CN112898134B - Dehydration and catalytic synthesis method and device for polymethoxy dimethyl ether - Google Patents
Dehydration and catalytic synthesis method and device for polymethoxy dimethyl ether Download PDFInfo
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Abstract
A dehydration and catalytic synthesis method and a device for polymethoxy dimethyl ether are provided, and the process is as follows: mixing formaldehyde aqueous solution with a carrier, vacuum dehydrating the mixture in a stripping section of a dehydration tower to obtain flowable polyoxymethylene, mixing the flowable polyoxymethylene with a reclaimed material, feeding the mixture into a catalytic rectifying tower from the upper part of a section filled with catalyst filler, enabling the mixture to flow downwards in a dispersed manner under certain conditions, enabling the mixture to pass through a catalyst filler layer, enabling the mixture to be in countercurrent contact with methylal entering from the lower part of the section filled with catalyst filler after vaporization, enabling water and methanol generated by reaction to be carried out along with methylal azeotropy, generating polymethoxy dimethyl ether, continuing to move downwards, obtaining a polymethoxy dimethyl ether crude product after passing through the stripping section filled with aluminosilicate molecular sieve filler, and obtaining polymethoxy dimethyl ether with different grades after further separating and recycling low-boiling substances and macromolecules; the device mainly comprises: a dehydration tower 1, a catalytic rectifying tower 2, a dilute formaldehyde condenser 3, a vacuum receiving tank 4, a mixer 5, an azeotrope condenser 6 and a gasification tower 25.
Description
Technical Field
The invention belongs to the technical field of energy and chemical industry, and particularly relates to a dehydration and catalytic synthesis method and a device thereof for polymethoxy dimethyl ether.
Background
Polymethoxy dimethyl ether, also known as paraformaldehyde dimethyl ether, english name: polyoxymethylene dimethyl ethers, PODE or DMMn for short, is a low molecular weight acetal polymer with dimethoxy methane as a matrix and methyleneoxy as a main chain, and has the general formula shown as follows: CH3O (CH 2O) nCH3. Wherein, the polymethoxy dimethyl ether with the polymerization degree of 3-8 is abbreviated as DMM3-8, which is used for cleaning the blending components of diesel oil, the physical properties of the blending components are similar to those of the diesel oil, and the blending components are used in the diesel oil without modifying the oil supply system of the vehicle engine. The cetane number of the diesel oil is up to 76, the oxygen content is 47% -50%, the diesel oil is free of sulfur and aromatic hydrocarbon, 10% -20% of the diesel oil is blended in the diesel oil, the cold filter plugging point of the diesel oil can be obviously reduced, the combustion quality of the diesel oil in an engine can be improved, and the thermal efficiency is improved. Meanwhile, DMM2, DMM3, DMM4 and DMM5 are solvents with extremely strong dissolving capacity and are applied to paint, coating, printing ink, adhesives, cleaning agents, electrolyte solvents and the like.
Polymethoxy dimethyl ether is generally prepared by reacting methanol or methylal with trioxymethylene or paraformaldehyde in the presence of an acidic catalyst, and the basic equation of the reaction is as follows:
the acid catalyst catalyzed synthesis of polymethoxy dimethyl ether is an equilibrium reaction, the content of finished components (DMM 3-8) is low, the DMM3-8 content in the synthetic liquid is generally below 40%, but the existence of a small amount of water promotes the reverse movement of balance and has larger influence, so that a large amount of methanol, formaldehyde, paraformaldehyde, hemiacetal and the like remain in the reaction liquid, the content of effective components is lower, the purification and low-cost preparation of polymethoxy dimethyl ether are difficult, so people think of using formaldehyde with no water or low-moisture content, think of using trioxymethylene, paraformaldehyde, synthesizing gaseous formaldehyde with no water or low-moisture, or think of using a relatively concentrated formaldehyde aqueous solution to synthesize and remove water of the system in the synthesis process.
However, the trioxymethylene is synthesized by sulfuric acid catalysis, a large amount of reflux is carried out in the production process under the condition of water, the vaporization heat of the water is high, the energy consumption is high, the solvent is used for extraction and dehydration, the synthesis cost per se is high, the melting point of the trioxymethylene is high (61 ℃), the trioxymethylene is easy to sublimate, the pipeline is easy to block, dangerous accidents and the like occur, and once strong acid substances are mixed in the storage and transportation processes of the trioxymethylene, the high-molecular polymer is polymerized, so that the equipment is scrapped.
The paraformaldehyde is in a solid form prepared by dewatering formaldehyde aqueous solution under vacuum condition until the water content is below 15%, and then granulating or crushing, drying and other procedures, although the manufacturing cost is reduced, the paraformaldehyde is further used as a reactant, and has lower reactivity due to the property of insolubility, and in the continuous production process, the paraformaldehyde is inconvenient to feed from synthesis to application, has larger formaldehyde odor, larger toxicity and harm to the health of workers, and the moisture content is difficult to be below 6% even though the paraformaldehyde is dried, so that the balance reaction of the paraformaldehyde is still greatly influenced.
There are reports of preparing polyoxymethylene dimethyl ether (DMM 3-8) by reacting formaldehyde aqueous solution with higher concentration (containing more than 20% of water) with methanol or methylal in China, and although the process is smooth and convenient to operate in theory, the problems of difficult re-dehydration of synthetic solution, low conversion rate, more formaldehyde residues, difficult separation and the like exist, and the high concentration formaldehyde aqueous solution is easy to polymerize and block a pipeline, the process is immature and the industrialization is difficult to realize.
