ to obtain zirconium and titanium modified alumina. And (3) taking the zirconium and titanium modified alumina, placing the zirconium and titanium modified alumina into a 5% diluted phosphoric acid solution, treating the mixture for 5 hours at 30 ℃, drying the mixture for 5 hours at 120 ℃ after the treatment, and roasting the mixture for 5 hours at 550 ℃ to obtain the composite modified alumina. And (3) taking the composite modified alumina, treating the composite modified alumina for 10 hours under the water vapor condition of 400 ℃, and drying the composite modified alumina for 5 hours at 120 ℃ after the treatment is finished to obtain the first methylation catalyst.
The first methylation catalyst composition is: 90% Al 2 O 3 ，3％ZrO 2 ，2％TiO 2 ，5％P 2 O 5 。
2) Preparation of a second methylation catalyst:
100g of aluminum oxide is taken, zirconium nitrate and tetraethyl titanate are immersed by an isovolumetric immersion method, and the mixture is subjected to 120℃ after completionDrying for 5 hours, and roasting for 5 hours at 550 ℃ to obtain the zirconium and titanium modified alumina. The modified alumina is treated for 10 hours under the water vapor condition of 400 ℃, and after the treatment is finished, the second methylation catalyst is obtained after drying for 5 hours at 120 ℃. The second methylation catalyst composition is: 97% Al 2 O 3 ，1.5％ZrO 2 ，1.5％TiO 2 。
3) The first and second methylation catalysts are used for O-methylation of catechol
(1) In the presence of hydrogen, catechol and a first methylation reagent are mixed and then enter a reactor to contact and react with a first methylation catalyst;
(2) And (3) mixing the reaction product obtained in the step (1) with a second methylation catalyst, performing contact reaction with the second methylation catalyst, and separating to obtain guaiacol.
The reaction conditions of the step (1) are as follows:
the reaction temperature is 180 ℃, the reaction pressure is 1MPa, the first methylation reagent is dimethyl carbonate, the mol ratio of the first methylation reagent to catechol is 3mol/mol, and the weight space velocity of the feed is 1h -1 The molar ratio of hydrogen to catechol was 4mol/mol.
The reaction conditions of the step (2) are as follows:
the reaction temperature is 240 ℃, the reaction pressure is 1MPa, the second methylation reagent is dimethyl carbonate, the molar ratio of the second methylation reagent to catechol is 6mol/mol, and the feeding weight airspeed is 0.5h -1 . The reaction results are shown in Table 1.
Example 6
The differences from example 1 are: the reaction temperature of the step (1) is the same as that of the step (2); the reaction temperature of the step (1) and the reaction temperature of the step (2) are both 250 ℃. The other conditions were the same as in example 1.
Comparative example 1
The first methylation catalyst was prepared as in example 1, step 1). The first methylation catalyst composition is: 96% Al 2 O 3 3% MgO,1% P 2 O 5 。
Of a second methylation catalystThe preparation is the same as in example 1, step 2). The second methylation catalyst composition is: 98.5% of Al 2 O 3 1.5% MgO.
The first and second methylation catalysts are used for catechol O-methylation reactions. Unlike example 1, the comparative methylating agent does not employ staged feeding. The methylating agent is introduced into the reactor at the inlet of the reactor. The reaction conditions were as follows: the reaction temperature is 280 ℃, the reaction pressure is 2MPa, the methylating agent is methanol, the mol ratio of the methylating agent to catechol is 10mol/mol, and the weight space velocity of the feed is 1h -1 The molar ratio of hydrogen to catechol was 4mol/mol.
The reactivity is shown in Table 1.
Comparative example 2
The first methylation catalyst and the second methylation catalyst of this example have the same composition. The preparation process is the same as in example 1, step 1). The first methylation catalyst and the second methylation catalyst are composed of the following components: 96% Al 2 O 3 3% MgO,1% P 2 O 5 。
The first and second methylation catalysts are used for catechol O-methylation reactions. The reaction procedure is as described in example 1. The reaction conditions in the steps (1) and (2) were the same as in example 1. The difference is that the second methylation catalyst described in this example has the same composition as the first methylation catalyst. Namely, the catalyst comprises the following components: 96% Al 2 O 3 3% MgO,1% P 2 O 5 。
The reactivity is shown in Table 1.
Comparative example 3
The first methylation catalyst and the second methylation catalyst of this example have the same composition. The preparation process is the same as in example 1, step 2). The composition of the first methylation catalyst and the second methylation catalyst is 98.5 percent of Al 2 O 3 1.5% MgO.
