CN109776289B - Method and device for separating and refining polymethoxy dimethyl ether - Google Patents
Method and device for separating and refining polymethoxy dimethyl ether Download PDFInfo
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Abstract
The invention relates to a method and a device for separating and refining polymethoxy dimethyl ether, which adopts multi-stage rectification and adopts methylal, methanol, water, formaldehyde, trioxymethylene and PODE as feed materials2Make-up water is introduced into the rectifying tower of the mixture, and the aqueous solution of formaldehyde and trioxymethylene are extracted from the tower kettle, thereby realizing the purpose of separating formaldehyde and trioxymethylene. The process may employ different separation sequences. The formaldehyde separated by the process can not be polymerized to block condensers and pipelines, the use continuity of equipment is improved, and unreacted raw materials of formaldehyde, and reaction byproducts of methyl formate and PODE (dimethyl formiate) can be effectively recovered2And the like.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, relates to a technology for synthesizing a synthetic product mixture of polymethoxy dimethyl ether by adopting multistage rectification separation of methanol and formaldehyde aqueous solution, and particularly relates to a method for synthesizing polymethoxy dimethyl ether by adopting methylal, methanol, water, formaldehyde, trioxymethylene and PODE as raw materials2The method and the device for realizing the separation and the refining of the polymethoxy dimethyl ether by introducing the make-up water into the rectifying tower of the mixture.
Background
The polyoxymethylene dimethyl ether is a novel diesel additive with the chemical formula of CH3O(CH2O)nCH3(wherein n is more than or equal to 1 and generally less than 10), has higher oxygen content (42-51%) and cetane number (average value is up to 76), and PODE (peroxidase)3-5Is the most ideal diesel oil additive, and PODE is added into the diesel oil3-5Can be effectiveReduce the emission of soot and Particulate Matters (PM) of the diesel engine and improve the fuel economy. PODEn is a homologue component formed from the etherification end group-providing starting material and the methoxy group-providing starting material via polycondensation under acid catalysis. The compounds providing terminal groups include methanol, dimethyl ether, methylal, etc., and the compounds providing methoxy groups include formaldehyde, trioxymethylene, paraformaldehyde, etc.
For many years, a large amount of researches on the synthesis and separation processes of PODEN have been carried out by domestic and foreign research teams mainly based on BASF corporation, and the main reports include a methylal and trioxymethylene route (US 20070260094) of BASF corporation and a methylal and paraformaldehyde route (CN104974025A) of Qinghua university and Yuhuang chemical cooperation, but because the reaction raw materials are anhydrous trioxymethylene and paraformaldehyde, the reaction product composition is simple, and the separation process can not be suitable for the separation of the synthesis product of methanol and formaldehyde aqueous solution; in addition, the reaction and separation processes of methanol and formaldehyde aqueous solution (US 2008207954, US 20080221368, US 7671240 and US 7700809) of BASF company have the disadvantages of low single-pass conversion rate, complex separation process, large energy consumption for repeated heating and separation of materials and serious equipment corrosion, and greatly limit the industrialization of the process flow.
Disclosure of Invention
The synthesis process of preparing PODEN by using methanol and formaldehyde aqueous solution as raw materials is divided into two steps, wherein the first step is a reaction stage of formaldehyde and methanol reacting to generate methylal, and the second step is a reaction stage of methylal and formaldehyde reacting to generate PODEN.
The invention aims to provide a method for preparing a catalyst in the presence of methylal, methanol, water, formaldehyde, trioxymethylene and PODE2The method and the device for realizing the separation and the refining of the polyoxymethylene dimethyl ethers by introducing make-up water into a rectifying tower of the mixture. Separating the synthesized product of PODEN with methanol and formaldehyde solution as material by distillation, refining to obtain PODEN suitable for diesel oil component, and recovering part of the material for the first and second stage reaction.
The invention is characterized in that the feed materials are methylal, methanol, water, formaldehyde, trioxymethylene and PODE2Introducing make-up water into the rectifying tower of the mixture to realize the separation of the polymethoxy dimethyl etherAnd a refining method and apparatus comprising six rectifying columns and a dehydration unit.