In Chinese patents 2015110128377. X and 201610147992.X, the preparation of DMMn synthetic liquid by catalytic reaction of gaseous formaldehyde and methylal in the presence of catalyst, and DMM3-8 is obtained after treatment and separation, but the preparation method of gaseous formaldehyde in the patent uses monohydric alcohol such as isobutanol as auxiliary agent, and has low atom utilization rate; such adjuvants have a low boiling point, are easily introduced into the synthesis liquid and the finished product with formaldehyde, and are expensive, which is disadvantageous for industrialization, and more importantly, the water solubility of the adjuvants is enhanced after the formation of the hemiacetal, unlike the case of the water-splitting, which is described in the patent, but rather difficult to separate from water, or special separation equipment is required, and during the subsequent distillative dehydration, the reformed auxiliary additive is distilled out and mixed into the diluted formaldehyde solution due to the influence of equilibrium.
In chinese patent 201610076437.2, the preparation of formaldehyde gas by oxidation of methanol or methylal with air in an oxidation reactor is mentioned; and then the prepared formaldehyde gas is introduced into a cooler to be cooled to 20-99 ℃, and then the formaldehyde gas enters a gas-water separator to remove condensed water, so that the fact proves that the formaldehyde gas formed by oxidizing the methanol contains about 30% of generated water, and formaldehyde hydrate (methyl glycol) is quickly formed to be liquefied or polymerized to be liquefied or solidified when the temperature is reduced to 20-99 ℃, so that industrialization is not facilitated.
Other conventional processes for preparing anhydrous gaseous formaldehyde include: 1. the paraformaldehyde is heated and depolymerized to prepare gaseous formaldehyde, but the bound water of the paraformaldehyde is about 6%, so that the synthesis yield of DMMn and the further recycling of intermediate products are greatly influenced, the solid paraformaldehyde is relatively complicated to prepare, and further feeding and conveying are not beneficial to large-scale continuous production, and have great potential safety hazards. 2. Under the action of an acid catalyst, the trioxymethylene is heated, decomposed and gasified, so that the trioxymethylene which is not decomposed is gasified along with gaseous formaldehyde, the conveying pipeline is easy to be blocked, and the cost of the trioxymethylene is higher, so that the industrialization is not facilitated.
Disclosure of Invention
(1) The invention aims to:
the invention aims to solve a series of problems existing in the existing synthesis of polyoxymethylene dimethyl ether by using paraformaldehyde, trioxymethylene, gaseous formaldehyde or formaldehyde aqueous solution, and provides a new synthesis technical route, a new synthesis technical process and a new synthesis device, wherein the method has the advantages of easily available raw materials, low price, convenience for realizing continuity and automation, dehydration and condensation, active control of reaction balance, higher total yield, normal-pressure operation, lower cost, less waste water, little pollution, safety and environmental protection, and suitability for industrial production.
(2) The technical scheme is as follows:
the invention relates to a dehydration and catalytic synthesis method of polymethoxy dimethyl ether and a device thereof, which are characterized in that formaldehyde aqueous solution is mixed with a carrier and then enters a stripping section of a dehydration tower for vacuum dehydration to prepare flowable polyoxymethylene, then the flowable polyoxymethylene is heated and gasified or mixed with reclaimed materials, enters a catalytic rectifying tower from the upper part of a filling section filled with catalyst, and flows downwards in a dispersed manner under certain conditions, passes through a catalyst filling layer, contacts methylal entering from the lower part of the filling section filled with catalyst in a countercurrent manner after being gasified, water generated by reaction is carried out along with methylal azeotropy, the polymethoxy dimethyl ether is generated to continue to move downwards, and then the crude polymethoxy dimethyl ether is obtained after passing through the stripping section filled with aluminosilicate molecular sieve filling, and different grades of polymethoxy dimethyl ether are obtained after further separation and recovery of low-boiling substances and macromolecules, wherein the basic reaction equation is as follows:
the synthesizing device mainly comprises: a dehydration tower 1, a catalytic rectifying tower 2, a dilute formaldehyde condenser 3, a vacuum receiving tank 4, a mixer 5, an azeotrope condenser 6 and a gasification tower 25.
(3) The technical effects are as follows: the dehydration and catalytic synthesis method and the device for the polymethoxy dimethyl ether have the advantages of low price, liquid and gaseous operation under normal pressure and negative pressure, simple procedures, convenience for realizing continuity and automation, gradual movement of reaction balance in a positive direction during catalytic reaction control, low energy consumption, high atomic utilization rate, higher yield, higher product purity, lower cost, less wastewater pollution, safety and environmental protection, and suitability for industrial production.
The specific aspects are as follows:
1. the invention adopts formaldehyde aqueous solution (or gaseous formaldehyde synthetic gas) as raw material of formaldehyde source, which simplifies the production and reduces the cost of the product;
2. the invention adopts ethylene glycol or propylene glycol as carrier auxiliary agent to prepare the fluidity polyformaldehyde with low moisture content, and the hemiacetal etherate has stable and reliable melting point, can not sublimate, has low cost, high efficiency, easy operation and no pollution to subsequent materials;
3. the invention solves the problems that the polyformaldehyde itself forms a solid state which is insoluble and infusible, has low activity and is difficult to convey when the polyformaldehyde is in a waterless state;
4. in the reaction process, the water generated by the reaction is brought out through azeotropy, so that the reaction balance is promoted to move forward, all hydroxyl groups are almost completely sealed, the etherification rate is high, the effective product yield is high, and the synthesis efficiency is high;
5. the reaction process of the invention controls the molecular weight distribution of the synthetic liquid by proper adjustment, thereby greatly improving the synthetic efficiency;
6. the continuous device can make the productivity of a single device bigger;
7. the invention uses the solid acid catalyst, has good catalytic effect, and is safe and environment-friendly;
8. the invention uses molecular sieve filler to fill the extracting section, plays a role in stabilizing the synthetic liquid, and improves the separation efficiency and the separation yield.
