CN115260147A - Process device and method for synthesizing dioxolane by using extractive catalytic distillation - Google Patents
Process device and method for synthesizing dioxolane by using extractive catalytic distillation Download PDFInfo
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- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 title claims abstract description 149
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000008569 process Effects 0.000 title claims abstract description 36
- 238000004821 distillation Methods 0.000 title claims abstract description 30
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 224
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 138
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 58
- 238000000605 extraction Methods 0.000 claims abstract description 54
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002351 wastewater Substances 0.000 claims abstract description 26
- 238000007670 refining Methods 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 239000010865 sewage Substances 0.000 claims abstract description 5
- 238000000895 extractive distillation Methods 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 238000004065 wastewater treatment Methods 0.000 claims description 8
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000005202 decontamination Methods 0.000 claims description 3
- 230000003588 decontaminative effect Effects 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims 1
- 239000002910 solid waste Substances 0.000 abstract description 7
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- 238000011049 filling Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229910000885 Dual-phase steel Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
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- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention discloses a process unit and a method for synthesizing dioxolane by extractive catalytic distillation, wherein glycol and formaldehyde are subjected to synthesis reaction under the catalytic action of a catalyst to generate dioxolane, the dioxolane and water are subjected to extractive distillation after azeotropy to form an azeotrope, and the residual wastewater is subjected to sewage treatment; the azeotrope formed by the dioxolane and the water is contacted with the extractant ethylene glycol, the ethylene glycol breaks the azeotrope of the dioxolane and the water due to the different solubility of the dioxolane and the water in the ethylene glycol, the separation of the dioxolane and the water is realized, and the separation of the dioxolane and the ethylene glycol is further realized due to the different boiling points of the dioxolane and the ethylene glycol, so that the dioxolane containing a small amount of water is obtained; part of the dioxolane containing a small amount of water is refluxed, and the other part is sent to a crude dioxolane refining unit. The invention couples the three processes of extraction, catalysis and rectification into one tower, which simplifies the process flow and avoids the generation of solid wastes.
Description
Technical Field
The invention relates to a synthesis process of dioxolane, in particular to a process device and a method for synthesizing dioxolane by using extraction catalytic distillation.
Background
Dioxolane is a second monomer of the co-formaldehyde, is also a good solvent, can dissolve grease, fuel, cellulose derivatives and various polymers, and is used for producing coatings and adhesives; can also be used as a stabilizer of trichloroethane, a photosensitive solution and a component of a developing solution; furthermore, dioxolane can also be used as an electrolyte for lithium disposable batteries. In recent years, dioxolane has been widely used in various fields, and has attracted much attention at home and abroad.
At present, concentrated formaldehyde and ethylene glycol are mainly used as raw materials for synthesizing dioxolane, sulfuric acid or ion exchange resin is used as a catalyst, catalytic reaction is carried out in a reaction kettle to prepare dioxolane, then dioxolane and water are evaporated out of the kettle in an azeotrope form, the dioxolane is condensed and then enters an extraction tower, a high-concentration sodium hydroxide or sodium chloride solution is used as an extracting agent to reduce the water content in dioxolane, and then the dioxolane enters a light-ends removal tower to remove light-boiling substances such as water, methanol and the like in dioxolane, so that high-purity dioxolane is obtained. The process has low raw material conversion rate, a large amount of unreacted materials are discharged from the kettle, so that raw material waste is caused, and the difficulty of sewage treatment is increased; in order to improve the conversion rate, the concentration of the raw material formaldehyde needs to be improved, so that the formaldehyde needs to be prepared by formaldehyde concentration, the generated dilute formaldehyde also needs to be recycled at high temperature and high pressure, and the problems of high energy consumption, serious equipment corrosion and the like exist. And sodium hydroxide or sodium chloride used in the extraction dehydration process can generate solid waste, so that the production cost is increased.