The technical scheme of the invention is as follows:
a process for separating and refining polymethoxy dimethyl ether includes multi-stage rectification with methylal, methanol, water, formaldehyde, trioxymethylene and PODE as raw materials2Make-up water is introduced into the rectifying tower of the mixture, and the aqueous solution of formaldehyde and trioxymethylene are extracted from the tower kettle, thereby realizing the purpose of separating formaldehyde and trioxymethylene.
And the mass ratio of the addition amount of the make-up water to the feeding material is 0.2: 1-0.8: 1.
Furthermore, make-up water is added from the same feed port as the feed or from two separate feed ports.
The first scheme is as follows:
the feed materials are methylal, methanol, water, formaldehyde, trioxymethylene and PODE2The device for introducing the supplementary water into the rectifying tower of the mixture to separate PODEN comprises six rectifying towers and a dehydration unit, wherein the tower kettle outlet of the first rectifying tower is connected with the feed inlet of the second rectifying tower through a pipeline, the tower top outlet of the second rectifying tower is connected with the feed inlet of the fourth rectifying tower through a pipeline, the tower kettle outlet of the second rectifying tower is connected with the feed inlet of the third rectifying tower through a pipeline, the tower top discharge port of the fourth rectifying tower is connected with the feed inlet of the fifth rectifying tower through a pipeline, the tower kettle discharge port of the fifth rectifying tower is connected with the feed inlet of the dehydration unit through a pipeline, the discharge port of the dehydration unit is connected with the feed inlet of the sixth rectifying tower, supplementary water is introduced into the fourth rectifying tower, and is added from the feed inlet of the fourth rectifying tower or a supplementary water inlet is arranged on the fourth rectifying tower.
One in-feed is methylal, methanol, water, formaldehyde, trioxymethylene and PODE2Introducing a method for supplementing water and separating PODEN into a rectifying tower of the mixture, wherein the flow is as follows: feeding PODEN raw material into a first rectifying tower, and extracting a material of methyl formate from the top of the first rectifying tower; the material at the bottom of the first rectifying tower enters a second rectifying tower, and methylal, methanol, water, formaldehyde, trioxymethylene and PODE are extracted from the top of the second rectifying tower2The mixed materials of (1); second oneThe material in the tower bottom of the rectifying tower enters a third rectifying tower, and PODE is extracted from the tower top of the third rectifying tower3-5The material and the tower bottom are PODE6-10The material (2); feeding the material at the top of the second rectifying tower into a fourth rectifying tower, introducing make-up water into the fourth rectifying tower, and extracting a mixed material of a formaldehyde water solution and trioxymethylene from the tower kettle of the fourth rectifying tower; feeding the material at the top of the fourth rectifying tower into a fifth rectifying tower, and extracting a mixed material of methylal and methanol from the top of the fifth rectifying tower; the tower bottom material of the fifth rectifying tower enters a dehydration unit, and the moisture is removed; the material after water removal enters a sixth rectifying tower, the material of methanol is extracted from the tower top of the sixth rectifying tower, and PODE is extracted from the tower bottom2The material of (1). The operation pressure of the first rectifying tower is 100-200KPa, the operation temperature of the tower top is 30-60 ℃, the operation pressure of the second rectifying tower is 80-120KPa, the operation temperature of the tower top is 70-100 ℃, the operation pressure of the third rectifying tower is 1-50KPa, the operation temperature of the tower top is 50-150 ℃, the operation pressure of the fourth rectifying tower is 80-120KPa, the operation temperature of the tower top is 70-120 ℃, the operation pressure of the fifth rectifying tower is 100-200KPa, the operation temperature of the tower top is 35-70 ℃, the operation pressure of the sixth rectifying tower is 100-200KPa, and the operation temperature of the tower top is 60-90 ℃.