4. Description of the drawings:
fig. 1 is a diagram of the apparatus of the present invention, which mainly comprises: a dehydration tower 1, a catalytic rectifying tower 2, a dilute formaldehyde condenser 3, a vacuum receiving tank 4, a mixer 5, an azeotrope condenser 6 and a gasification tower 25.
Fig. 2 is a diagram of the apparatus of the present invention, comprising: the catalyst comprises a dehydration tower 1, a catalytic rectifying tower 2, a dilute formaldehyde condenser 3, a vacuum receiving tank 4, a mixer 5, an azeotrope condenser 6, a dehydration tower heater 7, a catalytic rectifying tower heater 8, a formaldehyde-ethylene glycol mixture feeding pipe 9, a flowable polyoxymethylene discharging pipe 10, a water return pipe 11, a vacuum pipe 12, a water outlet pipe 13, a recovery feeding pipe 14, a mixture feeding pipe 15, a fine methylal feeding pipe 16, an azeotrope return pipe 17, a crude DMMn discharging pipe 18, an azeotrope discharging pipe 19, a dehydration tower stripping section 20, a dehydration tower rectifying section 21, a catalytic rectifying tower stripping section 22, a catalytic rectifying tower catalytic reaction section 23 and a catalytic rectifying tower rectifying section 24.
Fig. 3 is a diagram of the apparatus of the present invention, comprising: the catalyst comprises a dehydration tower 1, a catalytic rectifying tower 2, a dilute formaldehyde condenser 3, a vacuum receiving tank 4, a mixer 5, an azeotrope condenser 6, a dehydration tower heater 7, a catalytic rectifying tower heater 8, a formaldehyde-ethylene glycol mixture feeding pipe 9, a flowable polyoxymethylene discharging pipe 10, a water return pipe 11, a vacuum pipe 12, a water outlet pipe 13, a recovery feeding pipe 14, a mixture feeding pipe 15, a fine methylal feeding pipe 16, an azeotrope return pipe 17, a crude DMMn discharging pipe 18, an azeotrope discharging pipe 19, a dehydration tower stripping section 20, a dehydration tower rectifying section 21, a catalytic rectifying tower stripping section 22, a catalytic rectifying tower catalytic reaction section 23, a catalytic rectifying tower rectifying section 24, a gasification tower 25, a gasification tower heater 26, a gaseous formaldehyde discharging pipe 27 and a residual carrier collecting pipe 29.
5. The specific embodiments of the present invention are as follows:
the invention will now be described in further detail with reference to the drawings and by means of specific examples, which are given by way of illustration only and are not intended to limit the scope of the invention.
As shown in fig. 2, the device of the dehydration and catalytic synthesis method of the polymethoxy dimethyl ether comprises: the catalyst comprises a dehydration tower 1, a catalytic rectifying tower 2, a dilute formaldehyde condenser 3, a vacuum receiving tank 4, a mixer 5, an azeotrope condenser 6, a dehydration tower heater 7, a catalytic rectifying tower heater 8, a formaldehyde-ethylene glycol mixture feeding pipe 9, a flowable polyoxymethylene discharging pipe 10, a water return pipe 11, a vacuum pipe 12, a water outlet pipe 13, a recovery feeding pipe 14, a mixture feeding pipe 15, a fine methylal feeding pipe 16, an azeotrope return pipe 17, a crude DMMn discharging pipe 18, an azeotrope discharging pipe 19, a dehydration tower stripping section 20, a dehydration tower rectifying section 21, a catalytic rectifying tower stripping section 22, a catalytic rectifying tower catalytic reaction section 23 and a catalytic rectifying tower rectifying section 24.
The preparation method comprises the following steps: the mass ratio of the 37% formaldehyde aqueous solution to the carrier is as follows: formaldehyde (fold purity) =0.1-10:10 ratio, after mixing through formaldehyde-glycol mixture feed pipe 9, continuously entering into the upper end distributor of stripping section 20 of dehydration tower 1, after the liquid level of dehydration tower bottom heater 7 is accumulated to normal liquid level, maintaining the tower bottom temperature of dehydration tower to 40-120 deg.C, and pumping system vacuum degree to above-0.080 MP through vacuum receiving tank 4, after formaldehyde and carrier are combined, molecular weight is large, downward flow, water is gasified, moved to tower top, condensed by dilute formaldehyde condenser 3, collected in vacuum receiving tank 4, and the water content of formaldehyde below 8% is finally extracted from water outlet pipe 13 through reflux ratio control of reflux port 11, dehydration tower bottom flow polyformaldehyde discharging pipe 10 is made into polyformaldehyde (etherified between paraformaldehyde and carrier) with water content below 8%.