Disclosure of Invention
The invention aims to solve the technical problem that the prior art has the defects, and provides a process device and a method for synthesizing dioxolane by using extraction, catalysis and rectification, wherein three processes of extraction, catalysis and rectification are coupled into one tower, the concentration of a formaldehyde raw material is not required to be specially improved, the conversion rate of the raw material (calculated by formaldehyde) can approach 100 percent, and a formaldehyde concentration and dilute aldehyde recovery working section is omitted; and the raw material ethylene glycol is used as an extractant to extract the dioxolane, so that the azeotropy of the dioxolane and water is broken, the water content in the dioxolane is reduced, an industrial alkali or salt extraction working section is omitted, the process flow is simplified, and the generation of solid waste is avoided. The process belongs to an energy-saving and consumption-reducing green process.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly provides a process method for synthesizing dioxolane by extractive catalytic distillation, which comprises the following steps:
(1) Catalytic synthesis reaction:
performing synthetic reaction on ethylene glycol and formaldehyde under the catalytic action of a catalyst to generate dioxolane, performing extractive distillation after the dioxolane and water are azeotroped to form an azeotrope, and performing sewage treatment on the residual wastewater;
(2) And (3) extraction and rectification:
the azeotrope formed by the dioxolane and the water in the step (1) is contacted with the extractant glycol, the glycol breaks the azeotrope of the dioxolane and the water due to the different solubility of the dioxolane and the water in the glycol, the separation of the dioxolane and the water is realized, and the separation of the dioxolane and the glycol is further realized due to the different boiling points of the dioxolane and the glycol, so that the dioxolane containing a small amount of water is obtained;
(3) Refining treatment:
and (3) refluxing one part of the dioxolane containing a small amount of water obtained in the step (2), and sending the other part of the dioxolane into a crude dioxolane refining unit for refining treatment.
In the technical scheme, the process method specifically comprises the following steps:
(1) Catalytic synthesis reaction:
ethylene glycol enters the extraction catalytic rectifying tower from an ethylene glycol feed port at the top of the extraction section, formaldehyde enters the extraction catalytic rectifying tower from formaldehyde feed ports at the top and the bottom of the reaction section respectively, and the ethylene glycol and the formaldehyde perform synthetic reaction under the catalytic action of a catalyst in the reaction section to generate dioxolane; after the dioxolane and water are azeotroped to form an azeotrope, the azeotrope rises to an extraction section, and the residual wastewater falls to a stripping section and is discharged to a wastewater treatment unit from a wastewater discharge port at the bottom of the tower;
(2) Extraction and rectification:
the azeotrope formed by the dioxolane and the water in the step (1) rises from the reaction section to the extraction section, the ethylene glycol is continuously introduced from the ethylene glycol feed inlet to be used as an extracting agent, the azeotrope is contacted with the ethylene glycol, the ethylene glycol breaks the azeotrope of the dioxolane and the water due to the different solubility of the dioxolane and the water in the ethylene glycol, the separation of the dioxolane and the water is realized, the water is discharged from a wastewater discharge port at the bottom of the tower to a wastewater treatment unit after falling, the mixture of the ethylene glycol and the dioxolane rises to the rectification section, and the separation of the dioxolane and the ethylene glycol is realized under the action of rectification due to the different boiling points of the dioxolane and the ethylene glycol, so that the dioxolane with a small amount of water is obtained at the top of the tower, and the dioxolane with a small amount of water is discharged from the dioxolane discharge port to a condenser;
(3) Refining treatment:
and (3) enabling the dioxolane containing a small amount of water obtained in the step (2) to sequentially flow through a condenser, a reflux tank and a reflux pump, enabling a product to flow back to the extraction catalytic rectifying tower from a discharge port III of the reflux pump, and enabling another part of the product to be sent to a crude dioxolane refining unit for refining treatment.
In the above technical scheme, in the step (1), the molar ratio of the ethylene glycol to formaldehyde (pure formaldehyde) is 1.0-1.2.