The second scheme is as follows:
one in-feed is methylal, methanol, water, formaldehyde, trioxymethylene and PODE2The device for introducing the supplementary water into the rectifying tower of the mixture to separate PODEN comprises six rectifying towers and a dehydration unit, wherein the tower kettle outlet of the first rectifying tower is connected with the feed inlet of the second rectifying tower through a pipeline, the tower top outlet of the second rectifying tower is connected with the feed inlet of the fourth rectifying tower through a pipeline, the tower kettle outlet of the second rectifying tower is connected with the feed inlet of the third rectifying tower through a pipeline, the tower kettle discharge port of the fourth rectifying tower is connected with the feed inlet of the fifth rectifying tower through a pipeline, the tower top discharge port of the fifth rectifying tower is connected with the feed inlet of the dehydration unit through a pipeline, the discharge port of the dehydration unit is connected with the feed inlet of the sixth rectifying tower, supplementary water is introduced into the fourth rectifying tower, and is added from the feed inlet of the fourth rectifying tower or a supplementary water inlet is arranged on the fourth rectifying tower.
The feed materials are methylal, methanol,Water, formaldehyde, trioxymethylene and PODE2Introducing a method for supplementing water and separating PODEN into a rectifying tower of the mixture, wherein the flow is as follows: feeding PODEN raw material into a first rectifying tower, and extracting a material of methyl formate from the top of the first rectifying tower; the material at the bottom of the first rectifying tower enters a second rectifying tower, and methylal, methanol, water, formaldehyde, trioxymethylene and PODE are extracted from the top of the second rectifying tower2The mixed materials of (1); the material at the bottom of the second rectifying tower enters a third rectifying tower, and PODE is extracted from the top of the third rectifying tower3-5The material and the extraction from the tower bottom are PODE6-10The material (2); the material at the top of the second rectifying tower enters a fourth rectifying tower, and the fourth rectifying tower introduces make-up water, and the material at the top of the fourth rectifying tower is a mixed material of methylal and methanol; feeding the tower bottom material of the fourth rectifying tower into a fifth rectifying tower, and collecting a mixed material of a formaldehyde water solution and trioxymethylene from the tower bottom of the fifth rectifying tower; feeding the material at the top of the fifth rectifying tower into a dehydration unit; the material after water removal enters a sixth rectifying tower, the material of methanol is extracted from the tower top of the sixth rectifying tower, and PODE is extracted from the tower bottom2The material of (1). The operation pressure of the first rectifying tower is 100-200KPa, the operation temperature of the tower top is 30-60 ℃, the operation pressure of the second rectifying tower is 80-120KPa, the operation temperature of the tower top is 70-100 ℃, the operation pressure of the third rectifying tower is 1-50KPa, the operation temperature of the tower top is 50-150 ℃, the operation pressure of the fourth rectifying tower is 100-200KPa, the operation temperature of the tower top is 35-70 ℃, the operation pressure of the fifth rectifying tower is 80-120KPa, the operation temperature of the tower top is 70-120 ℃, the operation pressure of the sixth rectifying tower is 100-200KPa, and the operation temperature of the tower top is 60-90 ℃.
The dehydration unit adopts membrane dehydration, molecular sieve dehydration and adsorption dehydration. Membrane dehydration is preferred.
The invention has the following beneficial effects:
the invention provides a method for preparing polyoxymethylene dimethyl ethers (PODEN) by using methanol and formaldehyde aqueous solution as raw materials, aiming at the technical current situations that the components of the product are complex, formaldehyde is easy to polymerize in the rectification separation process, and unreacted raw materials need to be respectively recovered2Introducing make-up water into the rectifying tower of the mixture to realize methyl peroxide accumulationThe method and the device for separating and refining the dimethyl ether have the following unique points:
1. other intermediate components such as methylal and the like and formaldehyde are discharged together, so that the concentration of easily-polymerized substances such as hemiacetal, methylene glycol and the like is reduced, the pipeline is prevented from being blocked by polymerization, and the use continuity of equipment is improved.
2. Through introducing make-up water, the aqueous solution that contains formaldehyde is extracted to the tower kettle, prevents that formaldehyde polymerization from blockking up condenser and pipeline, and improve equipment uses the continuity, and the aqueous solution that contains formaldehyde of retrieving simultaneously can return to formaldehyde and methanol catalytic synthesis methylal's reaction unit, and the reasonable unreacted raw materials that retrieves improves utilization ratio of raw materials.
