CN114163303A - Continuous preparation method of 3-methyl-3-butene-1-ol - Google Patents
Continuous preparation method of 3-methyl-3-butene-1-ol Download PDFInfo
- Publication number
- CN114163303A CN114163303A CN202111351163.0A CN202111351163A CN114163303A CN 114163303 A CN114163303 A CN 114163303A CN 202111351163 A CN202111351163 A CN 202111351163A CN 114163303 A CN114163303 A CN 114163303A
- Authority
- CN
- China
- Prior art keywords
- isobutene
- content
- hydrogen
- reaction
- carbon monoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/043—Catalysts; their physical properties characterised by the composition
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a continuous preparation method of 3-methyl-3-butylene-1-alcohol, which can effectively improve selectivity by controlling the contents of impurities of carbon dioxide, carbon monoxide and hydrogen in raw material isobutene, solve the problem of device blockage in the production process of preparing the 3-methyl-3-butylene-1-alcohol, improve the running stability of the device, reduce the treatment cost of waste gas, reduce carbon emission and improve the economy of carbon atoms by recycling the carbon monoxide, the hydrogen and the carbon dioxide in the waste gas.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a continuous preparation method of 3-methyl-3-butene-1-ol.
Background
The 3-methyl-3-butene-1-ol can be used as an initiator for synthesizing the polycarboxylic acid high-efficiency water reducing agent side chain TPEG polyether. In addition, 3-methyl-3-buten-1-ol is isomerized into 3-methyl-2-buten-1-ol, which is the main raw material for synthesizing pesticide ethyl methyl benzoate. The 3-methyl-3-butene-1-ol liquid is also applied to the fields of medicines, dyes, spices and the like, and is an important raw material for artificially synthesizing citral.
CN103333048A describes that paraformaldehyde is depolymerized in a solvent methanol, and is reacted with isobutene under the action of a catalyst alkali metal phosphate to synthesize 3-methyl-3-butene-1-ol, wherein the reaction temperature is 200-300 ℃, the pressure is 8-10 MPa, and the conversion rate of the obtained product is 68%.
CN102060667A discloses a solvent-free and catalyst-free method for preparing 3-methyl-3-butene-1-ol from formaldehyde and isobutene at 200-300 ℃ and 9-15 MPa, wherein the yield is 90% based on isobutene and 97% based on formaldehyde.
CN106582788A discloses a method for synthesizing 3-methyl-3-butene-1-ol by formaldehyde and isobutene under the action of a transition metal salt catalyst, wherein the reaction temperature is 200-260 ℃, and the pressure is 15-23 MPa.
CN1544400A describes the synthesis of isobutene and isobutane from carbon monoxide, hydrogen and carbon dioxide in the presence of a zirconia or zirconia-doped catalyst, but with low carbon monoxide conversion and low isobutene and isobutane yields.
The published patent shows that the conditions for preparing 3-methyl-3-buten-1-ol from formaldehyde and isobutene are high temperature and high pressure, under which the formaldehyde is easily disproportionated to generate formic acid, the formaldehyde is directly decomposed to generate carbon monoxide and hydrogen, the disproportionated formic acid is continuously decomposed to carbon dioxide and hydrogen at high temperature, which causes the system to contain carbon dioxide, carbon monoxide and hydrogen, thereby bringing about a plurality of side reactions, and the isobutene and formaldehyde are hydrogenated under the conditions of high temperature and high pressure, thereby causing the selectivity of isobutene and formaldehyde to be reduced. In addition, the existence of carbon dioxide and carbon monoxide can accelerate the polymerization and carbonization speed of formaldehyde and isobutene under high-temperature conditions, accelerate the blockage of the device and influence the stable operation of the device.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a continuous process for preparing 3-methyl-3-buten-1-ol, which increases the selectivity of formaldehyde and isobutylene in the process of synthesizing 3-methyl-3-buten-1-ol and recycles the byproduct waste gas. The invention finds that the selectivity can be effectively improved by controlling the contents of impurities of carbon dioxide, carbon monoxide and hydrogen in the raw material isobutene, the problem of device blockage in the production process of preparing the 3-methyl-3-buten-1-ol is solved, the running stability of the device is improved, and the carbon monoxide, the hydrogen and the carbon dioxide in the waste gas are recycled, so that the waste gas treatment cost is reduced, the carbon emission is reduced, and the carbon atom economy is improved.
Different from the conventional method that a specific catalyst is added and reaction conditions are changed to improve the selectivity of isobutene and formaldehyde, the invention unexpectedly discovers that the content of impurities of carbon dioxide, carbon monoxide and hydrogen in isobutene has a certain relation with the product selectivity in the research process of preparing 3-methyl-3-butene-1-ol, if the content of carbon dioxide, carbon monoxide and hydrogen in isobutene raw materials is controlled within a certain range and the lower content of carbon dioxide, carbon monoxide and hydrogen in a system is kept in the reaction process, the selectivity of 3-methyl-3-butene-1-ol can be obviously improved, meanwhile, the side reaction of polymerization and carbonization can be eliminated, a device is not easy to block, and the operation stability is improved. In addition, in the research of the recovery process of the waste gases of carbon monoxide, hydrogen and carbon dioxide, the byproduct waste gas can be synthesized into isobutene with high activity and high selectivity by catalysis of the modified zirconia, and the isobutene is recovered and applied to isobutene raw materials.
Based on the research, the invention provides a continuous preparation method of 3-methyl-3-butene-1-ol, which adopts the following technical scheme:
the invention provides a continuous preparation method of 3-methyl-3-butene-1-ol, which comprises the following steps:
1) carrying out continuous reaction on isobutene and formaldehyde under the conditions of high temperature and high pressure to prepare a reaction solution, wherein the total content of carbon dioxide, carbon monoxide and hydrogen in the raw material isobutene is 0.05-0.5 wt%, and preferably 0.05-0.35 wt%;
2) transferring the reaction liquid into a rectifying tower, separating to obtain a tower top light component containing unreacted isobutene, carbon dioxide, carbon monoxide and hydrogen and a tower bottom heavy component containing a 3-methyl-3-butene-1-ol product, and separating and refining the tower bottom heavy component to obtain the 3-methyl-3-butene-1-ol product;
3) carrying out gas-liquid separation on the light components at the top of the tower obtained in the step 2), and continuously extracting noncondensable gas containing isobutene;
4) carrying out cryogenic separation on the non-condensable gas extracted in the step 3) to obtain a liquid phase containing unreacted isobutene, mixing the liquid phase with the liquid remaining from the gas-liquid separation in the step 3), and applying the liquid phase to the isobutene raw material in the step 1);
optionally, 5) carrying out cryogenic separation on the residual mixed gas phase containing carbon monoxide, carbon dioxide and hydrogen in the step 4), reacting under the action of a composite modified zirconia catalyst to prepare isobutene, and mechanically applying the isobutene to the isobutene raw material in the step 1).