In the technical scheme, in the step (1), the feeding mass airspeed of the formaldehyde is 0.5-2.5 h < -1 >.
In the above technical solution, in the step (1), the catalyst is any one of macroporous cation resins, preferably D006 resin or KC107 resin.
In the technical scheme, the temperature in the rectifying section of the extraction catalytic rectifying tower (1) is controlled to be 60-75 ℃, the pressure is 0-0.2 MPa, the temperature in the extracting section is controlled to be 70-85 ℃, the pressure is 0-0.22 MPa, the temperature in the reaction section is controlled to be 80-95 ℃, the pressure is 0-0.24 MPa, the temperature in the stripping section is controlled to be 110-140 ℃, and the pressure is 0-0.25 MPa.
In the above technical scheme, in the step (3), the reflux ratio is 2-6:1.
The invention also provides a process device for synthesizing dioxolane by using extractive catalytic distillation, which comprises an extractive catalytic distillation tower, a condenser, a reflux tank and a reflux pump which are connected in sequence, and is characterized in that:
extraction catalysis rectifying column, upper portion is provided with the ethylene glycol feed inlet in the tower wall, the well lower part is provided with the formaldehyde feed inlet, the top of the tower is provided with the dioxolane bin outlet, the tower is provided with the waste water bin outlet at the bottom of, tower wall upper portion is provided with the backward flow mouth, wherein: the ethylene glycol feed inlet is connected with a device capable of providing ethylene glycol, the formaldehyde feed inlet is connected with a device capable of providing formaldehyde, and the wastewater discharge outlet is connected with the wastewater decontamination water treatment unit;
the condenser, be provided with import I and export I, wherein: the inlet I is connected with a dioxolane discharge port of the extractive catalytic distillation tower;
the reflux tank is provided with an inlet II and an outlet II, wherein: the inlet II is connected with the outlet I of the condenser;
the reflux pump is provided with an inlet III and an outlet III, wherein: the inlet III is connected with the outlet II of the reflux tank, the outlet III is divided into two paths, one path is connected with the reflux port of the extraction catalytic distillation tower, and the other path is connected with the crude dioxolane refining unit.
In the technical scheme, the extractive catalytic distillation tower comprises a distillation section, an extraction section, a reaction section and a stripping section from top to bottom; the rectifying section and the stripping section are respectively filled with tower plates or fillers, and the reaction section is filled with a catalyst.
In the technical scheme, when the rectifying section and the stripping section are respectively filled with the tower plates, the number of filling layers is N, N is more than or equal to 5 and less than or equal to 40, and the interlayer spacing is 0.1-2.0 m; when the rectifying section and the stripping section are respectively filled with structured packing, the number of the filling sections is N, N is more than or equal to 5 and less than or equal to 40, and the height of each section is 0.1-2.0 m.
In the above technical solution, the catalyst is a macroporous cation resin catalyst, and the packing form is preferably a packed catalyst or a module catalyst (preferably, the packing form is set with reference to the structures of the packed catalyst in 201720485329.0 and the module catalyst in 201620189748.5 of the keley environmental protection technologies ltd).
In the technical scheme, the ethylene glycol feeding port and the formaldehyde feeding port are positioned on the same side of the tower wall of the extraction catalytic distillation tower.
In the technical scheme, the ethylene glycol feeding hole is positioned at the top of the extraction section; the two formaldehyde feeding ports are respectively positioned at the top and the bottom of the reaction section.