3. By feeding methylal, methanol, water, formaldehyde, trioxymethylene and PODE2Make-up water is introduced into the rectifying tower of the mixture, more methanol is taken out along with methylal at the top of the tower, and the energy consumption of a subsequent dehydration unit and a sixth rectifying tower is reduced.
Drawings
FIG. 1 is a schematic flow diagram of the separation process of examples 1 and 2;
FIG. 2 is a schematic flow diagram of the separation process of example 3.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, which are illustrative only and not limiting, and the scope of the present invention is not limited thereby.
Example 1
In FIG. 1, 1-A is a first rectifying tower, 1-B is a second rectifying tower, 1-C is a third rectifying tower, 1-D is a fourth rectifying tower, 1-E is a fifth rectifying tower, 1-F is a dehydration unit, and 1-G is a sixth rectifying tower;
the tower kettle outlet of the first rectifying tower 1-A is connected with the feed inlet of the second rectifying tower 1-B through a pipeline, the tower top outlet of the second rectifying tower 1-B is connected with the feed inlet of the fourth rectifying tower 1-D through a pipeline, the tower kettle outlet of the second rectifying tower 1-B is connected with the feed inlet of the third rectifying tower 1-C through a pipeline, the tower top discharge port of the fourth rectifying tower 1-D is connected with the feed inlet of the fifth rectifying tower 1-E through a pipeline, the tower kettle discharge port of the fifth rectifying tower 1-E is connected with the feed inlet of the dehydrating unit 1-F through a pipeline, and the discharge port of the dehydrating unit 1-F is connected with the feed inlet of the sixth rectifying tower 1-G.
The make-up water can enter the fourth rectifying tower 1-D together with the tower top discharge of the second rectifying tower 1-B or be added separately, if the make-up water is added separately, a make-up water feed inlet is additionally arranged on the fourth rectifying tower 1-D.
1-1 of material is PODEN raw material to be refined, 1-2 of material is methyl formate, 1-3 of material to be refined is raw material containing no methyl formate, 1-4 of material is methylal, methanol, water, formaldehyde, trioxymethylene and PODE21-5 is PODE3-101-6 is PODE3-51-7 is PODE6-101-8 is pure water material, 1-9 is methylal, methanol, water and PODE21-10 is a formaldehyde aqueous solution and a trioxymethylene material, 1-11 is a methylal and methanol material, and 1-12 is PODE2Water and methanol materials, 1-13 are water materials, 1-14 are methanol and PODE2Materials, 1-15 are methanol materials, 1-16 are PODE2And (3) feeding.
Feeding PODEN raw material (1-1) into a first rectifying tower (1-A), and extracting a material (1-2) of methyl formate from the top of the first rectifying tower (1-A); the materials (1-3) at the bottom of the first rectifying tower (1-A) enter a second rectifying tower (1-B), and methylal, methanol, water, formaldehyde, trioxymethylene and PODE are extracted from the top of the second rectifying tower (1-B)2The material (1-4); the tower bottom material (1-5) of the second rectifying tower (1-B) enters a third rectifying tower (1-C), and PODE is extracted from the tower top of the third rectifying tower (1-C)3-5The material (1-6) and the tower bottom are PODE6-10The material (1-7); feeding the materials (1-4) at the top of the second rectifying tower (1-B) into a fourth rectifying tower (1-D), introducing make-up water (1-8) into the fourth rectifying tower (1-D), and extracting materials (1-10) of formaldehyde water solution and trioxymethylene from the tower bottom of the fourth rectifying tower (1-D); materials (1-9) at the top of the fourth rectifying tower (1-D) enter a fifth rectifying tower (1-E), and materials (1-11) of methylal and methanol are extracted from the top of the fifth rectifying tower (1-E); feeding tower bottom materials (1-12) of a fifth rectifying tower (1-E) into a dehydration unit (1-F), and removing moisture (1-13); the materials (1-14) after water removal enter a sixth rectifying tower (1-G), the materials (1-15) of methanol are extracted from the top of the tower, and PODE is extracted from the bottom of the tower2Of (1-16)；