In the method, in the step 1), the isobutene raw material comprises fresh isobutene, isobutene for cyclic use and isobutene recovered from waste gas, wherein the fresh isobutene accounts for 5-20%, preferably 10-15%, the isobutene for cyclic use accounts for 80-95%, preferably 85-90%, and the isobutene recovered from waste gas accounts for 0-10%, preferably 0.5-5%, more preferably 1-3%, based on 100% of the total mass of the raw material isobutene;
the fresh isobutene is a common commercial raw material, the purity is more than or equal to 99.9%, the total content of carbon dioxide, carbon monoxide and hydrogen is preferably required to be controlled to be less than or equal to 0.03%, and the content of carbon dioxide, carbon monoxide and hydrogen is more preferably less than or equal to 0.01%, the content of carbon monoxide is less than or equal to 0.01% and the content of hydrogen is less than or equal to 0.01%;
the recycling use of the isobutene comes from step 4), namely a mixed liquid of a liquid phase containing unreacted isobutene obtained by deep cooling separation in step 4) and a residual liquid of gas-liquid separation in step 3); preferably, the content of carbon dioxide in the mixed solution is less than or equal to 0.04 percent, the content of carbon monoxide is less than or equal to 0.03 percent, and the content of hydrogen is less than or equal to 0.03 percent;
the isobutene recovered from the waste gas is obtained in the step 5), namely the isobutene prepared by the reaction of the residual mixed gas phase containing carbon monoxide, carbon dioxide and hydrogen through the cryogenic separation in the step 4), wherein preferably, the content of the carbon dioxide is less than or equal to 1.2 percent, the content of the carbon monoxide is less than or equal to 1 percent and the content of the hydrogen is less than or equal to 0.8 percent.
After the raw material isobutene is mixed, the total content of carbon dioxide, carbon monoxide and hydrogen is required to be controlled to be 0.05-0.5 wt%, if the total content is higher than 0.5%, the content of impurities of carbon dioxide, carbon monoxide and hydrogen in the isobutene can be reduced or removed by the existing separation means before feeding so as to be reduced to be below 0.5%.
In the method of the invention, in step 1), the formaldehyde raw material is selected from any one of formaldehyde solution, paraformaldehyde, methylal and hemiacetal or a combination of at least two of the formaldehyde solution, the paraformaldehyde, the methylal and the hemiacetal, and preferably any one of the formaldehyde solution, the methylal and the hemiacetal or a combination of at least two of the formaldehyde solution, the methylal and the hemiacetal.
In the method, in the step 1), the molar ratio of the isobutene to the formaldehyde is 3-30: 1, preferably 8 to 25: 1.
in the method, in the step 1), the reaction temperature is 160-400 ℃, preferably 180-320 ℃, the reaction pressure is 5-30 MPaG, preferably 10-25 MPaG, and the reaction residence time is 5-45 min, preferably 15-30 min.
In the method of the present invention, in step 1), the reaction may be performed in a solvent or in a solvent-free condition, specifically, depending on the presence of the formaldehyde raw material, and is generally used for depolymerizing paraformaldehyde, diluting formaldehyde to increase the solubility of the formaldehyde solution in isobutylene, reduce formaldehyde aggregation, further reduce disproportionation and decomposition of formaldehyde, and increase selectivity, preferably, the solvent is selected from any one or a combination of at least two of water, methanol, ethanol, tert-butanol, n-butanol, octanol, pentanol, and isopentenol, preferably any one or a combination of at least two of methanol, tert-butanol, n-butanol, and isopentenol; preferably, the dosage of the solvent is 0.5-3 times of the mass of the formaldehyde.
In the step 1), the reaction process can control the lower contents of carbon dioxide, carbon monoxide and hydrogen in the reaction kettle system by continuously transferring the reaction liquid into the rectifying tower in the step 2), preferably, the contents of the carbon dioxide, the carbon monoxide and the hydrogen are controlled to be less than or equal to 0.2 percent, less than or equal to 0.15 percent and less than or equal to 0.15 percent
In the step 2), the number of theoretical plates of the rectifying tower is 10-35, preferably 25-30, the pressure at the top of the rectifying tower is controlled to be 300-1000 KPaG, preferably 400-700 KPaG, the temperature is 35-85 ℃, preferably 45-70 ℃, and the temperature at the bottom of the rectifying tower is 80-160 ℃, preferably 100-150 ℃.
In the step 2), the 3-methyl-3-butene-1-ol product is prepared by separating and refining the heavy component at the bottom of the tower containing the 3-methyl-3-butene-1-ol product, wherein the separation and refining are conventional operations in the field, the method does not make specific requirements, and can comprise dehydrogenation, rectification and the like, for example, light component impurities can be removed by a light component removing and refining tower, heavy component tar can be removed by rectifying tower bottoms, and the 3-methyl-3-butene-1-ol product can be obtained, and the purity of the prepared product can reach more than 99.7%.
In the step 3), the gas-liquid separation is carried out in a gas-liquid separation tank, the gas-liquid separation temperature is controlled to be 20-60 ℃, preferably 30-45 ℃, and the pressure is controlled to be 200-800 KPaG, preferably 400-600 KPaG.
In the step 4), the cryogenic separation is carried out at the normal pressure and the temperature of-30 to-10 ℃, preferably-20 to-15 ℃, and the separation time is 15 to 60min, preferably 20 to 35 min.
In the step 5), the mixed gas phase containing carbon monoxide, carbon dioxide and hydrogen comprises, by volume percentage, 10-20% of carbon dioxide, preferably 12-16%, 30-40% of carbon monoxide, preferably 32-36%, and 40-60% of hydrogen, preferably 45-55%.
In the method, in the step 5), the composite modified zirconia catalyst comprises a main catalyst zirconia, a cocatalyst and a modifier;
the cocatalyst is selected from any one or the combination of at least two of nickel oxide, chromium oxide, copper oxide, zinc oxide, aluminum oxide and palladium oxide, preferably any one or the combination of at least two of nickel oxide, zinc oxide and aluminum oxide;
the modifier is selected from any one or the combination of at least two of calcium phosphide, zinc phosphide, aluminum phosphide, copper phosphide and magnesium phosphide, and is preferably selected from any one or the combination of at least two of zinc phosphide, copper phosphide and magnesium phosphide.
The composite modified zirconia catalyst comprises, based on the total mass of the catalyst, 60-80% of zirconia, 15-30% of a cocatalyst and 0.1-1% of a modifier;
preferably, based on the total mass of the catalyst, the content of each component is 65-75% of zirconia, 20-25% of cocatalyst and 0.3-0.7% of modifier.
