CN114349597B - Method for stably producing 3-methyl-2-butenol for long period - Google Patents
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Abstract
The invention discloses a method for stably producing 3-methyl-2-butenol in a long period, which comprises the following steps: 1) Carrying out condensation reaction on isobutene and formaldehyde aqueous solution in the presence of an amine catalyst to prepare 3-methyl-3-butenol; before reaction, the oxidation-reduction potential value of the formaldehyde aqueous solution is controlled to be-100-400 mv; 2) 3-methyl-3-butenol and hydrogen-containing carrier gas are introduced into a reactor, and isomerization reaction is carried out in the presence of a hydroisomerization catalyst to obtain the 3-methyl-2-butenol. The inventor surprisingly discovers that the service life of the hydroisomerization catalyst in the subsequent process can be obviously prolonged by controlling the oxidation-reduction potential value of the raw material formaldehyde aqueous solution in the preparation process of the 3-methyl-3-butenol within a certain range, and the long-period stable operation of a continuous production device is favorably realized.
Description
Technical Field
The invention relates to a production method, in particular to a method for stably producing 3-methyl-2-butenol for a long period.
Background
3-methyl-2-butenol is an important organic compound and an important intermediate in the fields of synthetic spices, medicines, pesticide production and the like. Can be used as a basic raw material for producing high-efficiency low-toxicity pesticide pyrethrin and citral series essences and flavors, and also can be used as an intermediate for synthesizing vitamin A and carotenoid.
At present, the synthesis method of 3-methyl-2-butenol mainly comprises the steps of firstly preparing 3-methyl-3-butenol by condensation reaction of isobutene and formaldehyde, and then preparing the 3-methyl-2-butenol by continuous hydroisomerization reaction in the presence of a VIII-family transition metal catalyst. In order to ensure the long-period stable operation of the hydroisomerization reaction device, each large-scale manufacturer puts higher requirements on the service life of the catalyst. However, the group VIII transition metals are mostly noble metals, and the catalyst of the type is sensitive to impurities existing in a reaction system, is easy to be poisoned and inactivated, and is difficult to achieve a satisfactory stable operation period in an actual industrial production process, for example, the continuous production time of an industrial device is generally 200 to 400 days (the reaction conversion rate is reduced by 10%).
The patent publication CN107141197A discloses a method for preparing 3-methyl-2-butenol by using a carbonyl iron compound as a catalyst to catalyze 3-methyl-3-butenol to perform isomerization reaction, wherein the method uses a high-activity catalyst to improve the product selectivity, but adopts an intermittent preparation process which cannot realize continuous preparation, and only tests the catalytic effect within 5 times of catalyst application.
WO2008037693A1 discloses a fixed bed process for isomerizing 3-methyl-3-butenol to generate 3-methyl-2-butenol in a heterogeneous noble metal catalyst and hydrogen atmosphere, wherein the catalyst system comprises palladium, selenium, tellurium and other elements, wherein the high activation effect of palladium metal on double bonds and the coordination activity of selenium and tellurium elements can further react residual double bond structures, so that excessive hydrogenation products exist in the products, the separation is complicated, and the cost is increased.
Therefore, it is necessary to develop a method for stably producing 3-methyl-2-butenol for a long period of time, so as to reduce the production cost and improve the production efficiency of enterprises.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for stably producing 3-methyl-2-butenol for a long period. The inventor surprisingly finds that the service life of the hydroisomerization catalyst in the subsequent process can be remarkably prolonged by controlling the oxidation-reduction potential value of the raw material formaldehyde aqueous solution in the preparation process of the 3-methyl-3-butenol within a certain range, and the long-period stable operation of a continuous production device is favorably realized, thereby completing the invention.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a method for long-cycle stable production of 3-methyl-2-butenol, comprising the steps of:
1) Carrying out condensation reaction on isobutene and formaldehyde aqueous solution in the presence of an amine catalyst to prepare 3-methyl-3-butenol; before reaction, the oxidation-reduction potential value of the formaldehyde aqueous solution is controlled to be-100-400 mv, preferably-50-200 mv;
2) 3-methyl-3-butenol and hydrogen-containing carrier gas are introduced into a reactor, and isomerization reaction is carried out in the presence of a hydroisomerization catalyst to obtain the 3-methyl-2-butenol.