The flowable polyoxymethylene is continuously extracted from a discharging pipe 10 at the bottom of a dehydration tower, the flowable polyoxymethylene is mixed with a reclaimed material 14 in a mixer 5, the mixture enters a distributor of a catalytic rectifying tower from the upper part of a catalytic reaction section 23 filled with catalyst filler through a mixture feeding pipe 15, the dispersed type polyoxymethylene flows downwards, the temperature of the bottom 8 of the catalytic rectifying tower is controlled at 50-180 ℃ and the temperature of the catalytic reaction section 23 is controlled at 45-115 ℃ and the temperature of the top is controlled at 35-85 ℃, the material mixture passes through a catalyst filler layer 23 and is in countercurrent contact with refined methylal continuously entering from the lower part of the filled catalyst filler section 23 after being vaporized, water and methanol carried in by the flowable polyoxymethylene are azeotroped with the upward gaseous methylal, a part of the water and methanol produced by the reaction is refluxed to the top of the tower through an azeotrope reflux pipe 17 after being condensed through an azeotrope condenser 6, a part of the water and the tower top reflux is extracted through an azeotrope reflux pipe 19, the hydroxy groups in the mixed material are almost blocked by the methyl ether after being catalyzed to produce the polymethoxy dimethyl ether, the crude product is collected in the bottom 8 of the tower is subjected to the concentrated and the crude product of the dimethoxy dimethyl ether is separated from the distillation tower, and the crude product is further recovered from the crude product of the crude product is separated from the silicon-aluminum-dimethyl ether molecular sieve filling material after the crude product is separated from the tower bottom 8, and the crude product is further recovered from the distilled to obtain the crude product.
As shown in fig. 3, the device of the dehydration and catalytic synthesis method of the polymethoxy dimethyl ether comprises: the catalyst comprises a dehydration tower 1, a catalytic rectifying tower 2, a dilute formaldehyde condenser 3, a vacuum receiving tank 4, a mixer 5, an azeotrope condenser 6, a dehydration tower heater 7, a catalytic rectifying tower heater 8, a formaldehyde-ethylene glycol mixture feeding pipe 9, a flowable polyoxymethylene discharging pipe 10, a water return pipe 11, a vacuum pipe 12, a water outlet pipe 13, a recovery feeding pipe 14, a mixture feeding pipe 15, a fine methylal feeding pipe 16, an azeotrope return pipe 17, a crude DMMn discharging pipe 18, an azeotrope discharging pipe 19, a dehydration tower stripping section 20, a dehydration tower rectifying section 21, a catalytic rectifying tower stripping section 22, a catalytic rectifying tower catalytic reaction section 23, a catalytic rectifying tower rectifying section 24, a gasification tower 25, a gasification tower heater 26, a gaseous formaldehyde discharging pipe 27 and a residual carrier extracting pipe 28.
The preparation method comprises the following steps: the mass ratio of the 37% formaldehyde aqueous solution to the carrier is as follows: formaldehyde (fold purity) =0.1-10:10 ratio, after mixing through formaldehyde-glycol mixture feed pipe 9, continuously entering into the upper end distributor of stripping section 20 of dehydration tower 1, after the liquid level of dehydration tower bottom heater 7 is accumulated to normal liquid level, maintaining the tower bottom temperature of dehydration tower to 40-120 deg.C, and pumping system vacuum degree to above-0.080 MP through vacuum receiving tank 4, after formaldehyde and carrier are combined, molecular weight is large, downward flow, water is gasified, moved to tower top, condensed by dilute formaldehyde condenser 3, collected in vacuum receiving tank 4, and the water content of formaldehyde below 8% is finally extracted from water outlet pipe 13 through reflux ratio control of reflux port 11, dehydration tower bottom flow polyformaldehyde discharging pipe 10 is made into polyformaldehyde (etherified between paraformaldehyde and carrier) with water content below 8%.
The flowable polyformaldehyde is continuously extracted from a discharging pipe 10 at the bottom of a dehydration tower, firstly enters a vaporization tower 25, formaldehyde is heated and depolymerized and gasified in a heater 26 of the vaporization tower, residual carriers are discharged through a discharging pipe 28 of the carrier at the bottom of the tower and then returned to the dehydration tower for application, gaseous formaldehyde is mixed with reclaimed materials 14 in a mixer 5 through a discharging pipe 27 of the gaseous formaldehyde, enters a distributor of the catalytic rectifying tower from the upper part of a catalytic reaction section 23 filled with catalyst filler through a feeding pipe 15 of the mixed materials, flows downwards in a dispersed manner, flows through a heating 8 at the bottom of the tower and a reflux 17 at the top of the tower, the temperature of the bottom 8 of the catalytic rectifying tower is controlled to be 50-180 ℃, the temperature of the catalytic reaction section 23 is controlled to be 45-115 ℃, the temperature of the top of the tower is controlled to be 35-85 ℃, the mixed materials are contacted with refined methylal continuously entering from the lower part of the catalytic filling section 23 in a countercurrent manner after being vaporized through the catalyst filler layer 23, the water and methanol carried by the fluidity polyoxymethylene and the water and methanol generated by the reaction are carried out azeotropically along with upward gaseous methylal, after being condensed by an azeotrope condenser 6, one part of the water and methanol is returned to the top of the tower through an azeotrope return pipe 17, and the other part of the water and methanol is extracted by an azeotrope discharge pipe 19, the water and methanol are catalyzed to generate the polymethoxy dimethyl ether which continues to move downwards, the hydroxyl groups in the mixed material are almost completely capped and etherified, after passing through a stripping section 22 filled with aluminosilicate molecular sieve filler, the crude polymethoxy dimethyl ether is collected in a concentrated way at the bottom 8 of the tower, the crude polymethoxy dimethyl ether is continuously extracted from a DMMn discharge pipe 18 of the crude product at the bottom of the reaction rectifying tower, and the polymethoxy dimethyl ether finished products with different grades are obtained after further separating and recovering low boiling substances and macromolecules.