The composite modified zirconia catalyst can be prepared by any method disclosed in the prior art, and the invention has no specific requirement, such as the following method in some specific examples: mixing zirconia and a cocatalyst, fully grinding, washing with ammonia, washing to neutrality, drying, mixing with a modifier, fully grinding, and roasting (at 500-750 ℃ for 10-16 h) to obtain the composite modified zirconia catalyst.
In the method, in the step 5), the reaction is preferably carried out in a fixed bed reactor, the reaction pressure is 5-10 MpaG, preferably 6-8 MpaG, the reaction temperature is 280-500 ℃, preferably 320-400 ℃, and the reaction time is 30-90 min, preferably 40-60 min.
Preferably, the reaction space velocity in the reaction process is 0.2-1 h-1Preferably 0.3 to 0.6h-1。
Preferably, after the reaction is finished, the method also comprises a temperature-reducing pressure-reducing flash evaporation operation, which is a conventional operation in the field and does not make specific requirements, the purity of the obtained waste gas recovered isobutene is more than 97%, the conversion rate of carbon monoxide can reach more than 65%, and the yield of isobutene is more than 60%.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
in the process of synthesizing the 3-methyl-3-butene-1-ol, on one hand, the content of carbon dioxide, carbon monoxide and hydrogen in the isobutene raw material is controlled to be 0.05-0.5 wt%, the product selectivity is improved, the lower content of the carbon dioxide, the carbon monoxide and the hydrogen in the system is kept in the reaction process, the selectivity is further improved, the generation of tar and high polymers is reduced, the operation stability of the device is obviously improved, meanwhile, unreacted isobutene is recycled, and the conversion rate of formaldehyde and isobutene is obviously improved.
On the other hand, aiming at waste gas containing carbon dioxide, carbon monoxide and hydrogen generated by disproportionation and decomposition of formaldehyde at high temperature, the modified zirconia is catalyzed to synthesize isobutene with high activity and high selectivity, the isobutene is recycled and applied to isobutene raw materials to increase the product yield, and the waste gas is recycled to reduce carbon emission, reduce the product cost, improve the economic benefit and increase the product competitiveness.
Detailed Description
The present invention is further illustrated in detail by the following examples, but the scope of the present invention is not limited to the following examples.
The impurities of carbon dioxide, carbon monoxide and hydrogen in isobutene are measured by gas chromatography, and the analysis conditions are as follows:
an Agilent gas phase analysis method, a chromatographic column: 1. DB-WAX (30m-0.32mm-0.5 μm); 2. P-N column (1m, maximum use temperature 190 ℃); 3. MS-13X molecular sieve packed column (2m, maximum service temperature: 350 ℃); 4. a DC 200PEG column; SPL: 270 ℃ TCD: FID at 180 ℃: 250 ℃; temperature programming: keeping at 50 deg.C for 8 min; raising the temperature to 110 ℃ at the speed of 20 ℃/min and keeping the temperature for 3 min; raising the temperature to 170 ℃ at the speed of 20 ℃/min and keeping the temperature for 10 min; column flow rate: 1.5 ml/min; APC-1 (He): 265 kpa; APC-3 (H)2)：55kpa。
Detecting the content of 3-methyl-3-butene-1-ol in the reaction solution by adopting a gas chromatograph, wherein the specific analysis conditions are as follows:
the chromatograph was an Agilent 7890A, a column model HP-5, an internal diameter 320.00 μm, a length of 30.0m, and a maximum temperature of 325.0 ℃. The temperature raising program is that the temperature is kept for 1 minute at 40 ℃, is raised to 140 ℃ at 10 ℃/min and is kept for 2 minutes, is raised to 280 ℃ at 20 ℃/min and is kept for 6 minutes, and the total running time is 30 minutes.
The method comprises the following steps of (1) quantifying the formaldehyde content in a sample to be detected by adopting a liquid chromatography external standard method, wherein the specific analysis conditions are as follows:
chromatography apparatus: agilent-1260, column model: c18 silica gel column, length of column: 25cm, column inner diameter: 4.6mm, particle size: 5 μm, mobile phase: acetonitrile and ultrapure water, column flow rate: 1.0ml/min, column temperature: 40 ℃, detector temperature: 35 ℃, detection wavelength: 360nm, and the total running time is 35 min.
Pressure drop of the reactor: and (4) testing the pressure drop of the reactor continuously running for 500h, and judging the blockage condition of the reactor through the pressure drop.
In the following examples, unless otherwise specified, all are common commercial starting materials:
the fresh isobutene is purchased isobutene (Ming torch gas Co., Ltd.), the purity is more than 99.9%, the content of carbon dioxide impurities is less than 0.01%, the content of carbon monoxide is less than 0.01%, and the content of hydrogen is less than 0.01%.
The composite modified zirconia catalyst is prepared by the following method:
weighing 100g of pure zirconium oxide in a mortar, adding 28g of nickel oxide, fully grinding and mixing, adding 300ml of ammonia water, stirring for 10min, adding the mixture into a flask, heating to evaporate the ammonia water, then adding pure water, fully stirring, performing suction filtration, repeating the washing and suction filtration processes until the PH value of a washing solution is 7, filtering the washed mixture to obtain a composite catalyst solid, and drying the composite catalyst in an oven at 150 ℃ for 5 h;
and accurately weighing 64g of the obtained composite catalyst in a mortar, fully grinding, adding 0.3g of zinc phosphide, uniformly stirring and mixing, and roasting in a muffle furnace at 550 ℃ for 13 hours to obtain the composite modified zirconia catalyst-1.
According to the preparation method of the catalyst, the compound modified zirconia catalyst-2, the compound modified zirconia catalyst-3, the compound modified zirconia catalyst-4 and the compound modified zirconia catalyst-5 are prepared by adopting different types and dosages of the main catalyst, the cocatalyst and the modifier, and the components are as shown in the following table 1:
TABLE 1 catalyst composition
| Numbering | Main catalyst | Content (wt.) | Co-catalyst | Content (wt.) | Modifying agent | Content (wt.) |
| Catalyst 1 | Zirconium oxide | 70.13％ | Nickel oxide | 29.40％ | Zinc phosphide | 0.47％ |
| Catalyst 2 | Zirconium oxide | 74.81％ | Alumina oxide | 25.04％ | Copper phosphide | 0.15％ |
| Catalyst 3 | Zirconium oxide | 61.52％ | Chromium oxide | 38.17％ | Aluminium phosphide | 0.31％ |
| Catalyst 4 | Zirconium oxide | 79.12％ | Palladium oxide | 20.19％ | Calcium phosphide | 0.69％ |
| Catalyst 5 | Zirconium oxide | 64.94％ | Copper oxide | 34.10％ | Magnesium phosphide | 0.96％ |
Example 1
The continuous preparation method of 3-methyl-3-butene-1-ol comprises the following steps:
the total content of impurities of carbon dioxide, carbon monoxide and hydrogen in the isobutene raw material is 0.079%, the composition of the impurities is 10% of fresh isobutene, 88.5% of isobutene recycled for use, and 1.5% of isobutene recovered from waste gas, wherein the isobutene recycled for use is from a mixed solution in the following step 4), and the isobutene recovered from the waste gas is from the following step 5).