The first and second methylation catalysts are used for catechol O-methylation reactions. The reaction procedure is as described in example 1. The reaction conditions in the steps (1) and (2) were the same as in example 1. The difference is that the second methylation catalyst composition described in this example is from that of the firstThe methylation catalyst is the same. Namely, the catalyst comprises the following components: 98.5% of Al 2 O 3 1.5% MgO.
The reactivity is shown in Table 1.
TABLE 1O-methylation reactivity of catechol
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. A method for preparing guaiacol from catechol, comprising the steps of:
(1) In the presence of hydrogen, catechol and a first methylation reagent are mixed and then enter a reactor to contact and react with a first methylation catalyst;
(2) And (3) mixing the reaction product of the step (1) with a second methylation reagent, carrying out contact reaction with a second methylation catalyst, and separating to obtain guaiacol.
2. The method of claim 1, wherein the first methylating agent in step (1) and/or the second methylating agent in step (2) comprises at least one of methanol, dimethyl carbonate, dimethyl ether, dimethyl sulfate; at least one of methanol and dimethyl carbonate is preferable.
3. The process according to claim 1, wherein the first methylation catalyst in step (1) and/or the second methylation catalyst in step (2) is a modified alumina catalyst, preferably alumina is modified with at least one of Mg, ti, zr elements as modifying metal element.
4. A process according to claim 1 or claim 3, wherein in step (1) the first methylation catalyst is a co-modified alumina catalyst of element P and a modified metal element.
5. The process of any one of claims 1 to 4, wherein the composition of the first methylation catalyst in step (1) comprises:
based on the mass of the catalyst, the catalyst is used as a reference,
the mass content of the alumina is 90-97% in terms of oxide;
the mass content of the modified metal element is 2-5% based on oxide;
calculated by oxide, the P element is calculated by P 2 O 5 The mass content is 1-5%.
6. A process according to any one of claims 1 to 3, wherein the composition of the second methylation catalyst in step (2) comprises:
based on the mass of the catalyst, the catalyst is used as a reference,
the mass content of the alumina is 96-99% based on oxide;
the mass content of the modified metal element is 1-4% based on the oxide.
7. A process according to claim 1 or 3, characterized in that the content of the modifying metal element in the second methylation catalyst is 1 to 3 percentage points lower than the content of the modifying metal element in the first methylation catalyst on oxide basis.
8. A process according to claim 3, characterized in that the modification process of the first and/or second methylation catalyst is preferably an impregnation process; further, the method specifically comprises the following steps: modifying the alumina powder by an impregnation method; the impregnating solution is a solution containing modified metal elements; and then drying, roasting and steam treatment are carried out to obtain the catalyst.
9. The method according to claim 8, wherein in the modification of the first methylation catalyst, the impregnated product is treated in phosphoric acid after impregnation;
preferably, the temperature of the phosphoric acid treatment is 0 to 90 ℃, preferably 25 to 50 ℃; and/or the phosphoric acid treatment time is 0.5 to 24 hours, preferably 1 to 5 hours;
further preferably, the phosphoric acid is dilute phosphoric acid; the mass concentration of the dilute phosphoric acid is 0.1-20%, preferably 0.5-5%.
10. The method of claim 1, wherein the reaction conditions of step (1) are: the reaction temperature is 100-250 ℃, and the feeding airspeed is 0.5-1.0 h -1 The reaction pressure is 1-2 MPa;
and/or, the reaction conditions of step (2) are: the reaction temperature is 200-300 ℃, and the feeding airspeed is 0.5-1.0 h -1 The reaction pressure is 1-2 MPa.
11. The process according to claim 1, characterized in that the molar ratio of the first methylating agent to catechol in step (1) is between 1 and 10, preferably between 2 and 4;
and/or the molar ratio of the second methylating agent to catechol of step (2) is between 0.5 and 6mol/mol, preferably between 4 and 6mol/mol.
12. The process of claim 1, wherein the reactions of step (1) and step (2) are each carried out in the presence of hydrogen; the hydrogen is fed simultaneously with catechol; preferably, the molar ratio of hydrogen to catechol is between 1 and 15.
13. The process according to claim 1 or 10, characterized in that the reaction temperature of step (1) is lower than the reaction temperature of step (2), preferably 60-120 ℃.
14. The process according to claim 1 or 10, characterized in that the molar ratio of the first methylating agent to catechol in step (1) is lower than the molar ratio of the second methylating agent to catechol in step (2), preferably lower by 1 to 3.
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