Compared with the prior art, the method has the following characteristics:
(1): the process flow is simple, and because the reaction raw material formaldehyde does not need to be concentrated, two working sections of formaldehyde concentration and dilute aldehyde recovery are omitted; meanwhile, the coupling of extraction and catalytic rectification saves an alkali liquor or salt extraction dehydration section and a solid waste production flow, so that the process flow is greatly simplified;
(2): the technology adopts resin as a catalyst, avoids high corrosivity caused by using sulfuric acid as the catalyst, reduces the equipment material of a reaction system from a lining zirconium reaction kettle to a common material of dual-phase steel +316L, greatly reduces the investment and prolongs the service life;
(3): the conversion rate is high, and the generated dioxolane can be timely removed from a reaction system by a catalytic rectification mode, so that the reversible reaction can be carried out in the forward direction, the conversion rate of formaldehyde is improved to be close to 100 percent, and the conversion rate of the prior art is only 93 percent;
(4): the energy consumption is low, and as the characteristics I indicate, the process omits the working sections of formaldehyde concentration, dilute aldehyde recovery, solid waste production and the like, so that the energy consumption of the device is reduced by 40 percent;
(5): the production process has no solid waste, the technology adopts the ethylene glycol as the extracting agent, and no alkali liquor or sodium chloride is introduced, so that the generation of the solid waste is avoided and the production cost of the dioxolane is indirectly reduced under the condition of achieving the same target.
Drawings
FIG. 1 is a schematic flow diagram of a process for the synthesis of dioxolane by extractive catalytic distillation in accordance with the present invention;
FIG. 2 is a schematic diagram of the arrangement structure of the process unit for synthesizing dioxolane by extractive catalytic distillation according to the present invention;
wherein: 1 is an extractive catalytic distillation tower (11 is an ethylene glycol feed port, 12 is a formaldehyde feed port arranged at the middle lower part, 13 is a dioxolane discharge port, 14 is a wastewater discharge port, and 15 is a reflux port); 2 is a condenser (21 is an inlet I, and 22 is an outlet I); 3 is a reflux tank (31 is an inlet II, and 32 is an outlet II); and 4 is a reflux pump (41-position inlet III and 42-position outlet III).
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following descriptions:
the invention firstly provides a process method for synthesizing dioxolane by using extractive catalytic distillation, and the flow chart is shown in figure 1:
(1) Catalytic synthesis reaction:
performing synthetic reaction on ethylene glycol and formaldehyde under the catalytic action of a catalyst to generate dioxolane, performing extractive distillation after the dioxolane and water are azeotroped to form an azeotrope, and performing sewage treatment on the residual wastewater;
(2) And (3) extraction and rectification:
the azeotrope formed by the dioxolane and the water in the step (1) is contacted with the extractant glycol, the ethylene glycol breaks the azeotrope of the dioxolane and the water due to the different solubility of the dioxolane and the water in the ethylene glycol, the separation of the dioxolane and the water is realized, and the separation of the dioxolane and the ethylene glycol is further realized due to the different boiling points of the dioxolane and the ethylene glycol, so that the dioxolane containing a small amount of water is obtained;
(3) Refining treatment:
and (3) refluxing one part of the dioxolane containing a small amount of water obtained in the step (2), and sending the other part of the dioxolane into a crude dioxolane refining unit for refining treatment.
The invention firstly also relates to a process device for synthesizing dioxolane by using extractive catalytic distillation, which comprises an extractive catalytic distillation tower 1, a condenser 2, a reflux tank 3 and a reflux pump 4 which are connected in sequence, wherein the structure diagram is shown in figure 2:
extraction catalysis rectifying column 1, upper portion is provided with ethylene glycol feed inlet 11 in the tower wall, the well lower part is provided with formaldehyde feed inlet 12, the top of the tower is provided with dioxolane bin outlet (13), the bottom of the tower is provided with waste water bin outlet (14), tower wall upper portion is provided with backward flow mouth 15, wherein: the ethylene glycol feed inlet is connected with a device capable of providing ethylene glycol, the formaldehyde feed inlet is connected with a device capable of providing formaldehyde, and the wastewater discharge outlet is connected with the wastewater decontamination water treatment unit;
the extractive catalytic rectification tower 1 comprises a rectification section, an extraction section, a reaction section and a stripping section from top to bottom; the rectifying section and the stripping section are respectively filled with a tower plate or a filler, and the reaction section is filled with a catalyst; when the rectifying section and the stripping section are respectively filled with the tower plates, the number of filling layers is N, N is more than or equal to 5 and less than or equal to 40, and the interlayer spacing is 0.1-2.0 m; when the rectifying section and the stripping section are respectively filled with structured packing, the number of the filling sections is N, N is more than or equal to 5 and less than or equal to 40, and the height of each section is 0.1-2.0 m; the catalyst is macroporous cation resin catalyst, and the loading form is preferably packed catalyst or module catalyst (preferably referring to the packed catalyst in 201720485329.0 or the module catalyst structure in 201620189748.5).
The ethylene glycol feed port 11 and the formaldehyde feed port 12 are positioned on the same side of the tower wall of the extraction catalytic rectification tower 1; the ethylene glycol feed port is positioned at the top of the extraction section; two formaldehyde feed inlets are arranged and are respectively positioned at the top and the bottom of the reaction section;
the condenser 2 is provided with an inlet I21 and an outlet I22, wherein: the inlet I is connected with a dioxolane discharge port 13 of the extractive catalytic distillation tower 1;
the reflux tank 3 is provided with an inlet II 31 and an outlet II 32, wherein: the inlet II is connected with the outlet I22 of the condenser 2;
the reflux pump 4 is provided with an inlet III 41 and an outlet III 42, wherein: the inlet III is connected with the outlet II 32 of the reflux tank 3, the outlet III is divided into two paths, one path is connected with the reflux port 15 of the extraction catalytic rectifying tower 1, and the other path is connected with the crude dioxolane refining unit.
The invention is illustrated below with reference to specific examples:
example 1:
this example provides a process units for synthesizing dioxolane by extractive catalytic distillation, wherein: when the rectifying section and the stripping section are filled with tower plates, the number of filling layers is N =22, and the interlayer spacing is 0.8 m; the packing form of the catalyst is packed catalyst: the catalyst comprises a stainless steel corrugated wire mesh, an active catalyst and a planar wire mesh, wherein the active catalyst is uniformly distributed on the planar wire mesh, the stainless steel corrugated wire mesh is tiled, overlapped and covered with the active catalyst, the edge of the stainless steel corrugated wire mesh is sealed, and one end of the stainless steel corrugated wire mesh is used as an axis to be rolled into a packed catalyst; the active catalyst is granular, and the diameter or the minimum peripheral size of the active catalyst is larger than the mesh diameters of the stainless steel corrugated wire mesh and the flat wire mesh so as to prevent leakage; the packing catalyst is rolled into a solid cylindrical shape, and the diameter of the packing catalyst is more than or equal to 50 mm (100 mm in the embodiment) and the height of the packing catalyst is more than or equal to 100mm (300 mm in the embodiment); the active catalyst is distributed uniformly over the cross-section of the packed catalyst (see packed catalyst in 201720485329.0 for setup).
Example 2:
this embodiment provides a process units for synthesizing dioxolane by extractive catalytic distillation, wherein: regular packing is filled in the rectifying section and the stripping section, the number of filling sections is N =23, and the height of each section is 1 m; the filling form of the catalyst is a module catalyst, and comprises the following components: the module catalyst is arranged in parallel by the metal wire mesh and the metal wire mesh corrugated plate at intervals, a catalyst layer is formed by containing the catalyst between the two metal wire meshes, and the catalyst in the catalyst layer is arranged by the metal wire mesh corrugated plate at intervals; catalyst layers in the module catalyst are arranged at intervals, and the outer contour of the module catalyst is wrapped, fixed and closed by a metal wire mesh to form a cylindrical or cubic geometric shape (in the embodiment, the module catalyst is cylindrical); one or two layers of wire mesh corrugated plates (in the embodiment, one layer) are preferably arranged between the wire mesh and the wire mesh; the catalyst layer is preferably arranged by one or two layers of wire mesh corrugated plates (in the embodiment, one layer is arranged) at intervals, namely the catalyst layer is arranged by one layer of wire mesh corrugated plate at intervals between two layers of wire mesh, and the catalyst particles are filled in the catalyst layer; the wire mesh and the wire mesh corrugated plate are made of stainless steel materials; the wire mesh and the wire mesh corrugated plate are vertically arranged (refer to a module catalyst structure in 201620189748.5).
Example 3:
a process for synthesizing dioxolane by extractive catalytic distillation is carried out by using the device in example 1, and comprises the following steps:
(1) Catalytic synthesis reaction:
ethylene glycol enters the extraction catalytic rectification tower 1 from an ethylene glycol feed inlet 11 at the top of the extraction section at a feed flow of 70kg/h, 37 percent of formaldehyde enters the extraction catalytic rectification tower 1 from formaldehyde feed inlets 12 at the top and the bottom of the reaction section at a feed flow of 81kg/h respectively, and the feed mass space velocity of the formaldehyde is 1.5h -1 (ii) a Ethylene glycol and formaldehyde are subjected to synthesis reaction under the catalytic action of a D006 resin catalyst in the reaction section to generate dioxolane; dioxolane and water are azeotroped to form an azeotrope, the azeotrope rises to an extraction section, and the residual wastewater falls to a stripping section and is discharged to a wastewater treatment unit from a wastewater discharge port 14 at the bottom of the tower;
(2) Extraction and rectification:
an azeotrope formed by the dioxolane and the water in the step (1) rises from the reaction section to the extraction section, and the glycol is continuously introduced from a glycol feed port 11 to be used as an extracting agent, wherein the feed flow is 70kg/h; the azeotrope is contacted with the glycol, because the solubility of the dioxolane and water in the glycol is different, the glycol breaks the azeotrope of the dioxolane and the water, the separation of the dioxolane and the water is realized, the water is discharged from a wastewater discharge port 14 at the bottom of the tower to a wastewater treatment unit after falling, the mixture of the glycol and the dioxolane rises to a rectification section, and because the boiling points of the dioxolane and the glycol are different, the separation of the dioxolane and the glycol is realized under the action of rectification, so that the dioxolane containing a small amount of water is obtained at the top of the tower, and the dioxolane containing a small amount of water is discharged from a dioxolane discharge port to a condenser 2;
(3) Refining treatment:
and (3) allowing the dioxolane containing a small amount of water obtained in the step (2) to sequentially flow through a condenser 2, a reflux tank 3 and a reflux pump 4, discharging a product from a discharge hole III 42 of the reflux pump 4, refluxing one part of the dioxolane into the extractive catalytic rectification tower 1 through a reflux hole, and feeding the other part of the dioxolane into a crude dioxolane refining unit for refining treatment, wherein the reflux ratio is 5:1.
In this example, the temperature in the rectifying section of the extractive catalytic distillation column 1 was controlled at 67 ℃ and the pressure at 0.03MPa, the temperature in the extracting section at 78 ℃ and the pressure at 0.04MPa, the temperature in the reaction section at 87 ℃ and the pressure at 0.05MPa, and the temperature in the stripping section at 120 ℃ and the pressure at 0.07MPa.
In this example, the yield of the product was 99.2% and the content was 98.6%.
Example 4:
a process for synthesizing dioxolane by extractive catalytic distillation is carried out by using the device in example 2, and comprises the following steps:
(1) Catalytic synthesis reaction:
ethylene glycol enters the extraction catalytic rectification tower 1 from an ethylene glycol feed port 11 at the top of the extraction section at a feed flow rate of 150kg/h, 37 percent of formaldehyde enters the extraction catalytic rectification tower 1 from a formaldehyde feed port 12 at the bottom of the reaction section at a feed flow rate of 175kg/h, and the feed mass space velocity of the formaldehyde is 1.7h -1 (ii) a Ethylene glycol and formaldehyde are subjected to synthetic reaction under the catalytic action of a KC107 resin catalyst in a reaction section to generate dioxolane; dioxolane and water are azeotroped to form an azeotrope, the azeotrope rises to an extraction section, and the residual wastewater falls to a stripping section and is discharged to a wastewater treatment unit from a wastewater discharge port 14 at the bottom of the tower;
(2) Extraction and rectification:
an azeotrope formed by the dioxolane and the water in the step (1) rises from the reaction section to the extraction section, and the glycol is continuously introduced from a glycol feed port 11 to be used as an extracting agent, wherein the feed flow is 150kg/h; the azeotrope is contacted with the glycol, because the solubility of the dioxolane and water in the glycol is different, the glycol breaks the azeotrope of the dioxolane and the water, the separation of the dioxolane and the water is realized, the water is discharged from a wastewater discharge port 14 at the bottom of the tower to a wastewater treatment unit after falling, the mixture of the glycol and the dioxolane rises to a rectification section, and because the boiling points of the dioxolane and the glycol are different, the separation of the dioxolane and the glycol is realized under the action of rectification, so that the dioxolane containing a small amount of water is obtained at the top of the tower, and the dioxolane containing a small amount of water is discharged from a dioxolane discharge port to a condenser 2;
(3) Refining treatment:
and (3) enabling the dioxolane containing a small amount of water obtained in the step (2) to sequentially flow through a condenser 2, a reflux tank 3 and a reflux pump 4, enabling the product to flow out from a discharge hole III 42 of the reflux pump 4, enabling one part of the product to flow back to the extraction catalytic rectifying tower 1 through a reflux hole, and enabling the other part of the product to be sent into a crude dioxolane refining unit for refining treatment, wherein the reflux ratio is 4:1.
In this example, the temperature in the rectifying section of the extractive catalytic distillation column (1) was controlled to 68 ℃ and the pressure to 0.05MPa, the temperature in the extracting section was controlled to 80 ℃ and the pressure to 0.07MPa, the temperature in the reaction section was controlled to 90 ℃ and the pressure to 0.09MPa, and the temperature in the stripping section was controlled to 125 ℃ and the pressure to 0.1MPa.
In this example, the yield of the product was 99.8% and the content was 98.8%.
The above examples are only for illustrating the technical idea and technical features of the present invention, and the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered in the protection scope of the present invention.
Claims (8)
1. A process method for synthesizing dioxolane by utilizing extractive catalytic distillation is characterized by comprising the following steps:
(1) Catalytic synthesis reaction:
performing synthetic reaction on ethylene glycol and formaldehyde under the catalytic action of a catalyst to generate dioxolane, performing extractive distillation after the dioxolane and water are azeotroped to form an azeotrope, and performing sewage treatment on the residual wastewater;
(2) And (3) extraction and rectification:
the azeotrope formed by the dioxolane and the water in the step (1) is contacted with the extractant glycol, the glycol breaks the azeotrope of the dioxolane and the water due to the different solubility of the dioxolane and the water in the glycol, the separation of the dioxolane and the water is realized, and the separation of the dioxolane and the glycol is further realized due to the different boiling points of the dioxolane and the glycol, so that the dioxolane containing a small amount of water is obtained;
(3) Refining treatment:
and (3) refluxing one part of the dioxolane containing a small amount of water obtained in the step (2), and sending the other part of the dioxolane into a crude dioxolane refining unit for refining treatment.
2. The process method according to claim 1, comprising the following steps:
(1) Catalytic synthesis reaction:
ethylene glycol enters the extraction catalytic rectifying tower (1) from an ethylene glycol feed port (11) at the top of the extraction section, formaldehyde enters the extraction catalytic rectifying tower (1) from formaldehyde feed ports (12) at the top and the bottom of the reaction section respectively, and the ethylene glycol and the formaldehyde are subjected to synthetic reaction under the catalytic action of a catalyst in the reaction section to generate dioxolane; dioxolane and water are azeotroped to form an azeotrope, the azeotrope rises to an extraction section, and the residual wastewater falls to a stripping section and is discharged to a wastewater treatment unit from a wastewater discharge port (14) at the bottom of the tower;
(2) And (3) extraction and rectification:
an azeotrope formed by the dioxolane and the water in the step (1) rises from the reaction section to the extraction section, the glycol is continuously introduced from a glycol feed port (11) to be used as an extracting agent, the azeotrope is contacted with the glycol, the glycol breaks the azeotrope of the dioxolane and the water due to the different solubility of the dioxolane and the water in the glycol, the dioxolane and the water are separated, the water is discharged from a waste water discharge port (14) at the bottom of the tower to a waste water treatment unit after falling, the mixture of the glycol and the dioxolane rises to the rectification section, and the dioxolane and the glycol are separated under the action of rectification due to the different boiling points of the dioxolane and the glycol, so that the dioxolane with a small amount of water is obtained at the top of the tower, and the dioxolane with a small amount of water is discharged from a dioxolane discharge port to a condenser (2);
(3) Refining treatment:
and (3) enabling the dioxolane containing a small amount of water obtained in the step (2) to sequentially flow through a condenser (2), a reflux tank (3) and a reflux pump (4), enabling a product to flow back to the extraction catalytic rectifying tower (1) from a reflux port through a discharge port III (42) of the reflux pump (4), and enabling the other part to be sent to a crude dioxolane refining unit for refining treatment.
3. The process of claim 2, wherein in step (1), the molar ratio of ethylene glycol to formaldehyde is 1.0 to 1.2.
4. The process of claim 2, wherein in step (1), the feed mass space velocity of the formaldehyde is 0.5-2.5 h "1.
5. The process of claim 2, wherein in step (1), the catalyst is any one of macroporous cationic resins.
6. The process method as claimed in claim 2, wherein the temperature in the rectifying section of the extractive catalytic distillation column (1) is controlled to be 60-75 ℃, the pressure is 0-0.2 MPa, the temperature in the extracting section is controlled to be 70-85 ℃, the pressure is 0-0.22 MPa, the temperature in the reaction section is controlled to be 80-95 ℃, the pressure is 0-0.24 MPa, the temperature in the stripping section is controlled to be 110-140 ℃, and the pressure is 0-0.25 MPa.
7. The process of claim 2 wherein in step (3), said refluxing is carried out at a reflux ratio of 2 to 6:1.
8. The utility model provides an utilize extraction catalytic distillation to synthesize process units of dioxolane, includes extraction catalytic distillation tower (1), condenser (2), reflux drum (3) and backwash pump (4) that connect gradually, its characterized in that:
extraction catalysis rectifying column (1), upper portion is provided with ethylene glycol feed inlet (11) in the tower wall, the well lower part is provided with formaldehyde feed inlet (12), the top of the tower is provided with dioxolane bin outlet (13), the bottom of the tower is provided with waste water bin outlet (14), tower wall upper portion is provided with return opening (15), wherein: the ethylene glycol feed inlet is connected with a device capable of providing ethylene glycol, the formaldehyde feed inlet is connected with a device capable of providing formaldehyde, and the wastewater discharge outlet is connected with the wastewater decontamination water treatment unit;
the condenser (2) is provided with an inlet I (21) and an outlet I (22), wherein: the inlet I is connected with a dioxolane discharge port (13) of the extractive catalytic distillation tower (1);
the reflux tank (3) is provided with an inlet II (31) and an outlet II (32), wherein: the inlet II is connected with the outlet I (22) of the condenser (2);
the reflux pump (4) is provided with an inlet III (41) and an outlet III (42), wherein: the inlet III is connected with the outlet II (32) of the reflux tank (3), the outlet III is divided into two paths, one path is connected with the reflux port (15) of the extraction catalytic rectifying tower (1), and the other path is connected with the coarse dioxolane refining unit.
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