1) Continuously feeding an isobutene raw material and 37% formaldehyde aqueous solution into a reactor according to a molar ratio of isobutene/formaldehyde of 25, controlling the reaction temperature to be 260 ℃, the reaction pressure to be 18MPaG, and the reaction residence time to be 20min to prepare a reaction solution, wherein the content of carbon dioxide in a reaction process control system is less than or equal to 0.035%, the content of carbon monoxide is less than or equal to 0.021%, and the content of hydrogen is less than or equal to 0.023%;
2) step 1), continuously transferring the reaction liquid into a rectifying tower, controlling the number of theoretical plates to be 25, controlling the pressure at the top of the tower to be 500KPaG, controlling the temperature to be 57 ℃, controlling the temperature at the bottom of the tower to be 130 ℃, separating to obtain light components at the top of the tower containing unreacted isobutene, carbon dioxide, carbon monoxide and hydrogen and heavy components at the bottom of the tower containing 3-methyl-3-butene-1-ol products, removing light component impurities from the heavy components at the bottom of the tower by a light component removal rectifying tower, rectifying the liquid at the bottom of the tower to remove heavy component tar, and obtaining 3-methyl-3-butene-1-ol products with the purity of 99.85%;
3) carrying out gas-liquid separation on the light components at the top of the tower obtained in the step 2), wherein the temperature of a gas-liquid separation tank is 30 ℃, the pressure is 400KPaG, and the noncondensable gas containing isobutene is continuously extracted;
4) carrying out cryogenic separation on the non-condensable gas extracted in the step 3) at the normal pressure of-15 ℃, wherein the separation time is 24min, obtaining a liquid phase containing unreacted isobutene, mixing the liquid phase with the liquid remaining from the gas-liquid separation in the step 3), and mechanically applying the obtained mixed liquid containing 0.02% of carbon dioxide, 0.015% of carbon monoxide and 0.015% of hydrogen to the isobutene raw material in the step 1);
5) introducing the mixed gas phase containing 35 percent of carbon monoxide, 15 percent of carbon dioxide and 50 percent of hydrogen and remained by cryogenic separation in the step 4) into a fixed bed reactor filled with the composite modified zirconia catalyst 1 (space velocity of 0.4 h)-1) Reacting at 8MPaG and 350 ℃ for 50min, reducing the temperature, reducing the pressure and flashing to obtain waste gas and recovering isobutene, wherein the conversion rate of carbon monoxide is 67.8%, the yield of isobutene is 64.75%, the purity of the waste gas and recovering isobutene is 97.4%, the content of carbon dioxide is 1.1%, the content of carbon monoxide is 0.5%, and the content of hydrogen is 0.6%, and the waste gas and recovering isobutene are mechanically applied to the isobutene raw material in the step 1).
The continuous preparation method of the embodiment tests that the conversion rate of formaldehyde is 98.7 percent and the selectivity of 3-methyl-3-butene-1-ol is 98.4 percent. The pressure drop of the reactor is 0.010Mpa, no blockage occurs, and the running stability of the device is good.
Example 2
The continuous preparation method of 3-methyl-3-butene-1-ol comprises the following steps:
the total content of impurities of carbon dioxide, carbon monoxide and hydrogen in the isobutene raw material is 0.126%, the composition is 15% of fresh isobutene, 82% of isobutene recycled mechanically, and 3% of isobutene recovered from waste gas, wherein the isobutene recycled mechanically is a mixed solution obtained in the following step 4), and the isobutene recovered from the waste gas is obtained in the following step 5).
1) Continuously feeding an isobutene raw material and a methanol solution of 30 wt% formaldehyde into a reactor according to a molar ratio of isobutene/formaldehyde of 20, controlling the reaction temperature to be 320 ℃, the reaction pressure to be 25MPaG, and the reaction residence time to be 15min to prepare a reaction solution, wherein the content of carbon dioxide in a reaction process control system is less than or equal to 0.053%, the content of carbon monoxide is less than or equal to 0.041%, and the content of hydrogen is less than or equal to 0.032%;
2) step 1), continuously transferring the reaction liquid into a rectifying tower, controlling the number of theoretical plates to be 30, controlling the pressure at the top of the tower to be 700KPaG, controlling the temperature to be 68 ℃, controlling the temperature at the bottom of the tower to be 150 ℃, separating to obtain light components at the top of the tower containing unreacted isobutene, carbon dioxide, carbon monoxide and hydrogen and heavy components at the bottom of the tower containing 3-methyl-3-butene-1-ol products, removing light component impurities from the heavy components at the bottom of the tower by a light component removal rectifying tower, rectifying the liquid at the bottom of the tower to remove heavy component tar, and obtaining 3-methyl-3-butene-1-ol products with the purity of 99.86%;
3) carrying out gas-liquid separation on the light components at the top of the tower obtained in the step 2), wherein the temperature of a gas-liquid separation tank is 45 ℃, the pressure is 600KPaG, and continuously extracting noncondensable gas containing isobutene;
4) carrying out cryogenic separation on the non-condensable gas extracted in the step 3) at the normal pressure of-20 ℃ for 35min to obtain a liquid phase containing unreacted isobutene, mixing the liquid phase with the liquid remaining from the gas-liquid separation in the step 3), and mechanically applying the liquid phase to the isobutene raw material in the step 1), wherein the content of carbon dioxide in the obtained mixed liquid is 0.03%, the content of carbon monoxide in the mixed liquid is 0.02%, and the content of hydrogen in the mixed liquid is 0.02%;
5) the volume fraction of the residual content in the cryogenic separation of the step 4)Introducing a mixed gas phase of 40 percent of carbon monoxide, 12 percent of carbon dioxide and 48 percent of hydrogen into a fixed bed reactor filled with the composite modified zirconia catalyst 2 (space velocity of 0.6 h)-1) Reacting at 6MPaG and 400 ℃ for 40min, reducing the temperature, reducing the pressure, flashing, and obtaining waste gas and recovering isobutene, wherein the conversion rate of carbon monoxide is 68.8%, the yield of isobutene is 64.52%, the purity of the waste gas and recovering isobutene is 97.6%, the content of carbon dioxide is 0.9%, the content of carbon monoxide is 0.8%, and the content of hydrogen is 0.5%, and the waste gas and recovering isobutene are mechanically applied to the isobutene raw material in the step 1).
The continuous preparation method of the embodiment tests that the conversion rate of formaldehyde is 98.2 percent and the selectivity of 3-methyl-3-butene-1-ol is 97.8 percent. The pressure drop of the reactor is 0.023Mpa, no blockage occurs, and the running stability of the device is good.