Example 1:
according to the specific preparation method, a metering pump is used for continuously feeding 37% formaldehyde aqueous solution into a formaldehyde-ethylene glycol mixture feed pipe at the speed of 4000mL/h and ethylene glycol of 170mL/h, continuously feeding the mixture into a distributor at the upper end of a stripping section of a dehydration tower after mixing, maintaining the normal liquid level at the bottom of the tower, maintaining the temperature at the bottom of the dehydration tower to 90 ℃, raising the vacuum to-0.098 MP, controlling the temperature at the top of the tower to 35 ℃ through a reflux ratio, extracting water containing about 5% of formaldehyde from the top of the tower, and preparing polyoxymethylene (etherate between paraformaldehyde and ethylene glycol) with fluidity and the water content of about 5% from the bottom of the tower;
continuously extracting the fluidity polyoxymethylene from the bottom of the dehydration tower, mixing the fluidity polyoxymethylene with the recovered low-boiling substances and macromolecular materials in a mixer, feeding the mixture into a distributor of a catalytic rectifying tower from the upper part of a filling section filled with catalyst, flowing downwards, continuously feeding refined methylal from the lower part of the filling section filled with catalyst at a speed of 17000mL/h, heating and vaporizing, moving upwards, controlling the temperature of the bottom of the catalytic rectifying tower at 90 ℃ by heating and controlling the temperature of the catalytic section at 62 ℃, controlling the temperature of the top of the tower at 41 ℃ by refluxing the top of the tower, allowing the mixture to pass through a catalyst filling layer, countercurrent contacting with the rising gaseous refined methylal, carrying out azeotropic stripping with the water carried in by the fluidity polyoxymethylene and the water generated by the reaction, generating the polymethoxy dimethyl ether, continuously descending, almost completely blocking and etherifying the hydroxy groups in the mixture, intensively collecting the crude polymethoxy dimethyl ether at the bottom of the tower, continuously extracting the polymethoxy dimethyl ether from the bottom of the reaction rectifying tower, further separating and recovering the low-boiling substances and macromolecular substances (being different from the mixer), obtaining the mixture of the 30.3.3-5% and the 30.3-3 kg of the mixture after the continuous rectifying tower is subjected to the continuous distillation, and the 30.3-3 kg of the mixture is obtained after the mixture is subjected to the continuous distillation, and the 30.3-3% of the total methanol is subjected to the total methanol is obtained after the total recovery of the product is subjected to the high-3.3-3 kg of the product. The yield by weight to formaldehyde (dry) was 195.7%.
Example 2:
according to the specific preparation method, a metering pump is used for continuously feeding 37% formaldehyde aqueous solution into a formaldehyde-ethylene glycol mixture feeding pipe at the speed of 4000mL/h and 1, 2-propylene glycol of 170mL/h, mixing and then continuously feeding into a distributor at the upper end of a stripping section of a dehydration tower, maintaining the normal liquid level at the bottom of the tower, maintaining the temperature at the bottom of the dehydration tower to 90 ℃, raising the vacuum to-0.098 MP, controlling the temperature at the top of the tower to 35 ℃ through a reflux ratio, extracting water containing 5% of formaldehyde from the top of the tower, and obtaining polyoxymethylene (etherate between paraformaldehyde and ethylene glycol) with the water content of 5% and having fluidity at the bottom of the tower.
Continuously extracting the fluidity polyoxymethylene from the bottom of the dehydration tower, mixing the fluidity polyoxymethylene with the recovered low-boiling substances and macromolecular materials in a mixer, feeding the mixture into a distributor of a catalytic rectifying tower from the upper part of a filling section filled with catalyst, flowing downwards, continuously feeding refined methylal from the lower part of the filling section filled with catalyst at a speed of 17000mL/h, heating and vaporizing, moving upwards, controlling the temperature of the bottom of the catalytic rectifying tower at 90 ℃ through heating and controlling the temperature of the catalytic section at 62 ℃, controlling the temperature of the top of the tower at 41 ℃ through the reflux of the top of the tower, enabling the mixture to pass through a catalyst filling layer, enabling the mixture to be in countercurrent contact with the rising gaseous refined methylal, enabling water carried in by the fluidity polyoxymethylene and water generated by the reaction to be carried out together with the upward gaseous methylal, generating the polymethoxy dimethyl ether to continue to flow downwards, enabling hydroxyl groups in the mixture to be almost completely blocked, etherified, intensively collecting crude polymethoxy dimethyl ether at the bottom of the tower after passing through a stripping section filled with aluminosilicate molecular sieve, continuously extracting the polymethoxy dimethyl ether from the bottom of the reaction rectifying tower, further separating the low-boiling substances and macromolecular substances (being in the same with the mixer), obtaining the mixture of the 30.37-percent of the 30.37 kg of the mixture after the mixture is separated, and obtaining the 30.3-3 kg of the 30.3-3 percent of the mixture after the mixture is subjected to continuous distillation, and the total methanol is subjected to the recovery of the high-grade and 3.0.3-3 percent, and the total methanol is subjected to the total distillation, and the total recovery of the product, and the product is subjected to the recovery of 3.3-3.3 percent to 3-3 percent of the product. The yield by weight to formaldehyde (dry basis) was 194.8%.
Example 3: comparative example batch Synthesis
Mixing 440g of 37% formaldehyde aqueous solution and 19g of glycol, removing water under vacuum condition at the temperature below 95 ℃ to obtain 172g of anhydrous flowable polyoxymethylene etherate, transferring the flowable polyoxymethylene etherate into a mixture of 10g of acidic sulfonic acid resin and 360g of methylal, applying 200g of reclaimed materials (DMM 2, macromolecules and the like), carrying out catalytic reaction at the temperature of 65 ℃ to obtain 511g of reaction solution, filtering out the catalyst, and distilling out about 271g of DMM1 and about 179g of DMM2 at normal pressure until-0.098 MP is distilled out of 154g of DMM3-8, and 89.5g of residual macromolecules. The weight yield to formaldehyde (on dry basis) was 94.6%. The yield is low, and the product has poor fat solubility.