1800t/h PODEN synthesis product mixture, composition as follows:
| numbering | Components | Content% |
| 1 | Formic acid methyl ester | 1.80 |
| 2 | Methylal | 36.66 |
| 3 | Methanol | 5.19 |
| 4 | Formaldehyde (I) | 9.08 |
| 5 | Water (W) | 1.17 |
| 6 | Trioxymethylene | 2.50 |
| 7 | PODE2 | 20.96 |
| 8 | PODE3-5 | 20.03 |
| 9 | PODE6-10 | 2.41 |
By adopting the method scheme 1 for separation, the operating pressure of a first rectifying tower (1-A) is 100KPa, the operating temperature of the top of the tower is 32 ℃, the operating pressure of a second rectifying tower (1-B) is 80KPa, the operating temperature of the top of the tower is 86 ℃, the operating pressure of a third rectifying tower (1-C) is 1KPa, the operating temperature of the top of the tower is 52 ℃, the operating pressure of a fourth rectifying tower (1-D) is 80KPa, the mass ratio of the make-up water (1-8) to the materials (1-4) is 0.2:1, the operating temperature of the top of the tower is 76 ℃, the operating pressure of a fifth rectifying tower (1-E) is 100KPa, the operating temperature of the top of the tower is 80 ℃, a dehydration unit (1-F) adopts a molecular sieve for dehydration, the operating pressure of a sixth rectifying tower (1-G) is 100KPa, and the operating temperature of the top of the tower is 64 ℃.
Separating to obtain 32t/h of PODE (dimethyl Formate), 670t/h and 377t/h of methyl formate, methylal and methanol materials2PODE of 360t/h3-5Qualified products and about 42 percent of formaldehyde aqueous solution with the mass fraction of 389t/h are recovered.
Example 2
2400t/h PODEN synthesis product mixture, composition as follows:
the method and the device are adopted for separation in the embodiment 1, the operation pressure of a first rectifying tower (1-A) is 200KPa, the operation temperature of the top of the tower is 52 ℃, the operation pressure of a second rectifying tower (1-B) is 120KPa, the operation temperature of the top of the tower is 98 ℃, the operation pressure of a third rectifying tower (1-C) is 50KPa, the operation temperature of the top of the tower is 144 ℃, the operation pressure of a fourth rectifying tower (1-D) is 120KPa, the mass ratio of the make-up water (1-8) to the materials (1-4) is 0.8:1, the operation temperature of the top of the tower is 96 ℃, the operation pressure of a fifth rectifying tower (1-E) is 200KPa, the operation temperature of the top of the tower is 61 ℃, a dehydration unit (1-F) adopts membrane for dehydration, the operation pressure of a sixth rectifying tower (1-G) is 200KPa, and the operation temperature of the top of the tower is 82 ℃.
42t/h of methyl formate, methylal and methanol materials 893t/h and 503t/h of PODE are obtained by separation2PODE of 80t/h3-5Qualified products and the recovered formaldehyde solution with the mass fraction of about 20 percent of 1089 t/h.
Example 3:
in fig. 2, 2-A is a first rectifying tower, 2-B is a second rectifying tower, 2-C is a third rectifying tower, 2-D is a fourth rectifying tower, 2-E is a fifth rectifying tower, 2-F is a dehydration unit, and 2-G is a sixth rectifying tower.
The tower kettle outlet of the first rectifying tower 2-A is connected with the feed inlet of the second rectifying tower 2-B through a pipeline, the tower top outlet of the second rectifying tower 2-B is connected with the feed inlet of the fourth rectifying tower 2-D through a pipeline, the tower kettle outlet of the second rectifying tower 2-B is connected with the feed inlet of the third rectifying tower 2-C through a pipeline, the tower kettle discharge outlet of the fourth rectifying tower 2-D is connected with the feed inlet of the fifth rectifying tower 2-E through a pipeline, the tower top discharge outlet of the fifth rectifying tower 2-E is connected with the feed inlet of the dewatering unit 2-F through a pipeline, and the discharge outlet of the dewatering unit 2-F is connected with the feed inlet of the sixth rectifying tower 2-G.
The make-up water can enter the fourth rectifying tower 2-D together with the top discharge of the second rectifying tower 2-B or be added separately, if the make-up water is added separately, a make-up water feed inlet is additionally arranged on the fourth rectifying tower 2-D.
Material 2-1 is PODEN raw material to be refined, 2-2 is methyl formate, 2-3 is raw material to be refined without methyl formate, 2-4 is methylal, methanol, water, formaldehyde, trioxymethylene and PODE22-5 is PODE3-102-6 is PODE3-52-7 is PODE6-102-8 is pure water material, 2-9 is methyl shrinkageAldehyde and methanol, 2-10 is methanol, formaldehyde, water, trioxymethylene and PODE22-11 is PODE2Water and methanol, 2-12 is aqueous solution of formaldehyde and micro-trioxymethylene, 2-13 is water, 2-14 is methanol and PODE2Materials, 2-15 are methanol materials, 2-16 are PODE2And (3) feeding.
Feeding PODEN raw material (2-1) into a first rectifying tower (2-A), and extracting a material (2-2) of methyl formate from the top of the first rectifying tower (2-A); the tower bottom material (2-3) of the first rectifying tower (2-A) enters a second rectifying tower (2-B), and methylal, methanol, water, formaldehyde, trioxymethylene and PODE are extracted from the tower top of the second rectifying tower (2-B)22-4); the tower bottom material (2-5) of the second rectifying tower (2-B) enters a third rectifying tower (2-C), and PODE is extracted from the tower top of the third rectifying tower (2-C)3-5The material (2-6) and the tower bottom are PODE6-102-7); the material (2-4) at the top of the second rectifying tower (2-B) enters a fourth rectifying tower (2-D), and simultaneously, the fourth rectifying tower (2-D) introduces make-up water (2-8), and the material (2-9) of methylal and methanol is extracted from the top of the fourth rectifying tower (2-D); feeding the tower bottom material (2-10) of the fourth rectifying tower (2-D) into a fifth rectifying tower (2-E), and extracting a material (2-12) of formaldehyde water solution and trioxymethylene from the tower bottom of the fifth rectifying tower (2-E); the material (2-11) at the top of the fifth rectifying tower (2-E) enters a dehydration unit (2-F), and the moisture (2-13) is removed; the material (2-14) after water removal enters a sixth rectifying tower (2-G), the material (2-15) of methanol is extracted from the top of the tower, and PODE is extracted from the bottom of the tower22-16.
2700t/h PODEN synthesis product mixture, composition as follows:
| number of | Components | Content% |
| 1 | Formic acid methyl ester | 1.80 |
| 2 | Methylal | 36.66 |
| 3 | Methanol | 5.19 |
| 4 | Formaldehyde (formol) | 9.08 |
| 5 | Water (I) | 1.17 |
| 6 | Trioxymethylene | 2.50 |
| 7 | PODE2 | 20.96 |
| 8 | PODE3-5 | 20.03 |
| 9 | PODE6-10 | 2.41 |
The separation method is adopted, the operation pressure of the first rectifying tower (2-A) is 100KPa, the operation temperature of the top of the tower is 32 ℃, the operation pressure of the second rectifying tower (2-B) is 100KPa, the operation temperature of the top of the tower is 90 ℃, the operation pressure of the third rectifying tower (2-C) is 1KPa, the operation temperature of the top of the tower is 52 ℃, the operation pressure of the fourth rectifying tower (2-D) is 100KPa, the mass ratio of the supplementary water (2-8) to the materials (2-4) is 0.5:1, the operation temperature of the top of the tower is 40 ℃, the operation pressure of the fifth rectifying tower (2-E) is 100KPa, the operation temperature of the top of the tower is 80 ℃, the adsorption dehydration unit (2-F) adopts adsorption dehydration, the operation pressure of the sixth rectifying tower (2-G) is 100KPa, and the operation temperature of the top of the tower is 64 ℃.
48t/h of methyl formate, methylal and methanol materials 1004t/h and 566t/h of PODE are obtained by separation2PODE 540t/h3-5Qualified products and the formaldehyde water solution with the mass fraction of about 35 percent at 700t/h are recovered.