Example 3
The continuous preparation method of 3-methyl-3-butene-1-ol comprises the following steps:
the total content of impurities of carbon dioxide, carbon monoxide and hydrogen in the isobutene raw material is 0.09%, and the isobutene raw material consists of 16% of fresh isobutene, 82% of isobutene recycled mechanically and 2% of waste gas for isobutene recovery, wherein the isobutene recycled mechanically is a mixed solution obtained in the following step 4), and the waste gas for isobutene recovery is a step 5).
1) Continuously feeding an isobutene raw material and a tert-butyl alcohol solution of 45 wt% of formaldehyde into a reactor according to a molar ratio of isobutene/formaldehyde of 16, controlling the reaction temperature at 180 ℃, the reaction pressure at 10MPaG, and the reaction retention time for 40min to prepare a reaction solution, wherein the carbon dioxide content is less than or equal to 0.04%, the carbon monoxide content is less than or equal to 0.02%, and the hydrogen content is less than or equal to 0.03% in a reaction process control system;
2) step 1), continuously transferring the reaction liquid into a rectifying tower, controlling the number of theoretical plates to be 20, controlling the pressure at the top of the tower to be 400KPaG, controlling the temperature to be 46 ℃, controlling the temperature at the bottom of the tower to be 105 ℃, separating to obtain light components at the top of the tower containing unreacted isobutene, carbon dioxide, carbon monoxide and hydrogen and heavy components at the bottom of the tower containing 3-methyl-3-butene-1-ol products, removing light component impurities from the heavy components at the bottom of the tower by a light component removal rectifying tower, rectifying the liquid at the bottom of the tower to remove heavy component tar, and obtaining 3-methyl-3-butene-1-ol products with the purity of 99.89%;
3) carrying out gas-liquid separation on the light components at the top of the tower obtained in the step 2), wherein the temperature of a gas-liquid separation tank is 60 ℃, the pressure is 800KPaG, and continuously extracting noncondensable gas containing isobutene;
4) carrying out cryogenic separation on the non-condensable gas extracted in the step 3) at the normal pressure of-30 ℃ for 57min to obtain a liquid phase containing unreacted isobutene, mixing the liquid phase with the liquid remaining from the gas-liquid separation in the step 3), and mechanically applying the liquid phase to the isobutene raw material in the step 1), wherein the content of carbon dioxide in the obtained mixed liquid is 0.035%, the content of carbon monoxide in the mixed liquid is 0.015% and the content of hydrogen in the mixed liquid is 0.025%;
5) introducing the mixed gas phase containing 32 percent of carbon monoxide, 13 percent of carbon dioxide and 55 percent of hydrogen left by cryogenic separation in the step 4) into a fixed bed reactor filled with a composite modified zirconia catalyst 3 (space velocity of 0.5 h)-1) Reacting for 85min at 285 ℃ under 10MPaG, reducing the temperature, reducing the pressure, flashing, and obtaining waste gas and recovering isobutene, wherein the conversion rate of carbon monoxide is 67.5%, the yield of isobutene is 65.2%, the purity of the waste gas and recovering isobutene is 97.7%, the content of carbon dioxide is 0.55%, the content of carbon monoxide is 0.30%, and the content of hydrogen is 0.40%, and the waste gas and recovering isobutene are mechanically applied to the isobutene raw material in the step 1).
The continuous preparation method of the embodiment tests that the conversion rate of formaldehyde is 97.8 percent and the selectivity of 3-methyl-3-butene-1-ol is 98.2 percent. The pressure drop of the reactor is 0.016MPa, no blockage occurs, and the running stability of the device is good.
Example 4
The continuous preparation method of 3-methyl-3-butene-1-ol comprises the following steps:
the total content of isobutene raw material impurities of carbon dioxide, carbon monoxide and hydrogen is 0.312%, the composition of the isobutene raw material impurities is 6% of fresh isobutene, 84% of isobutene recycled and 10% of isobutene recovered from waste gas, wherein the isobutene recycled and recycled is a mixed solution obtained in the following step 4), and the isobutene recovered from the waste gas is obtained in the following step 5).
1) Continuously feeding an isobutene raw material and a n-butanol solution of hemiacetal with the concentration of 60 wt% into a reactor according to the molar ratio of isobutene/hemiacetal being 8, controlling the reaction temperature to be 380 ℃, the reaction pressure to be 30MPaG, and the reaction retention time to be 6min to prepare a reaction solution, wherein the carbon dioxide content is less than or equal to 0.132%, the carbon monoxide content is less than or equal to 0.085%, and the hydrogen content is less than or equal to 0.094% in a reaction process control system;
2) step 1), continuously transferring the reaction liquid into a rectifying tower, controlling the number of theoretical plates to be 12, controlling the pressure at the top of the tower to be 900KPaG, controlling the temperature to be 81 ℃, controlling the temperature at the bottom of the tower to be 155 ℃, separating to obtain light components at the top of the tower containing unreacted isobutene, carbon dioxide, carbon monoxide and hydrogen and heavy components at the bottom of the tower containing 3-methyl-3-butene-1-ol products, removing light component impurities from the heavy components at the bottom of the tower by a light component removal rectifying tower, rectifying the liquid at the bottom of the tower to remove heavy component tar, and obtaining 3-methyl-3-butene-1-ol products with the purity of 99.85%;
3) carrying out gas-liquid separation on the light components at the top of the tower obtained in the step 2), wherein the temperature of a gas-liquid separation tank is 25 ℃, the pressure is 200KPaG, and continuously extracting noncondensable gas containing isobutene;
4) carrying out cryogenic separation on the non-condensable gas extracted in the step 3) at the normal pressure of-10 ℃ for 16min to obtain a liquid phase containing unreacted isobutene, mixing the liquid phase with the residual liquid obtained in the step 3) for gas-liquid separation, and mechanically applying the liquid phase to the isobutene raw material obtained in the step 1), wherein the content of carbon dioxide is 0.032%, the content of carbon monoxide is 0.018%, and the content of hydrogen is 0.017%;
5) introducing the mixed gas phase containing 38 percent of carbon monoxide, 10 percent of carbon dioxide and 52 percent of hydrogen left by cryogenic separation in the step 4) into a fixed bed reactor filled with the composite modified zirconia catalyst 4 (space velocity of 0.3 h)-1) Reacting at 5MPaG and 320 ℃ for 60min, cooling, depressurizing and flashing to obtain waste gas and recycling isobutene, wherein the conversion rate of carbon monoxide is 68.5%, the yield of isobutene is 64.32%, the purity of the waste gas and recycling isobutene is 97.3%, the content of carbon dioxide is 1.05%, the content of carbon monoxide is 0.7%, and the content of hydrogen is 0.8%, and the waste gas and recycling isobutene are mechanically applied to the isobutene raw material in the step 1).