Further, in the step 1), the concentration of the aqueous formaldehyde solution is 30 to 50%, preferably 35 to 40%.
The method does not limit the mode of controlling the oxidation-reduction potential value of the formaldehyde aqueous solution, and on the basis of the consideration of convenient operation and simple and easily obtained raw materials, the method preferably adjusts the oxidation-reduction potential value to be-100-400 mv, preferably-50-200 mv by adding a reducing agent into the formaldehyde aqueous solution.
Further, the reducing agent is selected from one or more of hydrogen peroxide aqueous solution, sodium sulfite aqueous solution, sodium thiosulfate aqueous solution and hydrazine aqueous solution, and sodium sulfite aqueous solution is more preferable.
Further, in the step 1), the amine catalyst is selected from one or more of trialkylamine (shown in formula I), dialkylamine (shown in formula II), alkylamine (shown in formula III) and nitrogen-containing heterocyclic compound, preferably one or more of trimethylamine, dimethylamine, triethylamine, diethylamine, triisopropylamine, diisopropylamine, 1-propylamine, butan-2-amine, methylpropan-2-amine, pyridine (shown in formula IV), piperidine (shown in formula V) and urotropin (shown in formula VI), and more preferably urotropin.
Wherein R is 1 Is a C1-C6 linear or branched saturated alkane, R 2 Is a C1-C6 linear or branched saturated alkane, R 3 Is C1-C8 straight-chain or branched saturated alkane.
Further, in the step 1), the using amount of the amine catalyst is 0.001-2.0% of the mass of the isobutene;
preferably, the molar ratio of the isobutene to the formaldehyde aqueous solution is (5-10): 1.
Further, the condensation reaction conditions in the step 1) are as follows: the reaction temperature is from 300 to 360 ℃ and preferably from 310 to 340 ℃, the absolute pressure of the reaction is from 150 to 250 bar, preferably from 180 to 200 bar, and the reaction time is from 0.1 to 2 hours, preferably from 0.2 to 1 hour.
Further, 3-methyl-3-butenol obtained by rectifying and purifying the reaction liquid obtained in the step 1) is used as the raw material in the step 2).
Further, in step 2), the hydroisomerization catalyst is selected from one or more of metal catalysts containing group viii transition metal elements, preferably supported catalysts of skeletal nickel, platinum, palladium and nickel, and metal oxide catalysts, more preferably one or two of palladium carbon or palladium alumina.
Further, the reaction temperature of the isomerization reaction is 80-300 ℃, preferably 100-180 ℃; the reaction pressure is from 0.1 to 3MPa (A), preferably from 0.1 to 2MPa (A).
Furthermore, the mass space velocity of the raw material 3-methyl-3-butenol is 0.3 to 30h -1 Preferably 0.5 to 10 hours -1 ；
Preferably, the volume space velocity of the hydrogen-containing carrier gas is 20-800 h -1 Preferably 50 to 500h -1 。
Further, the carrier gas in the hydrogen-containing carrier gas is nitrogen, wherein the hydrogen content is 0.5 to 10vol%, preferably 0.5 to 5vol%, and the nitrogen content is 90 to 99.5vol%, preferably 95 to 99.5vol%.
The method has the advantages that the effect of unexpectedly prolonging the service life of the hydroisomerization catalyst in the preparation process of the 3-methyl-2-butenol is achieved by controlling the oxidation-reduction potential value of the formaldehyde aqueous solution as the raw material in the preparation process of the 3-methyl-3-butenol, the long-period stable operation of a production device is favorably ensured, and the economic benefit of an enterprise is improved.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be merely illustrative of the invention and not limiting of its scope.
The raw materials in the examples and comparative examples of the present invention are all commercial products unless otherwise specified.
< test and analysis methods >
(1) Oxidation-reduction potentiometer: ORP-760, hengode instruments, beijing; measurement range: -1000mV to 1000mV; accuracy: +/-2 mV; ambient temperature: 0 to 50 ℃; relative humidity: less than or equal to 85 percent; power supply: AC 220V. + -. 10% by weight of 50/60Hz.
(2) Gas chromatograph: agilent7890, chromatographic column DB-5, injection port temperature: 300 ℃, split ratio: 50, carrier gas flow: 52.8mL/min; temperature rising procedure: at 95 ℃ for 40min, increasing to 180 ℃ at a rate of 10 ℃/min for 40min, detector temperature: 280 ℃.
[ example 1 ]
3-methyl-2-butenol was prepared according to the following method:
220g of 50% formaldehyde aqueous solution is added into a stirring autoclave, 10% sodium sulfite aqueous solution is added into the stirring autoclave, the adding amount of the sodium sulfite is 0.3% of the mass of the formaldehyde, and the oxidation-reduction potential value of the formaldehyde aqueous solution is reduced to-50 mv from the initial 800 mv. 2000g of isobutene and 2g of urotropin were then added to the reaction vessel, the autoclave was sealed, stirred and heated to 300 ℃ and the autoclave was pressurized to 250 bar with nitrogen. The reaction mixture was stirred at 300 ℃ and 250 bar for 2 hours. The reaction mixture was then cooled to 25 ℃ and the pressure released.
The organic phase above the phase separation of the product was collected and distilled using a continuous distillation column at a pressure of 1013 mbar at a bottom temperature of 135 ℃ and a top temperature of 100 ℃ with the reflux ratio of the distillate stream being adjusted to 5. The 3-methyl-3-butenol product after rectification and purification is obtained at the tower top, wherein the content of the 3-methyl-3-butenol is 98.2 percent, and the content of the 3-methyl-2-butenol is 1.5 percent.
50mL of palladium alumina catalyst (palladium content 1%, shanxi Kaida chemical industry) is filled in the middle section of a 100mL fixed bed reactor along the material flow direction, hydrogen-containing carrier gas and the prepared 3-methyl-3-butenol pass through the reactor from top to bottom, and the flow rate is 15L/h (corresponding to the volume space velocity of 50 h) -1 ) And 150mL/h (corresponding to a volume space velocity of 0.5 h) -1 ) Carrying out hydroisomerization reaction; wherein the isomerization reaction temperature is controlled at 150 deg.C, the pressure is 1MPa (A), and the hydrogen content in the hydrogen-containing carrier gas is 0.5%(v/v) and the balance of nitrogen, discharging the product from the lower outlet of the reactor, then condensing the product in a heat exchanger, collecting and sampling the condensed product, determining the composition of the isomerization reaction solution by using gas chromatography analysis, and recording the reaction conversion rate at different times, as shown in table 1.
[ example 2 ] A method for producing a polycarbonate
3-methyl-2-butenol was prepared according to the following method:
200g of formaldehyde aqueous solution with the mass fraction of 35 percent is added into a stirring autoclave, 10 percent hydrogen peroxide aqueous solution is added into the stirring autoclave, and the adding amount of the hydrogen peroxide is 0.3 percent of the mass of the formaldehyde, so that the oxidation-reduction potential value of the formaldehyde aqueous solution is reduced to 100mv from the initial 800 mv. 700g of isobutene and 14g of triethylamine were then added to the reaction vessel, the autoclave was sealed, stirred and heated to 350 ℃ and the autoclave was pressurized to 150 bar with nitrogen. The reaction mixture was stirred at 350 ℃ and 150 bar for 0.1 h. The reaction mixture was then cooled to 25 ℃ and the pressure released.
The organic phase above the phase separation of the product was collected and distilled using a continuous distillation column at a pressure of 1013 mbar at a bottom temperature of 135 ℃ and a top temperature of 100 ℃. The reflux ratio of the distillate stream was adjusted to 5. The 3-methyl-3-butenol product after rectification and purification is obtained at the tower top, wherein the content of the 3-methyl-3-butenol is 98.4 percent, and the content of the 3-methyl-2-butenol is 1.3 percent.