The invention provides a method for preparing formaldehyde-containing catalyst by using methylal, methanol, water, formaldehyde, trioxymethylene and PODE as raw materials2The method and apparatus for separating and refining polymethoxy dimethyl ether by introducing make-up water into the distillation column of the mixture has been described by way of preferred embodiments, and it will be apparent to those skilled in the art that the technique of the present invention can be implemented by modifying or appropriately combining the structures and devices described herein without departing from the spirit, scope and spirit of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (1)
1. A method for separating and refining polyoxymethylene dimethyl ethers is characterized in that: adopting six-stage rectification, and feeding methylal, methanol, water, formaldehyde, trioxymethylene and PODE2Adding water into a rectifying tower of the mixture, extracting a formaldehyde aqueous solution and trioxymethylene from a tower kettle so as to realize the purpose of separating formaldehyde and trioxymethylene, feeding PODEN raw material into a first rectifying tower, and extracting a material of methyl formate from the top of the first rectifying tower; the material at the bottom of the first rectifying tower enters a second rectifying tower, and methylal, methanol, water, formaldehyde, trioxymethylene and PODE are extracted from the top of the second rectifying tower2The mixed materials of (1); second rectifying tower bottomFeeding the material into a third rectifying tower, and extracting PODE from the top of the third rectifying tower3-5The material and the tower bottom are PODE6-10The material (2); feeding the material at the top of the second rectifying tower into a fourth rectifying tower, and introducing supplementary water into the fourth rectifying tower, wherein the mass ratio of the supplementary water to the feed is 0.2: 1-0.8: 1, and the supplementary water and the feed are added from the same feed inlet or are added from two feed inlets separately;
the tower bottom of the fourth rectifying tower is extracted to be a mixed material of aqueous solution of formaldehyde and trioxymethylene; feeding the material at the top of the fourth rectifying tower into a fifth rectifying tower, and extracting a mixed material of methylal and methanol from the top of the fifth rectifying tower; feeding the tower bottom material of the fifth rectifying tower into a dehydration unit, and removing water; the material after water removal enters a sixth rectifying tower, the material of methanol is extracted from the tower top of the sixth rectifying tower, and PODE is extracted from the tower bottom2The material (2); the operation pressure of the first rectifying tower is 100-200KPa, the operation temperature of the tower top is 30-60 ℃, the operation pressure of the second rectifying tower is 80-120KPa, the operation temperature of the tower top is 70-100 ℃, the operation pressure of the third rectifying tower is 1-50KPa, the operation temperature of the tower top is 50-150 ℃, the operation pressure of the fourth rectifying tower is 80-120KPa, the operation temperature of the tower top is 70-120 ℃, the operation pressure of the fifth rectifying tower is 100-200KPa, the operation temperature of the tower top is 35-70 ℃, the operation pressure of the sixth rectifying tower is 100-200KPa, and the operation temperature of the tower top is 60-90 ℃;
or the top of the fourth rectifying tower is extracted to be a mixed material of methylal and methanol; feeding the tower bottom material of the fourth rectifying tower into a fifth rectifying tower, and extracting a mixed material of a formaldehyde water solution and trioxymethylene from the tower bottom of the fifth rectifying tower; feeding the material at the top of the fifth rectifying tower into a dehydration unit; the material after water removal enters a sixth rectifying tower, the material of methanol is extracted from the tower top of the sixth rectifying tower, and PODE is extracted from the tower bottom2The material (2); the operation pressure of the first rectifying tower is 100-200KPa, the operation temperature of the tower top is 30-60 ℃, the operation pressure of the second rectifying tower is 80-120KPa, the operation temperature of the tower top is 70-100 ℃, the operation pressure of the third rectifying tower is 1-50KPa, the operation temperature of the tower top is 50-150 ℃, the operation pressure of the fourth rectifying tower is 100-200KPa, the operation temperature of the tower top is 35-70 ℃, the operation pressure of the fifth rectifying tower is 80-120KPa,the operation temperature at the top of the tower is 70-120 ℃, the operation pressure of the sixth rectifying tower is 100-200KPa, and the operation temperature at the top of the tower is 60-90 ℃;
the dehydration unit adopts membrane dehydration or adsorption dehydration.
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