The continuous preparation according to this example was tested for a conversion of hemiacetal of 98.3% and a selectivity of 3-methyl-3-buten-1-ol of 96.9%. The pressure drop of the reactor is 0.028Mpa, no blockage occurs, and the running stability of the device is good.
Example 5
The continuous preparation method of 3-methyl-3-butene-1-ol comprises the following steps:
the total content of impurities of carbon dioxide, carbon monoxide and hydrogen in the isobutene raw material is 0.164%, and the composition of the isobutene raw material comprises 12% of fresh isobutene, 81% of isobutene recycled by recycling and 7% of isobutene recovered from waste gas, wherein the isobutene recycled by recycling is from a mixed solution in the following step 4), and the isobutene recovered from the waste gas is from the following step 5).
1) Continuously feeding an isobutene raw material and a 50 wt% methylal methanol solution into a reactor according to a molar ratio of isobutene/formaldehyde of 30, controlling the reaction temperature to be 240 ℃, the reaction pressure to be 8MPaG, and the reaction residence time to be 30min to prepare a reaction solution, wherein the carbon dioxide content is less than or equal to 0.037%, the carbon monoxide content is less than or equal to 0.068%, and the hydrogen content is less than or equal to 0.060% in a reaction process control system;
2) step 1), continuously transferring the reaction liquid into a rectifying tower, controlling the number of theoretical plates to be 27, controlling the pressure at the top of the tower to be 650KPaG, controlling the temperature to be 62 ℃ and the temperature at the bottom of the tower to be 143 ℃, separating to obtain light components at the top of the tower containing unreacted isobutene, carbon dioxide, carbon monoxide and hydrogen and heavy components at the bottom of the tower containing 3-methyl-3-butene-1-ol products, removing light component impurities from the heavy components at the bottom of the tower by a light component removal rectifying tower, rectifying the liquid at the bottom of the tower to remove heavy component tar, and obtaining 3-methyl-3-butene-1-ol products with the purity of 99.87%;
3) carrying out gas-liquid separation on the light components at the top of the tower obtained in the step 2), wherein the temperature of a gas-liquid separation tank is 40 ℃, the pressure is 500KPaG, and the noncondensable gas containing isobutene is continuously extracted;
4) carrying out cryogenic separation on the non-condensable gas extracted in the step 3) at the normal pressure of-25 ℃, wherein the separation time is 45min, obtaining a liquid phase containing unreacted isobutene, mixing the liquid phase with the liquid remaining from the gas-liquid separation in the step 3), and mechanically applying the obtained mixed liquid containing 0.015% of carbon dioxide, 0.026% of carbon monoxide and 0.01% of hydrogen to the isobutene raw material in the step 1);
5) introducing the mixed gas phase containing 42 percent of carbon monoxide, 8 percent of carbon dioxide and 50 percent of hydrogen left by cryogenic separation in the step 4) into a fixed bed reactor filled with a composite modified zirconia catalyst 5 (space velocity of 0.9 h)-1) Reacting at 7MPa and 375 deg.C for 55min, cooling, depressurizing and flashing to obtain waste gas, recovering isobutene, whose CO conversion rate is 68.1%, and isobuteneThe alkene yield is 65.15%, the purity of the waste gas recovered isobutene is 97.8%, wherein the content of carbon dioxide is 0.35%, the content of carbon monoxide is 0.66%, and the content of hydrogen is 0.73%, and the waste gas recovered isobutene is applied to the isobutene raw material in the step 1).
The continuous preparation according to this example was tested for methylal conversion of 97.9% and selectivity to 3-methyl-3-buten-1-ol of 97.5%. The pressure drop of the reactor is 0.024Mpa, no blockage occurs, and the running stability of the device is good.
Comparative example 1
Referring to example 1, except that the fresh isobutene in step 1) was replaced by 90% pure isobutene, the total content of carbon dioxide, carbon monoxide and hydrogen as impurities was 9.8%, and the total content of carbon dioxide, carbon monoxide and hydrogen as impurities in the isobutene raw material mixed with the recycled isobutene and the isobutene recovered from the waste gas was 1.046%, which was otherwise the same as in example 1.
The comparative example continuous preparation method was tested to have a formaldehyde conversion of 98.6% and a 3-methyl-3-buten-1-ol selectivity of 81.2%. The pressure drop of the reactor is 0.720Mpa, the discharging of the reactor is gradually reduced, the feeding pressure is gradually increased, and the operation of the device is unstable.
Comparative example 2
The difference with reference to step 5) of example 1 is that the composite modified zirconia catalyst 1 was replaced with zirconia, the other conditions were not changed, the carbon monoxide conversion rate was 10%, the isobutylene yield was 8%, and the isobutylene purity recovered from the exhaust gas was 46%, wherein the carbon dioxide content was 7%, the carbon monoxide content was 19%, and the hydrogen content was 28%, and the catalyst was used as the isobutylene raw material in step 1).
The comparative example continuous preparation method tested that the formaldehyde conversion was 97.8% and the 3-methyl-3-buten-1-ol selectivity was 87.4%. The pressure drop of the reactor is 0.320Mpa, the discharging of the reactor is gradually reduced, the feeding pressure is gradually increased, and the operation of the device is unstable.
Comparative example 3
The difference of step 5) in reference to example 1 is that the composite modified zirconia catalyst 1 is replaced by a composite catalyst of 90% zirconia and 10% zinc phosphide (i.e. nickel oxide without adding a promoter), the other conditions are not changed, the carbon monoxide conversion rate is 18%, the isobutene yield is 12%, the purity of the waste gas recovery isobutene is 26%, wherein the carbon dioxide content is 10%, the carbon monoxide content is 28%, and the hydrogen content is 36%, and the waste gas recovery isobutene is applied to the isobutene raw material in step 1).
The comparative example continuous preparation method was tested to have a formaldehyde conversion of 98.2% and a 3-methyl-3-buten-1-ol selectivity of 85.6%. The pressure drop of the reactor is 0.570Mpa, the discharging of the reactor is gradually reduced, the feeding pressure is gradually increased, and the operation of the device is unstable.
Comparative example 4
The difference of step 5) in reference to example 1 is that the composite modified zirconia catalyst 1 is replaced by a composite catalyst of 85% zirconia and 15% nickel oxide (i.e. zinc phosphide as a modifier is not added), the other conditions are not changed, the carbon monoxide conversion rate is 48%, the isobutene yield is 24%, the purity of the recovered waste gas isobutene is 49%, wherein the carbon dioxide content is 8%, the carbon monoxide content is 17%, and the hydrogen content is 26%, and the catalyst is applied to the isobutene raw material in step 1).