50mL of palladium-carbon catalyst (palladium content is 1 percent, shaanxi Kaida chemical industry) is filled in the middle section of a 100mL fixed bed reactor along the material flow direction, hydrogen-containing carrier gas and the prepared 3-methyl-3-butenol pass through the reactor from top to bottom, and the flow rate is 150L/h (corresponding to the volume space velocity of 500 h) -1 ) And 3000mL/h (corresponding to a volume space velocity of 10 h) -1 ) Carrying out hydroisomerization reaction; wherein the temperature of the isomerization reaction was controlled at 100 ℃, the pressure was 2MPa (a), the hydrogen content in the hydrogen-containing carrier gas was 5% (v/v), the remainder was nitrogen, the product was discharged from the lower outlet of the reactor, and then it was condensed in a heat exchanger, after condensation, collection and sampling were performed, the composition of the isomerization reaction solution was determined by gas chromatography analysis, and the reaction conversion at different times was recorded, as shown in table 1.
[ example 3 ]
3-methyl-2-butenol was prepared according to the following method:
200g of a 30% formaldehyde aqueous solution is added to a stirred autoclave, and a 10% sodium sulfite solution is added thereto, the sodium sulfite being added in an amount of 0.2% by mass based on the mass of formaldehyde, so that the redox potential value of the formaldehyde aqueous solution is reduced from 800mv initially to 0mv. 800g of isobutene and 0.008g of diisopropylamine were then added to the reaction vessel, the autoclave was sealed, stirred and heated to 330 ℃ and the autoclave was pressurized to 200 bar with nitrogen. The reaction mixture was stirred at 330 ℃ and 200 bar for 1 hour. The reaction mixture was then cooled to 25 ℃ and the pressure released.
The organic phase above the phase separation of the product was collected and distilled using a continuous distillation column at a pressure of 1013 mbar at a bottom temperature of 135 ℃ and a top temperature of 100 ℃. The reflux ratio of the distillate stream was adjusted to 5. The 3-methyl-3-butenol product after rectification and purification is obtained at the tower top, wherein the content of the 3-methyl-3-butenol is 98.1 percent, and the content of the 3-methyl-2-butenol is 1.4 percent.
50mL of skeletal nickel catalyst (Ni 8072, chemical engineering for large communication) is filled in the middle section of a 100mL fixed bed reactor along the material flow direction, hydrogen-containing carrier gas and the prepared 3-methyl-3-butenol pass through the reactor from top to bottom, and the flow rates are respectively 6L/h (corresponding to the volume space velocity of 20 h) -1 ) And 1500mL/h (corresponding to a volume space velocity of 5 h) -1 ) Carrying out hydroisomerization reaction; wherein the temperature of the isomerization reaction was controlled at 80 ℃, the pressure was 0.5MPa (a), the hydrogen content in the hydrogen-containing carrier gas was 10% (v/v), the remainder was nitrogen, the product was discharged from the lower outlet of the reactor, and then entered into a heat exchanger for condensation, after condensation, collection and sampling were performed, the composition of the isomerization reaction solution was determined by gas chromatography analysis, and the reaction conversion rate at different times was recorded, as shown in table 1.
[ example 4 ] A method for producing a polycarbonate
3-methyl-2-butenol was prepared according to the following method:
200g of formaldehyde aqueous solution with the mass fraction of 37 percent is added into a stirring autoclave, and then 10 percent of sodium thiosulfate aqueous solution is added into the stirring autoclave, wherein the addition amount of the sodium thiosulfate accounts for 0.3 percent of the mass of the formaldehyde, so that the oxidation-reduction potential value of the formaldehyde aqueous solution is reduced from the initial 800mv to 150mv. 1000g of isobutene and 20g of methylpropan-2-amine were then added to the reaction vessel, the autoclave was sealed, stirred and heated to 330 ℃ and the autoclave was pressurized to 250 bar with nitrogen. The reaction mixture was stirred at 330 ℃ and 250 bar for 1 hour. The reaction mixture was then cooled to 25 ℃ and the pressure released.
The organic phase above the phase separation of the product was collected and distilled using a continuous distillation column at a pressure of 1013 mbar at a bottom temperature of 135 ℃ and a top temperature of 100 ℃. The reflux ratio of the distillate stream was adjusted to 5. The 3-methyl-3-butenol product after rectification and purification is obtained at the tower top, wherein the content of the 3-methyl-3-butenol is 98.3 percent, and the content of the 3-methyl-2-butenol is 1.5 percent.