Example 4: comparative example: without a Carrier
The 37% aqueous formaldehyde solution was dehydrated under vacuum at a temperature of less than 95 c to give anhydrous, non-flowable paraformaldehyde particles 156, g, which were transferred into a mixture of 10g of an acidic sulfonic acid resin and 350g of methylal, and reacted catalytically at a temperature of 80 c for 24 hours, still containing a large amount of paraformaldehyde particles, failing to separate the catalyst and further give the product.
Example 5: (comparative example: no molecular sieve filler added)
According to the specific preparation method, a metering pump is used for continuously feeding 37% formaldehyde aqueous solution into a formaldehyde-ethylene glycol mixture feed pipe at the speed of 4000mL/h and ethylene glycol of 170mL/h, mixing, continuously feeding into a distributor at the upper end of a stripping section of a dehydration tower, maintaining the normal liquid level at the bottom of the tower, maintaining the temperature at the bottom of the dehydration tower to 90 ℃, raising the vacuum to-0.098 MP, controlling the temperature at the top of the tower to 35 ℃ through a reflux ratio, extracting water containing 5% of formaldehyde from the top of the tower, and preparing polyoxymethylene (an etherate between paraformaldehyde and ethylene glycol) with the water content of 5% and having fluidity from the bottom of the tower.
Continuously extracting the flowing polyformaldehyde from the bottom of the dehydration tower, mixing the mixture with the recovered low-boiling substances and macromolecular materials in a mixer, feeding the mixture into a distributor of a catalytic rectifying tower from the upper part of a filling section filled with catalyst, flowing downwards, continuously feeding refined methylal from the lower part of the filling section filled with catalyst at a speed of 17000mL/h, heating and vaporizing, moving upwards, controlling the temperature of the bottom of the catalytic rectifying tower to 90 ℃ through heating and controlling the temperature of the catalytic section to 62 ℃, controlling the temperature of the top of the tower to 41 ℃ through the reflux of the top of the tower, enabling the mixture to pass through a catalyst filling layer, enabling the mixture to be in countercurrent contact with the rising gaseous refined methylal, enabling water carried in by the flowing polyformaldehyde and water generated by the reaction to be carried out together with the upward gaseous methylal, generating the polymethoxy dimethyl ether to continue to flow downwards, enabling hydroxyl groups in the mixture to be almost completely blocked, intensively collecting crude polymethoxy dimethyl ether at the bottom of the tower after passing through a stripping section filled with ceramic ring filler, continuously extracting the crude polymethoxy dimethyl ether from the bottom of the reaction rectifying tower, further separating the low-methyl ether from the bottom of the tower to obtain the mixture, enabling the mixture to be different in terms of the mixture to obtain the mixture, and obtaining the dimethyl ether with the low-boiling substances and the high-boiling substances, and the low-boiling substances, and the total formaldehyde concentration of 20.9-20.8-9% and the total formaldehyde, and the total methanol-2.8-3-20% methanol, and the total methanol-2.3-3-20 kg-3-20% methanol-3-9-1-9 kg methanol after the dry methanol product is obtained after the continuous distillation.
Example 6: comparative example: without a Carrier
According to the specific preparation method, 37% formaldehyde aqueous solution is continuously fed into a distributor at the upper end of a stripping section of a dehydration tower at the speed of 4000mL/h by using a metering pump, the normal liquid level of the bottom of the tower is maintained, the temperature of the bottom of the dehydration tower is maintained to 80 ℃, the temperature of the top of the tower is increased to-0.090 MP, water containing about 5% formaldehyde is extracted from the top of the tower by controlling the temperature of the top of the tower at 35 ℃ through a reflux ratio, and the formaldehyde with fluidity and high concentration of 30% of water is prepared at the bottom of the tower.
Continuously extracting the fluidity polyoxymethylene from the bottom of the dehydration tower, mixing the fluidity polyoxymethylene with the recovered low-boiling substances and macromolecular materials in a mixer, feeding the mixture into a distributor of a catalytic rectifying tower from the upper part of a filling section filled with catalyst, flowing downwards, continuously feeding refined methylal from the lower part of the filling section filled with catalyst at a speed of 17000mL/h, heating and vaporizing, moving upwards, controlling the temperature of the bottom of the catalytic rectifying tower to 90 ℃ through heating and controlling the temperature of the catalytic section to 62 ℃ through the reflux of the top of the tower at 41 ℃, enabling the mixture to pass through a catalyst filling layer, enabling the mixture to be in countercurrent contact with the rising gaseous refined methylal, enabling water carried in by the fluidity polyoxymethylene and water generated by the reaction to be carried out together with the upward gaseous methylal, generating the polymethoxy dimethyl ether to continue to flow downwards, enabling hydroxyl groups in the mixture to be almost totally blocked, intensively collecting crude polymethoxy dimethyl ether at the bottom of the tower after the stripping section filled with ceramic ring filler, continuously extracting the crude polymethoxy dimethyl ether from the bottom of the reaction rectifying tower, further separating the low-boiling substances and macromolecular substances (being different in the mixer) and obtaining the mixture with the low-boiling substances and the macromolecular substances (being less than 10.37% of the total methanol, and the total methanol is separated from the mixture of 3.8% by weight, and the total 30% of the product is obtained after the methanol is separated, and the product is less than 8.8.37% of the total and the total methanol is separated, and the total and the product is less than 8% by weight, and the total by 3.8% of the total methanol is obtained after the product is separated after the 20% after the product is separated and is separated from the 20 weight and is more low by the 3 weight and is more low-75% and the 3.
Example 7: (gasification of formaldehyde)
Continuously feeding 37% formaldehyde aqueous solution into a formaldehyde-ethylene glycol mixture feeding pipe at the speed of 4000mL/h and at the speed of 170mL/h by using a metering pump, continuously feeding the mixed solution into a distributor at the upper end of a stripping section of a dehydration tower, maintaining the normal liquid level at the bottom of the tower, maintaining the temperature at the bottom of the dehydration tower to 90 ℃, raising the vacuum to-0.098 MP, controlling the temperature at the top of the tower to 35 ℃ by using a reflux ratio, extracting water containing about 5% of formaldehyde from the top of the tower, and preparing polyoxymethylene (an etherate between paraformaldehyde and ethylene glycol) with the water content of about 5% from the bottom of the tower.
Continuously extracting the flow polyformaldehyde from the bottom of the dehydration tower, firstly entering a vaporization tower, heating formaldehyde in a heater of the vaporization tower to depolymerize and gasify, discharging residual carrier through a carrier extraction pipe at the bottom of the vaporization tower, returning the residual carrier to the dehydration tower for application, mixing gaseous formaldehyde with recovered low-boiling substances and macromolecular materials in a mixer through a gaseous formaldehyde discharge pipe, entering a distributor of a catalytic rectification tower from the upper part of a filling catalyst filler section to flow downwards, continuously entering refined methylal from the lower part of the filling catalyst filler section at a speed of 17000mL/h, heating to gasify, moving upwards, controlling the temperature at the bottom of the catalytic rectification tower to 90 ℃ through heating, controlling the temperature at the catalytic section to 62 ℃ through reflux at the top of the catalytic rectification tower, controlling the temperature at the top of the catalytic rectification tower to 41 ℃ through the top of the catalytic filler layer, the water brought by the fluidity polyoxymethylene and the water generated by the reaction are carried out azeotropically along with the upward gaseous methylal, the polymethoxy dimethyl ether is generated to continue to move downwards, the hydroxyl groups in the mixed material are almost totally blocked and etherified, the crude polymethoxy dimethyl ether is collected in a concentrated way at the bottom of a stripping section filled with aluminosilicate molecular sieve filler, the crude polymethoxy dimethyl ether is continuously extracted from the bottom of a reaction rectifying tower, low-boiling substances and macromolecules are further separated and recovered (applied to a mixer), the polymethoxy dimethyl ether finished products with different grades are obtained, the mixture is continuously fed for 10 hours, the consumption of 37 percent formaldehyde is 45kg, the consumption of ethylene glycol is 1.72kg, the DMM3-8 mixture is 28.6kg after the rectification separation, and the total yield of the total organic matters is 97.8%. The weight yield of formaldehyde (dried) is 171.8%, and the carrier after formaldehyde vaporization returns to the dehydration tower for reuse.
The invention solves the problems of low yield, high energy consumption and higher cost when the conventional catalytic synthesis is carried out in the prior art of producing the polymethoxy dimethyl ether by taking paraformaldehyde, trioxymethylene and liquid formaldehyde as raw materials; residual formaldehyde, trioxymethylene and hemiacetal in the product are higher; the byproducts are more; the invention takes formaldehyde aqueous solution and methylal as raw materials, introduces a carrier, obtains the fluidity polyformaldehyde with lower moisture content through dehydration, utilizes a catalytic reaction rectifying tower to continuously catalyze and synthesize, breaks through the conventional reaction equilibrium etherification thoroughly, ensures that the process is simple, the synthetic conversion rate is higher, the separation is easy after the product is reformed by a molecular sieve filling section, the byproducts are less, and the content proportion of the excellent component DMM3-4 in the product DMM3-8 is higher. The invention has low investment cost, low production and driving risk and high operation profit.
Finally, the following is to be described: the foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but although the present invention has been described in detail with reference to the foregoing examples, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof. Such as: heating the flowable polyformaldehyde to above 100 ℃ to enable the flowable polyformaldehyde to be absorbed and mixed with reclaimed materials (as shown in figure 3), mixing a certain amount of trioxymethylene into the flowable polyformaldehyde, mixing a certain amount of paraformaldehyde into the flowable polyformaldehyde, enabling a catalytic rectifying tower to enter an auxiliary azeotropic water carrying agent along with methylal, and the like, wherein any modification, equivalent replacement, improvement and the like are included in the scope of the invention.
Claims (11)
1. A dehydration and catalytic synthesis method of polymethoxy dimethyl ether comprises the following steps: mixing formaldehyde aqueous solution and carrier, vacuum dewatering in dewatering tower to obtain flowable polyformaldehyde, heating and gasifying the flowable polyformaldehyde, mixing the flowable polyformaldehyde with recovered material, feeding the mixture into catalytic rectifying tower from the upper portion of the section filled with catalyst filler, making the mixture pass through catalyst filler layer, making the mixture pass through countercurrent contact with methylal which is fed from the lower portion of the section filled with catalyst filler after being gasified, making the water and methanol produced by reaction be azeotropic with methylal, making the formed product continuously go down, making the product pass through stripping section filled with aluminosilicate molecular sieve filler, collecting the product at the bottom of tower, collecting crude product of polymethoxy dimethyl ether from the bottom of tower, further separating and recovering low-boiling-point substances and macromolecules to obtain polymethoxy dimethyl ether with different grades, the device mainly comprises vacuum dewatering tower, gasifying tower and catalytic rectifying tower, and the above-mentioned steps: the device comprises a dehydration tower (1), a catalytic rectifying tower (2), a dilute formaldehyde condenser (3), a vacuum receiving tank (4), a mixer (5), an azeotrope condenser (6), a dehydration tower heater (7), a catalytic rectifying tower heater (8), a formaldehyde-ethylene glycol mixture feeding pipe (9), a flowable polyoxymethylene discharging pipe (10), a dilute formaldehyde return pipe (11), a vacuum pipe (12), a dilute formaldehyde discharging pipe (13), a reclaimed material feeding pipe (14), a mixture feeding pipe (15), a refined methylal feeding pipe (16), an azeotrope return pipe (17), a crude DMMn discharging pipe (18), an azeotrope discharging pipe (19), a dehydration tower stripping section (20), a dehydration tower rectifying section (21), a catalytic rectifying tower stripping section (22), a catalytic rectifying tower catalytic reaction section (23), a catalytic rectifying tower rectifying section (24), a gasification tower (25), a gasification tower heater (26), a gas formaldehyde discharging pipe (27) and a residual carrier collecting pipe (28).
2. A dehydration and catalytic synthesis method of polymethoxy dimethyl ether comprises the following steps: mixing formaldehyde aqueous solution with carrier, vacuum dewatering in dewatering tower to obtain flowable polyformaldehyde, mixing flowable polyformaldehyde with recovered material, feeding into catalytic rectifying tower from upper portion of filling catalyst filler section, under a certain condition, making the above-mentioned materials pass through catalyst filler layer, making them undergo the process of counter-current contact with methylal which is fed from lower portion of filling catalyst filler section, making the water and methanol produced by reaction be azeotropic-carried out with methylal so as to produce the described polymethoxy dimethyl ether continuously downward, making the above-mentioned materials pass through stripping section filled with aluminosilicate molecular sieve filler, collecting the above-mentioned materials into tower bottom, collecting polymethoxy dimethyl ether crude product from tower bottom, further separating and recovering low-boiling-point substances and macromolecules so as to obtain the polymethoxy dimethyl ether with different grades, and its equipment mainly is formed from vacuum dewatering tower and catalytic rectifying tower, in which the above-mentioned materials are included: the device comprises a dehydration tower (1), a catalytic rectifying tower (2), a dilute formaldehyde condenser (3), a vacuum receiving tank (4), a mixer (5), an azeotrope condenser (6), a dehydration tower heater (7), a catalytic rectifying tower heater (8), a formaldehyde-ethylene glycol mixture feeding pipe (9), a flowable polyoxymethylene discharging pipe (10), a dilute formaldehyde return pipe (11), a vacuum pipe (12), a dilute formaldehyde discharging pipe (13), a reclaimed material feeding pipe (14), a mixture feeding pipe (15), a refined methylal feeding pipe (16), an azeotrope return pipe (17), a crude DMMn discharging pipe (18), an azeotrope discharging pipe (19), a dehydration tower stripping section (20), a dehydration tower rectifying section (21), a catalytic rectifying tower stripping section (22), a catalytic rectifying tower catalytic reaction section (23) and a catalytic rectifying tower rectifying section (24).
3. The method according to claim 1 or 2, characterized in that: the aqueous formaldehyde solution is a commercial form of aqueous formaldehyde solution or a gaseous formaldehyde mixture of methanol, dimethyl ether or methylal with water vapor formed by catalytic dehydrogenation and oxidation.
4. The method according to claim 1 or 2, characterized in that: the carrier is ethylene glycol, 1, 2-propylene glycol, or a mixture thereof.
5. The method according to claim 1 or 2, characterized in that: the material obtained by mixing the formaldehyde aqueous solution and the carrier enters a distributor between a rectifying section and a stripping section of the dehydration tower.
6. The method according to claim 1 or 2, characterized in that: the mass ratio of the formaldehyde aqueous solution to the carrier is as follows: fold pure formaldehyde=0.1-10:10.
7. The method according to claim 1 or 2, characterized in that: the bottom temperature of the dehydration tower is controlled at 40-120 ℃ and the top temperature of the dehydration tower is controlled at 20-80 ℃.
8. The method according to claim 1 or 2, characterized in that: the catalyst filler is a solid acid catalyst and comprises sodium bisulfate, aluminum sulfate, sulfonic acid resin, fluorosulfonic acid resin, silica gel particles adsorbed with sulfuric acid and a mixture thereof.
9. The method according to claim 1 or 2, characterized in that: the aluminosilicate molecular sieve that the stripping section of the said catalytic rectifying column was packed, comprising: 3A molecular sieve, 4A molecular sieve, 5A molecular sieve, 13X molecular sieve, 13XAPG molecular sieve, 10Z molecular sieve, 13Z molecular sieve, and Y molecular sieve.
10. The method according to claim 1 or 2, characterized in that: the temperature of the top of the catalytic rectifying tower is controlled to be 35-85 ℃, the temperature of the catalytic section is controlled to be 45-115 ℃, and the temperature of the bottom of the catalytic rectifying tower is controlled to be 50-180 ℃.
11. The method according to claim 2, characterized in that: in the catalytic reaction section, two hydroxyl groups of the carrier are also blocked by methoxylmethylene to form a structural analogue of polymethoxy dimethyl ether, and the structural analogue enters a DMMn crude product material to form components of DMMn finished products with different grades during further separation.
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