The comparative example continuous preparation method was tested to have a formaldehyde conversion of 97.9% and a 3-methyl-3-buten-1-ol selectivity of 88.7%. The pressure drop of the reactor is 0.280Mpa, the discharging of the reactor is gradually reduced, the feeding pressure is gradually increased, and the operation of the device is unstable.
Comparative example 5:
referring to example 1, the process of recycling the waste gas to prepare isobutene in step 5) is not included, the isobutene raw material is fresh isobutene and the isobutene recycled, and the results show that:
in the reaction process of the step 1), the content of carbon dioxide in the system is less than or equal to 0.02 percent, the content of carbon monoxide is less than or equal to 0.014 percent, and the content of hydrogen is less than or equal to 0.014 percent.
The comparative example continuous preparation method was tested to have a formaldehyde conversion of 97.65% and a 3-methyl-3-buten-1-ol selectivity of 92.34%. The pressure drop of the reactor is 0.15Mpa, the discharging of the reactor is gradually reduced, the feeding pressure is gradually increased, and the operation of the device is unstable.
Claims (10)
1. A continuous preparation method of 3-methyl-3-buten-1-ol is characterized by comprising the following steps:
1) carrying out continuous reaction on isobutene and formaldehyde under the conditions of high temperature and high pressure to prepare a reaction solution, wherein the total content of carbon dioxide, carbon monoxide and hydrogen in the raw material isobutene is 0.05-0.5 wt%, and preferably 0.05-0.35 wt%;
2) transferring the reaction liquid into a rectifying tower, separating to obtain a tower top light component containing unreacted isobutene, carbon dioxide, carbon monoxide and hydrogen and a tower bottom heavy component containing a 3-methyl-3-butene-1-ol product, and separating and refining the tower bottom heavy component to obtain the 3-methyl-3-butene-1-ol product;
3) carrying out gas-liquid separation on the light components at the top of the tower obtained in the step 2), and continuously extracting noncondensable gas containing isobutene;
4) carrying out cryogenic separation on the non-condensable gas extracted in the step 3) to obtain a liquid phase containing unreacted isobutene, mixing the liquid phase with the liquid remaining from the gas-liquid separation in the step 3), and applying the liquid phase to the isobutene raw material in the step 1);
optionally, 5) carrying out cryogenic separation on the residual mixed gas phase containing carbon monoxide, carbon dioxide and hydrogen in the step 4), reacting under the action of a composite modified zirconia catalyst to prepare isobutene, and mechanically applying the isobutene to the isobutene raw material in the step 1).
2. The continuous preparation method according to claim 1, wherein in the step 1), the isobutene raw material comprises fresh isobutene, recycled isobutene and waste gas recovery isobutene, wherein the fresh isobutene accounts for 5-20%, preferably 10-15%, the recycled isobutene accounts for 80-95%, preferably 85-90%, and the waste gas recovery isobutene accounts for 0-10%, preferably 0.5-5%, more preferably 1-3%, based on 100% of the total mass of the raw material isobutene;
the fresh isobutene requires to control the total content of carbon dioxide, carbon monoxide and hydrogen to be less than or equal to 0.03 percent, preferably the content of carbon dioxide to be less than or equal to 0.01 percent, the content of carbon monoxide to be less than or equal to 0.01 percent and the content of hydrogen to be less than or equal to 0.01 percent;
the recycling use of the isobutene comes from step 4), namely a mixed liquid of a liquid phase containing unreacted isobutene obtained by deep cooling separation in step 4) and a residual liquid of gas-liquid separation in step 3); preferably, the content of carbon dioxide in the mixed solution is less than or equal to 0.04 percent, the content of carbon monoxide is less than or equal to 0.03 percent, and the content of hydrogen is less than or equal to 0.03 percent;
the isobutene recovered from the waste gas is obtained in the step 5), namely the isobutene prepared by the reaction of the residual mixed gas phase containing carbon monoxide, carbon dioxide and hydrogen through the cryogenic separation in the step 4), wherein preferably, the content of the carbon dioxide is less than or equal to 1.2 percent, the content of the carbon monoxide is less than or equal to 1 percent and the content of the hydrogen is less than or equal to 0.8 percent.
3. The continuous production method according to claim 1 or 2, wherein in step 1), the formaldehyde raw material is selected from any one of formaldehyde solution, paraformaldehyde, methylal and hemiacetal or a combination of at least two of them, preferably from any one of formaldehyde solution, methylal and hemiacetal or a combination of at least two of them;
preferably, the molar ratio of the isobutene to the formaldehyde is 3-30: 1, more preferably 8 to 25: 1.
4. the continuous production method according to any one of claims 1 to 3, wherein in the step 1), the reaction temperature is 160 to 400 ℃, preferably 180 to 320 ℃, the reaction pressure is 5 to 30MPaG, preferably 10 to 25MPaG, and the reaction residence time is 5 to 45min, preferably 15 to 30 min;
preferably, the reaction is carried out under solvent conditions, the solvent being selected from any one or a combination of at least two of water, methanol, ethanol, tert-butanol, n-butanol, octanol, pentanol, and isopentenol, more preferably any one or a combination of at least two of methanol, tert-butanol, n-butanol, and isopentenol; preferably, the using amount of the solvent is 0.5-3 times of the mass of the formaldehyde;
preferably, in the reaction process, the content of carbon dioxide in the reaction system is less than or equal to 0.2 percent, the content of carbon monoxide is less than or equal to 0.15 percent, and the content of hydrogen is less than or equal to 0.15 percent.
5. The continuous production method according to any one of claims 1 to 4, wherein in the step 2), the number of theoretical plates of the rectifying tower is 10 to 35, preferably 25 to 30, the pressure at the top of the rectifying tower is controlled to be 300 to 1000KPaG, preferably 400 to 700KPaG, the temperature is 35 to 85 ℃, preferably 45 to 70 ℃, and the temperature at the bottom of the rectifying tower is 80 to 160 ℃, preferably 100 to 150 ℃.
6. The continuous production method according to any one of claims 1 to 5, wherein the gas-liquid separation in step 3) is carried out in a gas-liquid separation tank, and the gas-liquid separation temperature is 20 to 60 ℃, preferably 30 to 45 ℃, and the pressure is 200 to 800KPaG, preferably 400 to 600 KPaG.
7. The continuous production method according to any one of claims 1 to 6, wherein in the step 4), the cryogenic separation is performed at normal pressure and at a temperature of-30 to-10 ℃, preferably-20 to-15 ℃, and the separation time is 15 to 60min, preferably 20 to 35 min.
8. The continuous production method according to any one of claims 1 to 7, wherein in the step 5), the mixed gas phase containing carbon monoxide, carbon dioxide and hydrogen comprises 10 to 20% by volume, preferably 12 to 16% by volume of carbon dioxide, 30 to 40% by volume, preferably 32 to 36% by volume of carbon monoxide and 40 to 60% by volume, preferably 45 to 55% by volume of hydrogen.