50mL of platinum copper oxide catalyst (platinum content 1%, kinghua platinum Rui catalysis science and technology Co., ltd.) is filled in the middle section of a 100mL fixed bed reactor along the material flow direction, hydrogen-containing carrier gas and the prepared 3-methyl-3-butenol pass through the reactor from top to bottom, and the flow rates are respectively 180L/h (corresponding to the volume space velocity of 600 h) -1 ) And 90mL/h (corresponding to a volume space velocity of 0.3 h) -1 ) Carrying out hydroisomerization reaction; wherein the temperature of the isomerization reaction was controlled at 180 ℃, the pressure was 0.1MPa (a), the hydrogen content in the hydrogen-containing carrier gas was 6% (v/v), the remainder was nitrogen, the product was discharged from the lower outlet of the reactor, and then entered into a heat exchanger for condensation, after condensation, collection and sampling, and the composition of the isomerization reaction solution was determined by gas chromatography analysis, and the reaction conversion rate at different times was recorded, as shown in table 1.
[ example 5 ]
3-methyl-2-butenol was prepared according to the following method:
200g of formaldehyde aqueous solution with the mass fraction of 37 percent is added into a stirring autoclave, and then 10 percent of hydrazine aqueous solution is added into the stirring autoclave, wherein the hydrazine is added in an amount of 0.2 percent of the mass of the formaldehyde, so that the oxidation-reduction potential value of the formaldehyde aqueous solution is reduced from the initial 800mv to 200mv. 1000g of isobutene and 5g of pyridine were then added to the reaction vessel, the autoclave was sealed, stirred and heated to 360 ℃ and the autoclave was pressurized to 200 bar with nitrogen. The reaction mixture was stirred at 360 ℃ and 200 bar for 1 hour. The reaction mixture was then cooled to 25 ℃ and the pressure released.
The organic phase above the phase separation of the product was collected and distilled using a continuous distillation column at a pressure of 1013 mbar at a bottom temperature of 135 ℃ and a top temperature of 100 ℃. The reflux ratio of the distillate stream was adjusted to 5. The 3-methyl-3-butenol product after rectification and purification is obtained at the tower top, wherein the content of the 3-methyl-3-butenol is 98.4 percent, and the content of the 3-methyl-2-butenol is 1.3 percent.
50mL of nickel zinc oxide catalyst (nickel content 10%, taozhou Toyobo regeneration resources Co., ltd.) is filled in the middle section of a 100mL fixed bed reactor along the material flow direction, hydrogen-containing carrier gas and the prepared 3-methyl-3-butenol pass through the reactor from top to bottom, and the flow rate is 240L/h (corresponding to the volume space velocity of 800 h) -1 ) And 9000mL/h (corresponding to a volumetric space velocity of 30 h) -1 ) Carrying out hydroisomerization reaction; wherein the temperature of the isomerization reaction was controlled at 250 ℃, the pressure was 3MPa (a), the hydrogen content in the hydrogen-containing carrier gas was 2% (v/v), the remainder was nitrogen, the product was discharged from the lower outlet of the reactor, and then it was condensed in a heat exchanger, after condensation, collection and sampling were performed, the composition of the isomerization reaction solution was determined by gas chromatography analysis, and the reaction conversion at different times was recorded, as shown in table 1.
[ example 6 ] A method for producing a polycarbonate
3-methyl-2-butenol was prepared according to the following method:
200g of a 37% formaldehyde aqueous solution was charged into a stirred autoclave, followed by addition of a 10% sodium sulfite aqueous solution in an amount of 0.4% by mass based on the mass of formaldehyde to reduce the oxidation-reduction potential of the formaldehyde aqueous solution from the initial 800mv to-100 mv. 1000g of isobutene and 0.1g of urotropin were then added to the reaction vessel, the autoclave was sealed, stirred and heated to 300 ℃ and the autoclave was pressurized to 200 bar with nitrogen. The reaction mixture was stirred at 300 ℃ and 200 bar for 1 hour. The reaction mixture was then cooled to 25 ℃ and the pressure released.
The organic phase above the phase separation of the product was collected and distilled using a continuous distillation column at a pressure of 1013 mbar at a bottom temperature of 135 ℃ and a top temperature of 100 ℃. The reflux ratio of the distillate stream was adjusted to 5. The 3-methyl-3-butenol product after rectification and purification is obtained at the tower top, wherein the content of the 3-methyl-3-butenol is 98.2 percent, and the content of the 3-methyl-2-butenol is 1.4 percent.
50mL of palladium chromium oxide catalyst (palladium content is 1 percent, shaanxi Kaida chemical industry) is filled in the middle section of a 100mL fixed bed reactor along the material flow direction, hydrogen-containing carrier gas and the prepared 3-methyl-3-butenol pass through the reactor from top to bottom, and the flow rate is 30L/h (corresponding to the volume space velocity of 100 h) -1 ) And 6000mL/h (corresponding to a volume space velocity of 20 h) -1 ) Carrying out hydroisomerization reaction; wherein the temperature of the isomerization reaction was controlled at 300 ℃, the pressure 1.5MPa (a), the hydrogen content in the hydrogen-containing carrier gas was 0.8% (v/v), the remainder was nitrogen, the product was discharged from the lower outlet of the reactor, and then entered into a heat exchanger for condensation, after condensation, collected and sampled, and the composition of the isomerization reaction solution was determined by gas chromatography analysis, and the reaction conversion at different times was recorded, as shown in table 1.
[ example 7 ]
3-methyl-2-butenol was prepared according to the following method:
200g of a 37% formaldehyde aqueous solution was charged into a stirred autoclave, followed by addition of a 10% sodium thiosulfate aqueous solution in an amount of 0.5% by mass based on the formaldehyde, to reduce the oxidation-reduction potential of the formaldehyde aqueous solution from the initial 800mv to 50mv. 1000g of isobutene and 0.05g of trimethylamine are then added to the reaction vessel, the autoclave is sealed, stirred and heated to 300 ℃ and the autoclave is pressurized to 200 bar with nitrogen. The reaction mixture was stirred at 300 ℃ and 200 bar for 1 hour. The reaction mixture was then cooled to 25 ℃ and the pressure released.
The organic phase above the phase separation of the product was collected and distilled using a continuous distillation column at a pressure of 1013 mbar at a bottom temperature of 135 ℃ and a top temperature of 100 ℃. The reflux ratio of the distillate stream was adjusted to 5. The 3-methyl-3-butenol product after rectification and purification is obtained at the tower top, wherein the content of the 3-methyl-3-butenol is 98.1 percent, and the content of the 3-methyl-2-butenol is 1.5 percent.
50mL of palladium-alumina catalyst (palladium content 1%, shan) is filled in the middle section of a 100mL fixed bed reactor along the material flow directionChemical engineering), passing hydrogen-containing carrier gas and the prepared 3-methyl-3-butenol raw material through a reactor from top to bottom, wherein the flow rates are respectively 90L/h (corresponding to the volume space velocity of 300 h) -1 ) And 4500mL/h (corresponding to a volume space velocity of 15 h) -1 ) Carrying out hydroisomerization reaction; wherein the temperature of the isomerization reaction was controlled at 200 ℃, the pressure was 0.8MPa (a), the hydrogen content in the hydrogen-containing carrier gas was 1% (v/v), the remainder was nitrogen, the product was discharged from the lower outlet of the reactor, and then entered into a heat exchanger for condensation, after condensation, collection and sampling, and the composition of the isomerization reaction solution was determined by gas chromatography analysis, and the reaction conversion rate at different times was recorded, as shown in table 1.
Comparative example 1
3-methyl-3-butenol was prepared according to substantially the same method as in example 1, except that: formaldehyde aqueous solution (without redox potential value adjustment) with initial redox potential value of 800mv is directly used as raw material to react with isobutene. Then, using the obtained 3-methyl-3-butenol as a starting material, 3-methyl-2-butenol was further prepared in accordance with the same method as in example 1, and the reaction conversion at different times was recorded as shown in Table 1.
TABLE 1, examples and comparative examples reaction conversion at various times in the preparation of 3-methyl-2-butenol
| 100 days | 200 days | 300 days | 400 days | 500 days | 600 days | 700 days | |
| Example 1 | 70.8％ | 70.6％ | 70.3％ | 70.0％ | 69.8％ | 69.7％ | 69.5％ |
| Example 2 | 72.5％ | 72.2％ | 71.9％ | 71.8％ | 71.6％ | 71.4％ | 71.1％ |
| Example 3 | 71.9％ | 71.7％ | 71.5％ | 71.4％ | 71.2％ | 71.1％ | 70.9％ |
| Example 4 | 70.7％ | 70.6％ | 70.4％ | 70.3％ | 70.1％ | 69.9％ | 69.7％ |
| Example 5 | 72.7％ | 72.6％ | 72.4％ | 72.2％ | 72.1％ | 71.8％ | 71.7％ |
| Example 6 | 71.7％ | 71.5％ | 71.4％ | 71.2％ | 71.1％ | 70.8％ | 70.6％ |
| Example 7 | 73.3％ | 73.2％ | 73.0％ | 72.8％ | 72.6％ | 72.5％ | 72.3％ |
| Comparative example 1 | 70.1％ | 68.3％ | 63.5％ | 58.4％ | 55.7％ | 51.4％ | 49.2％ |
The method adopts the index of the oxidation-reduction potential value to evaluate the total amount of all the oxidative impurities in the reaction raw materials, which means that the raw material formaldehyde hardly contains the oxidative impurities, the introduction of any one oxidative impurity in the 3-methyl-3-butenol can be avoided, and the service life of the catalyst in the subsequent hydroisomerization reaction stage can be remarkably prolonged, so that the long-period stable operation of the device is realized.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for a person skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be considered as the protection scope of the present invention.
Claims (21)
1. A method for producing 3-methyl-2-butenol stably for a long period, which is characterized by comprising the following steps:
1) Carrying out condensation reaction on isobutene and formaldehyde aqueous solution in the presence of an amine catalyst to prepare 3-methyl-3-butenol; before reaction, the oxidation-reduction potential value of the formaldehyde aqueous solution is controlled to be-100-400 mv;
2) Introducing 3-methyl-3-butenol and hydrogen-containing carrier gas into a reactor, and carrying out isomerization reaction in the presence of a hydroisomerization catalyst to obtain 3-methyl-2-butenol;
in the step 2), the hydroisomerization catalyst is selected from one or more of a carrier catalyst of framework nickel, platinum, palladium and nickel and a metal oxide catalyst.
2. The method for stably producing 3-methyl-2-butenol for a long period of time according to claim 1, wherein the redox potential value of the aqueous formaldehyde solution before the reaction in step 1) is controlled to be-50 to 200mv.
3. The method for long-term stable production of 3-methyl-2-butenol according to claim 1, wherein the concentration of the aqueous formaldehyde solution in the step 1) is 30 to 50%.
4. The method for long-term stable production of 3-methyl-2-butenol according to claim 3, wherein in the step 1), the concentration of the aqueous formaldehyde solution is from 35 to 40%.
5. The method for long-term stable production of 3-methyl-2-butenol according to any one of claims 1 to 4, wherein in the step 1), the amine catalyst is one or more selected from the group consisting of trialkylamine, dialkylamine, alkylamine and nitrogen-containing heterocyclic compound.
6. The method for long-term stable production of 3-methyl-2-butenol according to claim 5, wherein in the step 1), the amine catalyst is selected from one or more of trimethylamine, dimethylamine, triethylamine, diethylamine, triisopropylamine, diisopropylamine, 1-propylamine, butan-2-amine, methylpropan-2-amine, pyridine, piperidine and urotropin.
7. The method for long-term stable production of 3-methyl-2-butenol according to claim 6, wherein in the step 1), the amine catalyst is urotropin.
8. The method for long-term stable production of 3-methyl-2-butenol according to claim 5, wherein the amount of the amine catalyst used in the step 1) is 0.001 to 2.0% by mass based on isobutylene.
9. The method for long-term stable production of 3-methyl-2-butenol according to claim 8, wherein in the step 1), the amount of isobutylene to the aqueous formaldehyde solution is (5-10): 1 in terms of a molar ratio.
10. The method for long-term stable production of 3-methyl-2-butenol according to claim 8, wherein the condensation reaction conditions in step 1) are: the reaction temperature is 300-360 ℃, the absolute pressure of the reaction is 150-250 bar, and the reaction time is 0.1-2 hours.
11. The method for long-term stable production of 3-methyl-2-butenol according to claim 10, wherein the condensation reaction conditions in step 1) are: the reaction temperature is 310-340 ℃, the absolute pressure of the reaction is 180-200 bar, and the reaction time is 0.2-1 hour.
12. The method for stably producing 3-methyl-2-butenol for a long period of time according to any one of claims 1 to 4, wherein 3-methyl-3-butenol obtained by subjecting the reaction liquid obtained in the step 1) to rectification purification is used as a raw material in the step 2).
13. The method for long-term stable production of 3-methyl-2-butenol according to claim 12, wherein in the step 2), the hydroisomerization catalyst is one or two selected from palladium on carbon or palladium on alumina.
14. The method for the long-term stable production of 3-methyl-2-butenol according to claim 13, wherein the reaction temperature of the isomerization reaction is 80 to 300 ℃; the reaction pressure is 0.1-3 MPaA.
15. The method for the long-term stable production of 3-methyl-2-butenol according to claim 14, wherein the reaction temperature of the isomerization reaction is 100 to 180 ℃; the reaction pressure is 0.1-2 MPaA.
16. The method for long-period stable production of 3-methyl-2-butenol according to claim 14, wherein the mass space velocity of the raw material 3-methyl-3-butenol is 0.3 to 30 hours -1 。
17. The method for long-period stable production of 3-methyl-2-butenol as claimed in claim 16, wherein the mass space velocity of the starting material 3-methyl-3-butenol is 0.5-10 h -1 。
18. The method for long-term stable production of 3-methyl-2-butenol as claimed in claim 16, wherein the volume space velocity of the hydrogen-containing carrier gas is 20 to 800 hours -1 。
19. The method for the long-term stable production of 3-methyl-2-butenol of claim 18, wherein the volume space velocity of the hydrogen-containing carrier gas is 50 to 500 hours -1 。
20. The method for long-term stable production of 3-methyl-2-butenol according to claim 16, wherein the carrier gas in the hydrogen-containing carrier gas is nitrogen, wherein the hydrogen content is 0.5 to 10vol%, and the nitrogen content is 90 to 99.5vol%.
21. The method for long-term stable production of 3-methyl-2-butenol according to claim 20, wherein the carrier gas in the hydrogen-containing carrier gas is nitrogen, wherein the hydrogen content is 0.5 to 5vol%, and the nitrogen content is 95 to 99.5vol%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4219683A (en) * | 1978-09-25 | 1980-08-26 | Phillips Petroleum Company | Isomerization of unsaturated alcohols |
| US4219682A (en) * | 1977-03-29 | 1980-08-26 | Phillips Petroleum Company | Alkenol production |
| JPH08268939A (en) * | 1995-03-30 | 1996-10-15 | Kuraray Co Ltd | Production of 3-methyl-2-butenol |
| CN103804145A (en) * | 2014-01-23 | 2014-05-21 | 万华化学集团股份有限公司 | Preparation method for 3-methyl-3-butene-1-ol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4219682A (en) * | 1977-03-29 | 1980-08-26 | Phillips Petroleum Company | Alkenol production |
| US4219683A (en) * | 1978-09-25 | 1980-08-26 | Phillips Petroleum Company | Isomerization of unsaturated alcohols |
| JPH08268939A (en) * | 1995-03-30 | 1996-10-15 | Kuraray Co Ltd | Production of 3-methyl-2-butenol |
| CN103804145A (en) * | 2014-01-23 | 2014-05-21 | 万华化学集团股份有限公司 | Preparation method for 3-methyl-3-butene-1-ol |
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| Title |
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| 3-甲基-2-丁烯-1-醇的制备新工艺;周宝强等;《化工进展》;20150105(第01期);全文 * |
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