9. The continuous production method according to any one of claims 1 to 8, wherein in step 5), the composite modified zirconia catalyst comprises a main catalyst zirconia, a cocatalyst and a modifier;
the cocatalyst is selected from any one or the combination of at least two of nickel oxide, chromium oxide, copper oxide, zinc oxide, aluminum oxide and palladium oxide, preferably any one or the combination of at least two of nickel oxide, zinc oxide and aluminum oxide;
the modifier is selected from any one or the combination of at least two of calcium phosphide, zinc phosphide, aluminum phosphide, copper phosphide and magnesium phosphide, preferably any one or the combination of at least two of zinc phosphide, copper phosphide and magnesium phosphide;
the composite modified zirconia catalyst comprises, based on the total mass of the catalyst, 60-80% of zirconia, 15-30% of a cocatalyst and 0.1-1% of a modifier;
preferably, based on the total mass of the catalyst, the content of each group is 65-75% of zirconia, 20-25% of cocatalyst and 0.3-0.7% of modifier.
10. The continuous production method according to any one of claims 1 to 9, wherein in the step 5), the reaction is preferably carried out in a fixed bed reactor, the reaction pressure is 5 to 10MpaG, preferably 6 to 8MpaG, the reaction temperature is 280 to 500 ℃, preferably 320 to 400 ℃, and the reaction time is 30 to 90min, preferably 40 to 60 min.
Preferably, the reaction space velocity in the reaction process is 0.2-1 h-1Preferably 0.3 to 0.6h-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111351163.0A CN114163303B (en) | 2021-11-16 | 2021-11-16 | Continuous preparation method of 3-methyl-3-buten-1-ol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111351163.0A CN114163303B (en) | 2021-11-16 | 2021-11-16 | Continuous preparation method of 3-methyl-3-buten-1-ol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114163303A true CN114163303A (en) | 2022-03-11 |
| CN114163303B CN114163303B (en) | 2023-05-30 |
Family
ID=80479139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111351163.0A Active CN114163303B (en) | 2021-11-16 | 2021-11-16 | Continuous preparation method of 3-methyl-3-buten-1-ol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114163303B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573422A (en) * | 2022-03-15 | 2022-06-03 | 万华化学集团股份有限公司 | Treatment method of 3-methyl-3-butene-1-ol process waste liquid |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544400A (en) * | 2003-11-28 | 2004-11-10 | 清华大学 | Isobutene and isobutene preparation method |
| WO2008037693A1 (en) * | 2006-09-26 | 2008-04-03 | Basf Se | Continuous method for producing citral |
| CN105693470A (en) * | 2016-02-18 | 2016-06-22 | 江苏苏博特新材料股份有限公司 | Continuous 3-methyl-3-buten-1-ol production method |
| WO2018143104A1 (en) * | 2017-01-31 | 2018-08-09 | 株式会社クラレ | METHOD FOR PRODUCING γ,δ-UNSATURATED ALCOHOL |
| WO2020058119A1 (en) * | 2018-09-18 | 2020-03-26 | Basf Se | Process to recover high quality 3-methyl-but-3-en-1-ol |
| CN110981697A (en) * | 2019-12-18 | 2020-04-10 | 万华化学集团股份有限公司 | Method for synthesizing 3-methyl-3-butene-1-ol |
-
2021
- 2021-11-16 CN CN202111351163.0A patent/CN114163303B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1544400A (en) * | 2003-11-28 | 2004-11-10 | 清华大学 | Isobutene and isobutene preparation method |
| WO2008037693A1 (en) * | 2006-09-26 | 2008-04-03 | Basf Se | Continuous method for producing citral |
| CN105693470A (en) * | 2016-02-18 | 2016-06-22 | 江苏苏博特新材料股份有限公司 | Continuous 3-methyl-3-buten-1-ol production method |
| WO2018143104A1 (en) * | 2017-01-31 | 2018-08-09 | 株式会社クラレ | METHOD FOR PRODUCING γ,δ-UNSATURATED ALCOHOL |
| WO2020058119A1 (en) * | 2018-09-18 | 2020-03-26 | Basf Se | Process to recover high quality 3-methyl-but-3-en-1-ol |
| CN110981697A (en) * | 2019-12-18 | 2020-04-10 | 万华化学集团股份有限公司 | Method for synthesizing 3-methyl-3-butene-1-ol |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573422A (en) * | 2022-03-15 | 2022-06-03 | 万华化学集团股份有限公司 | Treatment method of 3-methyl-3-butene-1-ol process waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114163303B (en) | 2023-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106582788B (en) | A kind of modified zsm-5 zeolite and preparation method and catalysis prepare the synthetic method of 3- methyl-3-butene-1-alcohol | |
| KR20090014372A (en) | Preparation of reactive, essentially halogen-free polyisobutenes from c4-hydrocarbon mixtures which are low in isobutene | |
| JPS58109428A (en) | Manufacture of linear olefin product | |
| GB2054568A (en) | Process for production of tertiary butyl alcohol | |
| KR100715165B1 (en) | Method for producing highly reactive polyisobutenes | |
| CN111056913A (en) | Continuous production method of 1, 1, 1, 3-tetrachloropropane | |
| CN114163303A (en) | Continuous preparation method of 3-methyl-3-butene-1-ol | |
| CN110818566A (en) | Method for preparing cyclopentanol from cyclopentene | |
| CN104649878A (en) | Continuous synthesis technology of beta-isophorone | |
| CN110283076A (en) | A kind of method that the condensation of low-carbon aldehyde generates low-carbon ester | |
| CN110105186B (en) | Method for preparing ketene compounds | |
| CN112479841B (en) | Process for synthesizing butyraldehyde by hydroformylation of propylene | |
| CN110981697B (en) | Method for synthesizing 3-methyl-3-butene-1-ol | |
| CN111807956A (en) | Production process of isooctyl acrylate of ultralow-concentration oligomer | |
| US20040267045A1 (en) | Processes for producing (meth)acrylic acid compound | |
| CN111282595A (en) | Method for continuously preparing α, gamma-unsaturated dienone | |
| KR20050088246A (en) | Process for producing alcohol and/or ketone | |
| RU2368593C1 (en) | Method of extracting isobutylene | |
| CN110003149B (en) | Method for producing furfural by catalytic xylose extraction under normal pressure by glacial acetic acid | |
| CN103664520A (en) | Method for preparing isopropyl alcohol through hydration reaction of propylene | |
| CN108503595B (en) | Method for preparing quinazolinone compound | |
| CN110776389B (en) | Compound catalyst and method for preparing styrene | |
| CN105152833A (en) | Method for preparing n-butene | |
| CN106117001B (en) | A kind of method that the tert-butyl alcohol and formaldehyde prepare isoprene | |
| CN114105748B (en) | Preparation method, ketene compound prepared by preparation method and application of ketene compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |