CN113731320B - Dimethyl carbonate production device and method based on resource utilization - Google Patents
Dimethyl carbonate production device and method based on resource utilization Download PDFInfo
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- CN113731320B CN113731320B CN202111163590.6A CN202111163590A CN113731320B CN 113731320 B CN113731320 B CN 113731320B CN 202111163590 A CN202111163590 A CN 202111163590A CN 113731320 B CN113731320 B CN 113731320B
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 27
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 180
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 165
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 111
- 238000004821 distillation Methods 0.000 claims abstract description 60
- 238000007259 addition reaction Methods 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 9
- 230000005611 electricity Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 105
- 239000003054 catalyst Substances 0.000 claims description 100
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 58
- 238000011084 recovery Methods 0.000 claims description 38
- 239000007789 gas Substances 0.000 claims description 37
- 239000012295 chemical reaction liquid Substances 0.000 claims description 31
- 238000010992 reflux Methods 0.000 claims description 27
- 230000008878 coupling Effects 0.000 claims description 25
- 238000010168 coupling process Methods 0.000 claims description 25
- 238000005859 coupling reaction Methods 0.000 claims description 25
- 150000002148 esters Chemical group 0.000 claims description 16
- 230000005484 gravity Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 238000009834 vaporization Methods 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 1
- 229960004063 propylene glycol Drugs 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 description 18
- 238000002156 mixing Methods 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005381 potential energy Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229940090046 jet injector Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
- B01D3/322—Reboiler specifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
-
- 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
- C07D317/32—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/10—Greenhouse gas [GHG] capture, material saving, heat recovery or other energy efficient measures, e.g. motor control, characterised by manufacturing processes, e.g. for rolling metal or metal working
Abstract
The invention relates to a dimethyl carbonate production device and method based on resource utilization, belonging to the technical field of chemical industry, wherein the device comprises a hypergravity reactor, a jet reactor, a middle tank, a distillation kettle, a transesterification reaction kettle, a hypergravity rectifier I and a second; the raw materials are Propylene Oxide (PO), methanol and CO generated by light burned magnesium 2 Dimethyl carbonate (DMC) is obtained through addition reaction, distillation, transesterification and separation; the hypergravity reactor, the jet reactor and the hypergravity rectifier strengthen heat transfer and mass transfer; the heat of addition reaction is recovered to provide a heat source for a distillation kettle, light component steam separated by rectification is used for providing an auxiliary heat source for transesterification, the pressure energy of an addition reaction material flow is used for generating electricity, the energy-saving effect of a hypergravity rectifier is obvious, and the comprehensive energy saving of the device is 50%; the PO conversion rate is more than 99.5%, and the quality of DMC and 1, 2-propylene glycol is higher than that of the industrial national standard. The invention has mature process, continuous operation, high degree of automation, cyclic utilization of resources, environmental protection and realization of CO 2 And emission reduction.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a dimethyl carbonate production device and method based on resource utilization.
Background
The dimethyl carbonate production process is generally phosgene process, methanol oxidative carbosylation process and transesterification process. Since the phosgene method uses highly toxic phosgene as a main raw material, the two other methods become main methods for synthesizing DMC. The technology of synthesizing DMC by co-producing 1, 2-propylene glycol ester exchange method has been developed rapidly in recent years. The process is further developed to be key: firstly, transesterification is considered to be a reversible reaction, and the conversion rate is low; secondly, the configuration of the separation and refining tower and the screening of the extractant are very important to the improvement of the purity of the product; thirdly, the exothermic heat of the addition reaction is not well utilized, the energy consumption in the separation and refining stages is large, the cost is increased due to the increase of the energy consumption, and the industrial production is not facilitated.
The art is eager to find a low-energy-consumption DMC preparation process technology, which can overcome the technical problems.
Disclosure of Invention
Aiming at the engineering problems and market demands, the invention provides a dimethyl carbonate production device and method based on resource utilization, which have the advantages of simple process flow, continuous operation, high automation degree, resource recycling and environmental friendliness, meanwhile, advanced hypergravity reactors, hypergravity rectification machines, jet stirring reactors, MVR and other equipment are adopted, the DMC adopts the hypergravity rectification machines to directly carry out pressurized rectification to replace extraction rectification, so as to realize reasonable utilization of resources in the DMC synthesis process, recover addition reaction heat energy and pressure energy, recover heat generated in the separation and refining processes by using the MVR technology, and greatly reduce energy consumption.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a dimethyl carbonate production device based on resource utilization comprises a hypergravity reactor, a jet reactor, a middle tank, a distillation kettle, a transesterification reaction kettle and a hypergravity rectifier I which are connected in sequence; supergravity reactor for raw materials PO (propylene oxide) and CO 2 The spray reactor is used for continuously carrying out the addition reaction of the reaction liquid, the liquid PC (propylene carbonate) after the gas-liquid separation of the addition reaction liquid enters a middle tank, the distillation tank is used for distilling the liquid PC, and the distilled PC is cooledEntering an ester exchange reaction kettle, wherein the ester exchange reaction kettle is used for carrying out ester exchange reaction, and light components distilled out of the ester exchange reaction kettle enter a hypergravity rectifier I to obtain refined DMC (dimethyl carbonate) after rectification; wherein, the stirrers arranged in the jet reactor and the transesterification reaction kettle are jet stirrers;
the device also comprises a steam compressor, wherein the input end and the output end of the steam compressor are respectively connected with the hypergravity rectifying machine I and the transesterification reaction kettle, and MA (methanol) steam and DMC steam separated from the hypergravity rectifying machine I enter the transesterification reaction kettle after being boosted and heated by the steam compressor.
Further, the liquid outlet end of the reaction liquid of the hypergravity reactor is connected with the inlet of a heating tube bundle in the distillation still, and the outlet end of the heating tube bundle is connected with the jet reactor; the device also comprises a catalyst I recovery tank, wherein two ends of the catalyst I recovery tank are respectively connected with the distillation still and the hypergravity reactor 1, the catalyst I recovery tank is used for collecting liquid catalyst I extracted from the bottom of the distillation still, and the recovered catalyst I enters the hypergravity reactor 1 again to catalyze the addition reaction.
Further, the device also comprises a light component removing tower, a hypergravity rectifying machine II and a catalyst II recovery tank; heavy components at the lower part of the transesterification reaction kettle enter a light component removing tower, the top of the dehydrogenation tower is connected with the input end of a vapor compressor, and the removed light components enter the vapor compressor; the heavy component at the lower part enters a super gravity rectifying machine II7, the gravity rectifying machine II is used for rectifying 1,2-PG (propylene glycol), the catalyst II extracted from the lower part of the super gravity rectifying machine II enters a catalyst II recovery tank, and the recovered catalyst II is input into a transesterification reaction kettle to catalyze transesterification reaction.
The invention also provides a dimethyl carbonate production method based on the device, which comprises the following steps:
(1) Raw material PO, CO 2 The catalyst I enters a hypergravity reactor to carry out addition reaction;
(2) The reaction liquid discharged from the hypergravity reactor enters the jet reactor, and meanwhile, the gas discharged from the hypergravity reactor is sucked into the jet reactor to continue the addition reaction;
(3) The liquid PC separated from the addition reaction liquid of the jet reactor after gas-liquid separation enters an intermediate tank;
(4) The liquid PC in the middle tank enters a distillation kettle, and distilled PC enters an ester exchange reaction kettle after being cooled;
(5) Liquid PC of the PC tank, the catalyst II, a coupling distributor liquid inlet of a jet stirrer entering the transesterification reaction kettle, MA steam and DMC steam of a steam compressor, and fresh vaporization MA enter a gas inlet of the coupling distributor to carry out transesterification reaction in the transesterification reaction kettle; the light components (MA, DMC) distilled from the transesterification reactor are cooled and then enter a crude DMC tank;
(6) The crude DMC of the crude DMC pot enters a fractionating column (as reflux) of an ester exchange reaction kettle and a hypergravity rectifying machine I, and MA steam and DMC steam distilled from the top of the hypergravity rectifying machine I enter a steam compressor; and extracting the refined DMC from the lower part of the reboiler of the hypergravity rectifying machine I.
Further, the method comprises the steps of (7), continuously feeding heavy components (MA, DMC, propylene glycol, PC and catalyst II) at the lower part of the transesterification reaction kettle into a crude 1,2-PG tank, continuously feeding the crude 1,2-PG of the crude 1,2-PG tank into a light component removal tower through a crude 1,2-PG pump, continuously feeding the removed light component MA steam and DMC steam into a steam compressor, continuously feeding the heavy components at the lower part of a reboiler of the light component removal tower into the top of a hypergravity rectifying machine II, cooling the refined 1,2-PG at the top of the hypergravity rectifying machine II into a refined 1,2-PG tank through a condenser, and refluxing the refined 1,2-PG at the top of the hypergravity rectifying machine II through a refined 1,2-PG pump part, and partially extracting; PC, 1,2-PG and catalyst II are extracted from the lower part of a reboiler of the hypergravity rectifying machine II and enter a catalyst II recovery tank, and are returned to the transesterification reaction kettle for transesterification reaction through a catalyst II recovery pump.
Further, raw material CO 2 Recovered from light burned magnesium oxide, CO 2 The volume content is 99.9%, PO is industrial PO, MA is industrial MA, and the catalysts I, II are ionic liquid catalysts; the hypergravity reactor, the jet reactor, the transesterification reaction kettle, the hypergravity rectifier I and the hypergravity rectifier II all adopt jackets for heat exchange, and public engineering steam adopted for heat exchange is back pressure steam of 0.4MPa and 230 ℃ of a self-contained power plant; the utility steam is mainly provided for a hypergravity rectifier I, a hypergravity rectifier II and a light component removal towerA heat source, and simultaneously provides an auxiliary heat source for driving the hypergravity reactor, the jet reactor and the distillation kettle 4 and an auxiliary heat source for the transesterification reaction kettle 5; the supergravity reactor hot stream may provide the primary heat source for still 4; MA and DMC steam enter a steam compressor, and are subjected to Mechanical Vapor Recompression (MVR), namely, the compressor is boosted and heated to form secondary steam, the temperature of the secondary steam is 170 ℃, the pressure of the secondary steam is 0.15MPa, and the secondary steam can provide an auxiliary heat source for the transesterification reaction kettle.
Further, the addition reaction temperature of the hypergravity reactor in the step (1) is 190-195 ℃, the pressure is 6.5-7.0 MPa, the reaction time is 0.1-0.2 h, and the PO and CO are mixed 2 The mol ratio of the catalyst I is 1:1.3-1:1.5, and the dosage of the catalyst I is 1-2% (based on the total mass of the raw materials).
Further, the reaction temperature of the jet reactor in the step (2) is 195-200 ℃, the pressure is 6.0-6.5 MPa, and the addition reaction time is 0.9-1 h; the reaction liquid discharged from the hypergravity reactor heats the distillation still through a discharge pump, continuously enters the jet reactor after being cooled, and simultaneously sucks the gases PO and CO discharged from the hypergravity reactor 2 The addition reaction was continued.
Further, the temperature of the intermediate tank in the step (3) is 140-145 ℃, the pressure is 0.20-0.25 MPa, and the residence time is 2-2.5 h; the reaction liquid of the jet reactor continuously enters a turbine to drive a generator to generate electricity and recover pressure energy; the addition reaction liquid from the turbine is separated into PO and CO gases by a gas-liquid separation tank 2 Entering an exhaust gas treatment system; and the liquid PC separated by the gas-liquid separation tank enters the intermediate tank.
Further, the temperature of the distillation still in the step (4) is 150-155 ℃, the vacuum degree is-0.095 MPa to-0.098 MPa, and fractions with the temperature of 135-140 ℃ are collected; the liquid PC in the middle tank continuously enters a distillation kettle, distilled PC is cooled by a condenser and enters a PC tank, and the liquid in the PC tank continuously enters an ester exchange reaction kettle by a PC pump; the liquid catalyst I is extracted from the bottom of the distillation kettle, enters a catalyst I recovery tank through a pump at the bottom of the distillation kettle, and continuously enters a hypergravity reactor through a catalyst I recovery pump.
Further, the temperature of the transesterification reaction kettle in the step (5) is 75-78 ℃, the temperature of the top of the distillation tower is 64-66 ℃, the reflux ratio is 3-4, the pressure is normal pressure, and the residence time is 1.5-2 h; the molar ratio of MA to PC is 4:1-4.4:1, and the dosage of the catalyst II is 0.05-0.1% of the total mass of the materials.
Further, the temperature of the hypergravity rectifying machine I in the step (6) is 180-185 ℃, the distilling temperature is 137-139 ℃, the pressure is 1.0-1.02 MPa, the reflux ratio is 2-2.2, and the hypergravity factor is 40-41; the crude DMC in the crude DMC tank continuously enters the top of a hypergravity rectifying machine I through a crude DMC pump, the top of the hypergravity rectifying machine I is provided with refined DMC from a refined DMC pump as reflux, MA and DMC distilled from the top enter a buffer tank, and then steam enters a compressor.
Further, the temperature of the hypergravity rectifying machine II in the step (7) is 180-185 ℃, the distilling temperature is 130-132 ℃, the vacuum degree is minus 0.095MPa to minus 0.090MPa, the reflux ratio is 1.5-1.6, and the hypergravity factor is 40-41.
Compared with the prior art, the dimethyl carbonate production device and method based on resource utilization have the beneficial effects that:
1. raw material CO 2 The content of the recovered light burned magnesia is 99.9 percent (volume), and the utility steam is the back pressure steam of the self-contained power plant; the injection reactor pressure stream may provide a pressure energy source for a turbine of the generator; MA steam and DMC steam generated in the separation and refining process are subjected to mechanical steam recompression (MVR), and secondary steam can provide an auxiliary heat source for the transesterification reaction kettle; the hot material flow of the hypergravity reactor provides a heat source for the distillation kettle; the resources are effectively utilized, the energy is saved, and the environment is protected.
2. The two-stage addition reactor connected in series adopts a supergravity reactor and a jet reactor, so that the heat transfer and mass transfer are enhanced, and the gas-liquid mixing effect is improved; the transesterification reaction kettle adopts a jet stirrer to suck MA steam and DMC steam, so that the transesterification reaction is enhanced, and the production efficiency is improved;
3. the DMC adopts a hypergravity rectifier to directly rectify under pressure to replace extraction rectification; the PG rectification adopts a hypergravity rectification machine for rectification, thereby being safe and energy-saving;
4. PO conversion rate is more than 99.5%, DMC and 1,2-PG quality are superior to industrial national standard; the invention has mature process, continuous operation, high automation degree, cyclic utilization of resources, environmental protection, comprehensive energy saving of 50% of devices and realization of CO 2 And emission reduction.
Drawings
FIG. 1 is a schematic diagram of a dimethyl carbonate production device based on recycling;
reference numerals: 1. 1-1 parts of a hypergravity reactor, 1-2 parts of a hypergravity reactor jacket, 1-3 parts of a rotor, 1-4 parts of a filler, 1-5 parts of a liquid distributor, 1-6 parts of a discharge pump and a mechanical seal; 2. the device comprises a jet reactor, 2-1 parts of a jet stirrer coupling distributor, 2-2 parts of a jet stirrer ejector, 2-3 parts of a jet stirrer power fluid pump, 2-4 parts of a turbine, 2-5 parts of a generator; 3. an intermediate tank, 3-1, a gas-liquid separation tank; 4. 4-1 parts of distillation still, 4-2 parts of condenser, 4-2 parts of PC tank, 4-3 parts of PC pump, 4-4 parts of distillation still bottom pump, 4-5 parts of catalyst I recovery tank, 4-6 parts of catalyst I recovery pump; 5. the transesterification reaction kettle, 5-1, a jet mixer coupling distributor, 5-2, a jet mixer jet injector, 5-3, a jet mixer power fluid pump, 5-4, a condenser, 5-5, a crude DMC tank, 5-6, a crude DMC pump, 5-7, a crude 1,2-PG tank, 5-8, a crude 1,2-PG pump, 5-9, a light component removal tower, 5-10 and a light component removal tower reboiler; 6. 6-1 parts of a hypergravity rectifier I, a hypergravity rectifier I jacket, 6-2 parts of a rotor, 6-3 parts of a filler, 6-4 parts of a liquid distributor, 6-5 parts of a vapor compressor, 6-6 parts of a hypergravity rectifier I reboiler, 6-7 parts of a fine DMC tank, 6-8 parts of a fine DMC pump, 6-9 parts of a buffer tank; 7. the high gravity rectifier II,7-1, a high gravity rectifier II jacket, 7-2, a rotor, 7-3, a filler, 7-4, a liquid distributor, 7-5, a refined 1,2-PG condenser, 7-6, a refined 1,2-PG tank, 7-7, a refined 1,2-PG pump, 7-8, a high gravity rectifier II reboiler, 7-9, a catalyst II recovery tank, 7-10 and a catalyst II recovery pump.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
As shown in fig. 1, the invention provides a dimethyl carbonate production device based on resource utilization, which comprises a hypergravity reactor 1, a jet reactor 2, a middle tank 3, a distillation kettle 4, a transesterification reaction kettle 5 and a hypergravity rectifier I6 which are connected in sequence; the hypergravity reactor 1 is used for raw materials PO and CO 2 The addition reaction of the catalyst I is carried out, the jet reactor 2 is used for carrying out the addition reaction on the reaction liquid continuously, the liquid PC enters the middle tank 3 after the gas-liquid separation of the addition reaction liquid, the distillation kettle 4 is used for distilling the liquid PC, the distilled PC enters the transesterification reaction kettle 5 after being cooled, the transesterification reaction kettle 5 is used for the transesterification reaction of the PC and the catalyst II, and the light component distilled by the transesterification reaction kettle enters the hypergravity rectifier I to obtain refined DMC after rectification; wherein, the stirrers arranged in the jet reactor 2 and the transesterification reaction kettle 5 are jet stirrers;
the device also comprises a steam compressor 6-5, wherein the input end and the output end of the steam compressor are respectively connected with the hypergravity rectifying machine I6 and the transesterification reaction kettle 5, MA (methanol) steam and DMC steam separated from the hypergravity rectifying machine I are boosted and heated by the steam compressor and then enter the transesterification reaction kettle to carry out transesterification reaction, and an auxiliary heat source is provided for the transesterification reaction.
The liquid outlet end of the reaction liquid in the hypergravity reactor 1 is connected with the inlet of a heating tube bundle in the distillation kettle, the outlet end of the heating tube bundle is connected with the jet reactor 2, the distillation kettle 4 takes the reaction liquid in the hypergravity reactor 1 as a heat source, namely the reaction liquid in the hypergravity reactor 1 flows through the distillation kettle 4 firstly, and then enters the jet reactor 2 after being cooled; the device also comprises a catalyst I recovery tank 4-5, wherein two ends of the catalyst I recovery tank 4-5 are respectively connected with the distillation still 4 and the hypergravity reactor 1, the catalyst I recovery tank is used for collecting liquid catalyst I extracted from the bottom of the distillation still 4, and the recovered catalyst I enters the hypergravity reactor 1 again to catalyze the addition reaction.
The device also comprises a light component removing tower 5-9, a hypergravity rectifying machine II7 and a catalyst II recycling tank 7-9; heavy components at the lower part of the transesterification reaction kettle 5 enter a light component removing tower, the top of the dehydrogenation tower is connected with the input end of a vapor compressor, and the removed light components enter the vapor compressor; the heavy components at the lower part enter a super-gravity rectifying machine II7, the second gravity rectifying machine 7 is used for rectifying 1,2-PG, PC, 1,2-PG and a catalyst II extracted from the lower part of the super-gravity rectifying machine II enter a catalyst II recovery tank 7-9, and then are input into a transesterification reaction kettle 5 for catalyzing transesterification reaction.
The hypergravity rectifier I, II consists of jackets (6-1, 7-1), rotors (6-2, 7-2), fillers (6-3, 7-3) and liquid distributors (6-4, 7-4), wherein the hypergravity reactor 1, the jet reactor 2, the transesterification reaction kettle 5, the hypergravity rectifier I and the hypergravity rectifier 6II7 all adopt jacket heat exchange.
The production method of the dimethyl carbonate based on the device specifically comprises the following production steps:
(1) CO recovered from PO liquid and light burned magnesium as raw material 2 Continuously introducing gas, fresh liquid catalyst I and recovered liquid catalyst I into a hypergravity reactor 1 to perform addition reaction;
(2) The reaction liquid discharged from the hypergravity reactor 1 is cooled by a heating distillation kettle 4 and then continuously enters the jet reactor 2, and meanwhile, the gas discharged from the hypergravity reactor 1 is sucked for continuous addition reaction;
(3) The reaction liquid of the jet reactor 2 continuously enters a turbine 2-4 to drive a generator 2-5 to generate electricity and recover pressure energy; the addition reaction liquid from the turbine 2-4 is separated into gases PO and CO by a gas-liquid separation tank 3-1 2 Entering an exhaust gas treatment system; the liquid PC separated by the gas-liquid separation tank 3-1 enters the middle tank 3;
(4) The liquid PC in the intermediate tank 3 continuously enters the distillation kettle 4, the distilled PC is cooled by the condenser 4-1, the liquid enters the PC tank 4-2, and the liquid in the PC tank 4-2 continuously enters the transesterification reaction kettle 5 by the PC pump 4-3; the liquid catalyst I is extracted from the bottom of the distillation kettle 4, enters a catalyst I recovery tank 4-5 through a distillation kettle bottom pump 4-4, and continuously enters a hypergravity reactor 1 through a catalyst I recovery pump 4-6;
(5) Liquid PC of the PC tank 4-2, fresh liquid catalyst II, catalyst II recovered by the hypergravity rectifying machine II7 and liquid in the kettle continuously enter a liquid inlet of a coupling distributor 5-1 of a jet stirrer of the transesterification reaction kettle 5, methanol (MA) steam and DMC steam separated by the hypergravity rectifying machine I6, MA steam and DMC steam separated by a light component removal tower 5-9, and fresh vaporization MA is driven by a jet stirrer power fluid pump 5-3 to continuously suck power fluid into a gas inlet of the coupling distributor 5-1 to enter the transesterification reaction kettle 5 for transesterification reaction; the light components (MA, DMC) distilled from the transesterification reaction kettle 5 are cooled by a condenser 5-4 and enter a crude DMC tank 5-5, and the heavy components (MA, DMC, propylene glycol, PC, catalyst II) at the lower part of the transesterification reaction kettle 5 continuously enter a crude 1,2-PG tank 5-7;
(6) The crude DMC continuously enters a fractionating column (as reflux) of an ester exchange reaction kettle 5 and a hypergravity rectifying machine I6 through a crude DMC pump 5-6, the top of the hypergravity rectifying machine I6 is provided with refined DMC from a refined DMC pump 6-8 as reflux, MA steam and DMC steam distilled from the top enter a buffer tank 6-9, and the MA steam and the DMC steam are mechanically compressed again (MVR) through a compressor 6-5, namely secondary steam boosted and heated by the compressor provides an auxiliary heat source for the ester exchange reaction; the MA steam and DMC steam after the temperature and pressure increase are sucked into the transesterification reaction kettle 5 to carry out transesterification reaction through the spraying stirrer coupling distributor 5-1 of the transesterification reaction kettle 5; the refined DMC is extracted from the lower part of a reboiler 6-6 of the super-gravity rectifying machine I6 and enters a refined DMC tank 6-7;
(7) The crude 1,2-PG of the crude 1,2-PG tank 5-7 continuously enters a light component removal tower 5-9 through a crude 1,2-PG pump 5-8, removed light component MA steam and DMC steam enter a compressor 6-5, and secondary steam heated through mechanical steam recompression (MVR) provides an auxiliary heat source for transesterification reaction; the MA and DMC steam after the temperature and pressure increase are sucked into the transesterification reaction kettle 5 through the transesterification reaction kettle 5 jet stirrer coupling distributor 5-1 to carry out transesterification reaction; heavy components at the lower part of the light component removal tower reboiler 5-10 continuously enter the top of a hypergravity rectifying machine II7, and the top of the hypergravity rectifying machine II7 is provided with refined 1,2-PG from a refined 1,2-PG pump 7-7 as reflux; the refined 1,2-PG extracted from the top of the super-gravity rectifying machine II7 is cooled by a condenser 7-5 and enters a refined 1,2-PG tank 7-6, and part of the refined 1,2-PG is used as the top reflux of the super-gravity rectifying machine II7 by a refined 1,2-PG pump 7-7 and is extracted partially; PC, 1,2-PG and catalyst II are extracted from the lower part of a reboiler 7-8 of the hypergravity rectifying machine II and enter a catalyst II recovery tank 7-9, and are returned to the transesterification reaction kettle 5 through a catalyst II recovery pump 7-10 to carry out transesterification reaction by a jet stirrer coupling distributor 5-1.
The jet stirrer adopted by the invention consists of jet stirrer jet devices (2-2 and 5-2) and a jet stirrer coupling distributor (2-1 and 5-1), wherein the coupling distributor consists of a mixed liquid inlet pipe, a mixed liquid distribution cavity, a gas suction pipe, a gas distribution cavity and the like; the jet device adopts a venturi jet principle and consists of a power fluid inlet, a guide ring, a power fluid nozzle, a gas suction inlet, a mixing cavity, a diffusion cavity and a mixed liquid outlet; the circulating pump sucks mixed liquid in the tank during operation, the mixed liquid is pumped into the mixed liquid distribution cavity through the mixed liquid inlet pipe after being boosted by the pump impeller, and the mixed liquid distributed through the distribution cavity enters the ejector through the mixed liquid inlet of the ejector. The dynamic fluid passes through the nozzle to form high-speed fluid, at the moment, the kinetic energy of the fluid is maximum, the potential energy is minimum, the sucked gas rapidly expands in a negative pressure area and is beaten into tiny bubbles by the dynamic fluid, in the mixing cavity, the gas and the liquid are fully mixed, the fluid is strongly mixed and stirred in the mixing area, and is accelerated and discharged due to energy exchange, the potential energy of the mixed liquid is increased to the maximum through the diffusion cavity and is directed to the tank bottom, and the dragging effect of the mixed fluid further enhances the mixing and stirring effect. The gas is sucked into the tank by the jet mixing stirrer, and 300m/s high-speed jet flow can be generated in a gas-liquid mixing cavity of the jet mixing stirrer, so that the reaction of the gas and the liquid is facilitated;
the super-gravity reactor consists of a super-gravity reactor jacket 1-1, a rotor 1-2, a filler 1-3, a liquid distributor 1-4 and a mechanical seal 1-6, wherein the rotor with a specific structure rotates at high speed in a shell, gas phase enters the shell from a radial gas inlet, enters the rotor from the outer edge of the rotor, liquid phase enters the center of the rotor from an axial liquid inlet, is distributed by the liquid distributor, and forms a gas-liquid interface with a positive and continuously updated specific surface in the rotor, so that the super-gravity reactor has the advantages of extremely high mass transfer rate, energy conservation and pressure resistance. Finally, the gas phase leaves the bed body through the axial outlet; the liquid phase is led out from the radial liquid outlet after being collected in the shell.
When the production device is started, the supergravity reactor 1, the jet reactor 2 and the transesterification reaction kettle 5 adopt steam to be introduced into a jacket to heat materials, and the distillation kettle 4 adopts steam to be introduced into an inner heating tube bundle to heat the materials until the whole production device normally operates; after normal operation, cooling water is introduced into jackets of the hypergravity reactor 1 and the jet reactor 2 to control the reaction temperature, the transesterification reaction kettle 5 uses secondary steam as an auxiliary heat source, when the secondary steam is insufficient, public engineering steam is also used as an auxiliary heat source of the transesterification reaction kettle 5, and the distillation kettle 4 uses the reaction liquid of the hypergravity reactor 1 as a heat source; in the invention, all the device equipment is connected through corresponding pipelines, and when the pipelines in the figure 1 are crossed on the figure and are not crossed actually, the pipelines are drawn according to the principle of continuous vertical and horizontal cutting.
Example 2
A process for the production of dimethyl carbonate based on the apparatus described in example 1, comprising the steps of:
(1) Raw material CO 2 Recovered from light burned magnesium oxide, CO 2 The volume content is 99.9%, industrial PO, industrial MA; the addition reaction temperature of the hypergravity reactor 1 is 190 ℃, the pressure is 6.5MPa, the reaction time is 0.2h, and the PO and CO are mixed 2 The mol ratio of the catalyst I to the catalyst I is 1:1.3, and the dosage of the catalyst I is 2 percent (based on the total mass of raw materials); 1742.400kg/hPO liquid, 1716.371kg/h CO 2 The gas, 69.168kg/h fresh liquid catalyst I and the recovered liquid catalyst I continuously and axially enter the liquid distributor 1-4 and CO in the hypergravity reactor 1 2 The liquid and the gas enter into a filler 1-3 in the hypergravity reactor 1 in the radial direction through the hypergravity reactor 1, and carry out addition reaction in a rotor 1-2;
(2) The reaction temperature of the jet reactor 2 is 195 ℃, the pressure is 6.0MPa, and the addition reaction time is 1h; the reaction liquid discharged from the hypergravity reactor 1 heats the distillation still 4 through the discharge pump 1-5, continuously enters the jet reactor power fluid pump 2-3 after being cooled, enters the jet stirrer coupling distributor 2-1, and simultaneously sucks the gases PO and CO discharged from the hypergravity reactor 1 2 The addition reaction proceeds via the jet mixer ejector 2-2.
(3) The temperature of the intermediate tank is 140 ℃, the pressure is 0.20MPa, and the residence time is 2h; the reaction liquid of the jet reactor 2 continuously enters the turbine 2-4 to driveThe generator 2-5 generates electricity and recovers pressure energy; the addition reaction liquid from the turbine 2-4 is separated into gases PO and CO by a gas-liquid separation tank 3-1 2 Entering an exhaust gas treatment system; the liquid PC separated by the gas-liquid separation tank 3-1 enters the intermediate tank 3.
(4) The temperature of the distillation still 4 is 150 ℃, the vacuum degree is-0.095 MPa, and fractions at 140 ℃ are collected; the liquid PC in the intermediate tank 3 continuously enters the distillation kettle 4, the distilled PC is cooled by the condenser 4-1 and enters the PC tank 4-2, and the liquid in the PC tank 4-2 continuously enters the transesterification reaction kettle 5 by the PC pump 4-3; the liquid catalyst I is extracted from the bottom of the distillation kettle 4, enters a catalyst I recovery tank 4-5 through a distillation kettle bottom pump 4-4, and continuously enters a hypergravity reactor 1 through a catalyst I recovery pump 4-6.
(5) The temperature of the transesterification reaction kettle 5 is 75 ℃, the temperature of the top of the distillation column is 64 ℃, the reflux ratio is 3, the pressure is normal pressure, and the residence time is 2 hours; the molar ratio of MA to PC is 4:1, and the dosage of the catalyst II is 0.1% of the total mass of the materials; 2956.322kg/h of liquid PC of the PC tank 4-2, fresh liquid catalyst II, catalyst II recovered by the super-gravity rectifying machine II7 and liquid in the kettle continuously enter a liquid inlet of the jet stirrer coupling distributor 5-1 of the transesterification reaction kettle 5, MA steam recovered by the super-gravity rectifying machine I6, DMC steam and MA steam recovered by the light component removal tower 5-9, fresh vaporization MA is driven by the jet stirrer power fluid pump 5-3 to continuously suck power fluid into a gas inlet of the coupling distributor 5-1 to enter the transesterification reaction kettle 5 for transesterification reaction, MA is 3711.257kg/h in total, and catalyst II is 7.668kg/h in total; the light components (MA, DMC) distilled from the transesterification reaction kettle 5 are cooled by a condenser 5-4 and enter a crude DMC tank 5-5, and the heavy components (MA, DMC, propylene glycol, PC, catalyst II) at the lower part of the transesterification reaction kettle 5 continuously enter a crude 1,2-PG tank 5-7.
(6) The temperature of the hypergravity rectifying machine I6 is 180 ℃, the distilling temperature is 137 ℃, the pressure is 1.0MPa, the reflux ratio is 2, and the hypergravity factor is 40; the adoption of the hypergravity rectification improves the vapor-liquid phase contact specific surface area and the mass and heat transfer rate, so that the size of the equipment is greatly reduced, the mass transfer efficiency is very high, the flooding is not easy, the pressure resistance is realized, and the energy is saved; the crude DMC continuously enters the top of a hypergravity rectifying machine I6 through a crude DMC pump 5-6, the top of the hypergravity rectifying machine I6 is provided with refined DMC from a refined DMC pump 6-8 as reflux, MA and DMC distilled from the top enter a buffer tank 6-9, and steam is subjected to Mechanical Vapor Recompression (MVR) through a compressor 6-5, namely secondary steam which is boosted and heated by the compressor provides an auxiliary heat source for transesterification; the MA steam and DMC steam after the temperature and pressure increase are sucked into the transesterification reaction kettle 5 to carry out transesterification reaction through the spraying stirrer coupling distributor 5-1 of the transesterification reaction kettle 5; the lower part of a 6-reboiler of the super-gravity rectifying machine I6 is used for extracting refined DMC;
(7) The temperature of the hypergravity rectifier II7 is 180 ℃, the distillation temperature is 130 ℃, the vacuum degree is-0.095 MPa, the reflux ratio is 1.5, and the hypergravity factor is 40; the adoption of the hypergravity rectification improves the vapor-liquid phase contact specific surface area and the mass and heat transfer rate, so that the size of the equipment is greatly reduced, the mass transfer efficiency is very high, the flooding is not easy, the pressure resistance is realized, and the energy is saved; the crude 1,2-PG of the crude 1,2-PG tank 5-7 continuously enters a light component removal tower 5-9 through a crude 1,2-PG pump 5-8, removed light component MA steam and DMC steam enter a compressor 6-5, and secondary steam heated through mechanical steam recompression (MVR) provides an auxiliary heat source for transesterification reaction; the MA and DMC steam after the temperature and pressure increase are sucked into the transesterification reaction kettle 5 through the transesterification reaction kettle 5 jet stirrer coupling distributor 5-1 to carry out transesterification reaction; heavy components at the lower part of the light component removal tower reboiler 5-10 continuously enter the top of a hypergravity rectifying machine II7, and the top of the hypergravity rectifying machine II7 is provided with refined 1,2-PG from a refined 1,2-PG pump 7-7 as reflux; the refined 1,2-PG extracted from the top of the super-gravity rectifying machine II7 is cooled by a condenser 7-5 and enters a refined 1,2-PG tank 7-6, and part of the refined 1,2-PG is used as the top reflux of the super-gravity rectifying machine II7 by a refined 1,2-PG pump 7-7 and is extracted partially; PC, 1,2-PG and catalyst II are extracted from the lower part of a reboiler 7-8 of the hypergravity rectifying machine II and enter a catalyst II recovery tank 7-9, and are returned to the transesterification reaction kettle 5 through a catalyst II recovery pump 7-10 to carry out transesterification reaction by a jet stirrer coupling distributor 5-1. And packaging the dimethyl carbonate and the 1, 2-propylene glycol in a barreled manner to leave a factory.
Example 3
A process for the production of dimethyl carbonate based on the apparatus described in example 1, comprising the steps of:
a dimethyl carbonate production method based on resource utilization comprises the following steps:
(1) Raw materialsCO 2 Recovered from light burned magnesium oxide, CO 2 The volume content is 99.9%, industrial PO, industrial MA; the addition reaction temperature of the hypergravity reactor 1 is 195 ℃, the pressure is 7.0MPa, the reaction time is 0.1h, and the PO and CO are mixed 2 1:1.5, the catalyst I is used in an amount of 1% (based on the total mass of the raw materials); 1742.400kg/hPO liquid, 1980.428kg/hCO 2 The gas, 37.229kg/h fresh liquid catalyst I and the recovered liquid catalyst I continuously and axially enter the liquid distributor 1-4 and CO in the hypergravity reactor 1 2 The liquid and the gas enter into a filler 1-3 in the hypergravity reactor 1 in the radial direction through the hypergravity reactor 1, and carry out addition reaction in a rotor 1-2;
(2) The reaction temperature of the jet reactor 2 is 200 ℃, the pressure is 6.5MPa, and the addition reaction time is 0.9h; the reaction liquid discharged from the hypergravity reactor 1 heats the distillation still 4 through the discharge pump 1-5, continuously enters the jet reactor power fluid pump 2-3 after being cooled, enters the jet stirrer coupling distributor 2-1, and simultaneously sucks the gases PO and CO discharged from the hypergravity reactor 1 2 The addition reaction proceeds via the jet mixer ejector 2-2.
(3) The temperature of the intermediate tank is 145 ℃, the pressure is 0.25MPa, and the residence time is 2.5h; the reaction liquid of the jet reactor 2 continuously enters a turbine 2-4 to drive a generator 2-5 to generate electricity and recover pressure energy; the addition reaction liquid from the turbine 2-4 is separated into gases PO and CO by a gas-liquid separation tank 3-1 2 Entering an exhaust gas treatment system; the liquid PC separated by the gas-liquid separation tank 3-1 enters the intermediate tank 3.
(4) The temperature of the distillation still 4 is 155 ℃, the vacuum degree is-0.098 MPa, and the fraction at 135 ℃ is collected; the liquid PC in the intermediate tank 3 continuously enters the distillation kettle 4, the distilled PC is cooled by the condenser 4-1 and enters the PC tank 4-2, and the liquid in the PC tank 4-2 continuously enters the transesterification reaction kettle 5 by the PC pump 4-3; the liquid catalyst I is extracted from the bottom of the distillation kettle 4, enters a catalyst I recovery tank 4-5 through a distillation kettle bottom pump 4-4, and continuously enters a hypergravity reactor 1 through a catalyst I recovery pump 4-6.
(5) The temperature of the transesterification reaction kettle 5 is 78 ℃, the temperature of the top of the distillation column is 66 ℃, the reflux ratio is 4, the pressure is normal pressure, and the residence time is 1.5h; the molar ratio of MA to PC is 4.4:1, and the dosage of the catalyst II is 0.05% of the total mass of the materials; 2956.322kg/h of liquid PC of the PC tank 4-2, fresh liquid catalyst II, catalyst II recovered by the super-gravity rectifying machine II7 and liquid in the kettle continuously enter a liquid inlet of the jet stirrer coupling distributor 5-1 of the transesterification reaction kettle 5, MA steam recovered by the super-gravity rectifying machine I6, DMC steam and MA steam recovered by the light component removal tower 5-9, fresh vaporization MA is driven by the jet stirrer power fluid pump 5-3 to continuously suck power fluid into a gas inlet of the coupling distributor 5-1 to enter the transesterification reaction kettle 5 for transesterification reaction, MA is 3711.257kg/h in total, and catalyst II is 3.834kg/h in total; the light components (MA, DMC) distilled from the transesterification reaction kettle 5 are cooled by a condenser 5-4 and enter a crude DMC tank 5-5, and the heavy components (MA, DMC, propylene glycol, PC, catalyst II) at the lower part of the transesterification reaction kettle 5 continuously enter a crude 1,2-PG tank 5-7.
(6) The temperature of the hypergravity rectifying machine I6 is 185 ℃, the distilling temperature is 139 ℃, the pressure is 1.02MPa, the reflux ratio is 2.2, and the hypergravity factor is 41; the adoption of the hypergravity rectification improves the vapor-liquid phase contact specific surface area and the mass and heat transfer rate, so that the size of the equipment is greatly reduced, the mass transfer efficiency is very high, the flooding is not easy, the pressure resistance is realized, and the energy is saved; the crude DMC continuously enters the top of a hypergravity rectifying machine I6 through a crude DMC pump 5-6, the top of the hypergravity rectifying machine I6 is provided with refined DMC from a refined DMC pump 6-8 as reflux, MA and DMC distilled from the top enter a buffer tank 6-9, and steam is subjected to Mechanical Vapor Recompression (MVR) through a compressor 6-5, namely secondary steam which is boosted and heated by the compressor provides an auxiliary heat source for transesterification; the MA steam and DMC steam after the temperature and pressure increase are sucked into the transesterification reaction kettle 5 to carry out transesterification reaction through the spraying stirrer coupling distributor 5-1 of the transesterification reaction kettle 5; the lower part of a 6-reboiler of the super-gravity rectifying machine I6 is used for extracting refined DMC;
(7) The temperature of the hypergravity rectifier II7 is 185 ℃, the distillation temperature is 132 ℃, the vacuum degree is-0.090 MPa, the reflux ratio is 1.6, and the hypergravity factor is 41; the adoption of the hypergravity rectification improves the vapor-liquid phase contact specific surface area and the mass and heat transfer rate, so that the size of the equipment is greatly reduced, the mass transfer efficiency is very high, the flooding is not easy, the pressure resistance is realized, and the energy is saved; the crude 1,2-PG of the crude 1,2-PG tank 5-7 continuously enters a light component removal tower 5-9 through a crude 1,2-PG pump 5-8, removed light component MA steam and DMC steam enter a compressor 6-5, and secondary steam heated through mechanical steam recompression (MVR) provides an auxiliary heat source for transesterification reaction; the MA and DMC steam after the temperature and pressure increase are sucked into the transesterification reaction kettle 5 through the transesterification reaction kettle 5 jet stirrer coupling distributor 5-1 to carry out transesterification reaction; heavy components at the lower part of the light component removal tower reboiler 5-10 continuously enter the top of a hypergravity rectifying machine II7, and the top of the hypergravity rectifying machine II7 is provided with refined 1,2-PG from a refined 1,2-PG pump 7-7 as reflux; the refined 1,2-PG extracted from the top of the super-gravity rectifying machine II7 is cooled by a condenser 7-5 and enters a refined 1,2-PG tank 7-6, and part of the refined 1,2-PG is used as the top reflux of the super-gravity rectifying machine II7 by a refined 1,2-PG pump 7-7 and is extracted partially; PC, 1,2-PG and catalyst II are extracted from the lower part of a reboiler 7-8 of the hypergravity rectifying machine II and enter a catalyst II recovery tank 7-9, and are returned to the transesterification reaction kettle 5 through a catalyst II recovery pump 7-10 to carry out transesterification reaction by a jet stirrer coupling distributor 5-1. And packaging the dimethyl carbonate and the 1, 2-propylene glycol in a barreled manner to leave a factory.
According to the dimethyl carbonate production method based on resource utilization, the comprehensive energy conservation of the device is 50%; the quality of the dimethyl carbonate is higher than the standard of GB/T33107-2016 quality products, and the quality of the 1, 2-propylene glycol is higher than the standard of HG/T5392-2018 quality products.
The technical scheme of the invention is explained in the technical scheme, the protection scope of the invention cannot be limited by the technical scheme, and any changes and modifications to the technical scheme according to the technical substance of the invention belong to the protection scope of the technical scheme of the invention.
Claims (10)
1. Dimethyl carbonate apparatus for producing based on resource utilization, its characterized in that: a dimethyl carbonate production device based on resource utilization comprises a hypergravity reactor, a jet reactor, a middle tank, a distillation kettle, a transesterification reaction kettle and a hypergravity rectifier I which are connected in sequence; supergravity reactor for raw materials of propylene oxide PO and CO 2 The spray reactor is used for continuously carrying out the addition reaction of the reaction liquid, the liquid propylene carbonate PC enters the intermediate tank after the gas-liquid separation of the addition reaction liquid, and the distillation kettleThe method comprises the steps that the distilled PC is used for distilling liquid PC, cooled and enters an ester exchange reaction kettle, the ester exchange reaction kettle is used for carrying out ester exchange reaction, light components distilled by the ester exchange reaction kettle enter a hypergravity rectifier I, and refined dimethyl carbonate DMC is obtained after rectification; wherein, the stirrers arranged in the jet reactor and the transesterification reaction kettle are jet stirrers;
the device also comprises a vapor compressor, wherein the input end and the output end of the vapor compressor are respectively connected with the hypergravity rectifying machine I and the transesterification reaction kettle, and methanol MA vapor and DMC vapor separated from the hypergravity rectifying machine I enter the transesterification reaction kettle after being boosted and heated by the vapor compressor.
2. The recycling-based dimethyl carbonate production device according to claim 1, wherein: the liquid outlet end of the reaction liquid of the hypergravity reactor is connected with the inlet of a heating tube bundle in the distillation kettle, and the outlet end of the heating tube bundle is connected with the jet reactor; the device also comprises a catalyst I recovery tank, wherein two ends of the catalyst I recovery tank are respectively connected with the distillation still and the hypergravity reactor, the catalyst I recovery tank is used for collecting liquid catalyst I extracted from the bottom of the distillation still, and the recovered catalyst I enters the hypergravity reactor again to catalyze the addition reaction.
3. The recycling-based dimethyl carbonate production device according to claim 1, wherein: the device also comprises a light component removing tower, a hypergravity rectifying machine II and a catalyst II recovery tank; heavy components at the lower part of the transesterification reaction kettle enter a light component removing tower, the top of the light component removing tower is connected with the input end of a vapor compressor, and the removed light components enter the vapor compressor; the heavy component at the lower part enters a hypergravity rectifier II7, the hypergravity rectifier II is used for rectifying propylene glycol 1,2-PG, the catalyst II extracted from the lower part of the hypergravity rectifier II enters a catalyst II recovery tank, and the recovered catalyst II is then input into a transesterification reaction kettle to catalyze transesterification reaction.
4. A process for the production of dimethyl carbonate based on the apparatus according to any one of claims 1 to 3, characterized in that: the method specifically comprises the following steps:
(1) Raw material PO, CO 2 The catalyst I enters a hypergravity reactor to carry out addition reaction;
(2) The reaction liquid discharged from the hypergravity reactor enters the jet reactor, and meanwhile, the gas discharged from the hypergravity reactor is sucked into the jet reactor to continue the addition reaction;
(3) The liquid PC separated from the addition reaction liquid of the jet reactor after gas-liquid separation enters an intermediate tank;
(4) The liquid PC in the middle tank enters a distillation kettle, and distilled PC enters an ester exchange reaction kettle after being cooled;
(5) Liquid PC of the PC tank, the catalyst II, a coupling distributor liquid inlet of a jet stirrer entering the transesterification reaction kettle, MA steam and DMC steam of a steam compressor, and fresh vaporization MA enter a gas inlet of the coupling distributor to carry out transesterification reaction in the transesterification reaction kettle; cooling the light component distilled from the transesterification reaction kettle and then entering a crude DMC (methyl methacrylate) tank;
(6) The crude DMC of the crude DMC tank enters a fractionating column of an ester exchange reaction kettle and a hypergravity rectifying machine I, MA steam and DMC steam distilled from the top of the hypergravity rectifying machine I enter a steam compressor; and extracting the refined DMC from the lower part of the reboiler of the hypergravity rectifying machine I.
5. The method for producing dimethyl carbonate according to claim 4, wherein: the method further comprises the steps of (7), continuously feeding heavy components at the lower part of the transesterification reaction kettle into a crude 1,2-PG tank, continuously feeding the crude 1,2-PG of the crude 1,2-PG tank into a light component removal tower through a crude 1,2-PG pump, continuously feeding the removed light component MA steam and DMC steam into a steam compressor, continuously feeding the heavy components at the lower part of a reboiler of the light component removal tower into the top of a hypergravity rectifying machine II, collecting refined 1,2-PG at the top of the hypergravity rectifying machine II, cooling the refined 1,2-PG by a condenser, feeding the refined 1,2-PG into a refined 1,2-PG pump part as the top of the hypergravity rectifying machine II for reflux, and partially collecting the refined 1, 2-PG; PC, 1,2-PG and catalyst II are extracted from the lower part of a reboiler of the hypergravity rectifying machine II and enter a catalyst II recovery tank, and are returned to the transesterification reaction kettle for transesterification reaction through a catalyst II recovery pump.
6. The method for producing dimethyl carbonate according to claim 5, wherein: raw material CO 2 Recovered from light burned magnesium oxide, CO 2 The volume content is 99.9%, PO is industrial PO, MA is industrial MA, and the catalysts I, II are ionic liquid catalysts; the hypergravity reactor, the jet reactor, the transesterification reaction kettle, the hypergravity rectifier I and the hypergravity rectifier II all adopt jacket heat exchange, and public engineering steam adopted in heat exchange is back pressure steam of 0.4MPa and 230 ℃ of a self-contained power plant; the public engineering steam mainly provides heat sources for the hypergravity rectifier I, the hypergravity rectifier II and the light component removal tower, and also provides auxiliary heat sources for driving of the hypergravity reactor, the jet reactor and the distillation kettle and auxiliary heat sources for the transesterification reaction kettle; the hot material flow of the hypergravity reactor can provide a main heat source for the distillation still; MA and DMC steam enter a steam compressor, and are subjected to Mechanical Vapor Recompression (MVR), namely, the compressor is boosted and heated to form secondary steam, the temperature of the secondary steam is 170 ℃, the pressure of the secondary steam is 0.15MPa, and the secondary steam can provide an auxiliary heat source for the transesterification reaction kettle.
7. The method for producing dimethyl carbonate according to claim 4, wherein: the addition reaction temperature of the hypergravity reactor in the step (1) is 190-195 ℃, the pressure is 6.5-7.0 MPa, the reaction time is 0.1-0.2 h, and PO and CO are mixed 2 The mol ratio of the catalyst I is 1:1.3-1:1.5, and the dosage of the catalyst I is 1-2% of the total raw material mass; the reaction temperature of the jet reactor in the step (2) is 195-200 ℃, the pressure is 6.0-6.5 MPa, and the addition reaction time is 0.9-1 h; the reaction liquid discharged from the hypergravity reactor heats the distillation still through a discharge pump, continuously enters the jet reactor after being cooled, and simultaneously sucks the gases PO and CO discharged from the hypergravity reactor 2 The addition reaction was continued.
8. The method for producing dimethyl carbonate according to claim 4, wherein: the temperature of the intermediate tank in the step (3) is 140-145 ℃, the pressure is 0.20-0.25 MPa, and the residence time is 2-2.5 h; reaction liquid continuous feeding of jet reactorThe turbine is put into the generator to generate electricity, and the pressure energy is recovered; the addition reaction liquid from the turbine is separated into PO and CO gases by a gas-liquid separation tank 2 Entering an exhaust gas treatment system; the liquid PC separated by the gas-liquid separation tank enters the middle tank; the temperature of the distillation still in the step (4) is 150-155 ℃, the vacuum degree is-0.095 MPa to-0.098 MPa, and fractions with the temperature of 135-140 ℃ are collected; the liquid PC in the middle tank continuously enters a distillation kettle, distilled PC is cooled by a condenser and enters a PC tank, and the liquid in the PC tank continuously enters an ester exchange reaction kettle by a PC pump; the liquid catalyst I is extracted from the bottom of the distillation kettle, enters a catalyst I recovery tank through a pump at the bottom of the distillation kettle, and continuously enters a hypergravity reactor through a catalyst I recovery pump.
9. The method for producing dimethyl carbonate according to claim 4, wherein: the temperature of the transesterification reaction kettle in the step (5) is 75-78 ℃, the temperature of the top of the distillation column is 64-66 ℃, the reflux ratio is 3-4, the pressure is normal pressure, and the residence time is 1.5-2 h; the molar ratio of MA to PC is 4:1-4.4:1, and the dosage of the catalyst II is 0.05-0.1% of the total mass of the materials; the temperature of the hypergravity rectifying machine I in the step (6) is 180-185 ℃, the distilling temperature is 137-139 ℃, the pressure is 1.0-1.02 MPa, the reflux ratio is 2-2.2, and the hypergravity factor is 40-41; the crude DMC in the crude DMC tank continuously enters the top of a hypergravity rectifying machine I through a crude DMC pump, the top of the hypergravity rectifying machine I is provided with refined DMC from a refined DMC pump as reflux, MA and DMC distilled from the top enter a buffer tank, and then steam enters a compressor.
10. The method for producing dimethyl carbonate according to claim 5, wherein: the temperature of the super gravity rectifying machine II in the step (7) is 180-185 ℃, the distilling temperature is 130-132 ℃, the vacuum degree is minus 0.095MPa to minus 0.090MPa, the reflux ratio is 1.5-1.6, and the super gravity factor is 40-41.
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| CN202111163590.6A CN113731320B (en) | 2021-09-30 | 2021-09-30 | Dimethyl carbonate production device and method based on resource utilization |
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| CN201529413U (en) * | 2009-11-06 | 2010-07-21 | 北京化工大学 | Multistage counter flow hypergravity revolving bed device |
| CN107417534A (en) * | 2017-06-20 | 2017-12-01 | 中国科学院过程工程研究所 | A kind of system and technique of co-producing dimethyl carbonate and ethylene glycol |
| CN112479883A (en) * | 2020-12-16 | 2021-03-12 | 吴剑华 | Production device for dimethyl carbonate by ester exchange method and use method thereof |
| CN113387811A (en) * | 2021-08-02 | 2021-09-14 | 华东理工大学 | Energy-saving consumption-reducing method for producing dimethyl carbonate by ester exchange method |
| CN216419333U (en) * | 2021-09-30 | 2022-05-03 | 沈阳工业大学 | Dimethyl carbonate apparatus for producing based on resource utilization |
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| TWI382979B (en) * | 2006-02-22 | 2013-01-21 | Shell Int Research | Process for the production of alkylene carbonate and use of alkylene carbonate thus produced in the manufacture of an alkane diol and a dialkyl carbonate |
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| CN201529413U (en) * | 2009-11-06 | 2010-07-21 | 北京化工大学 | Multistage counter flow hypergravity revolving bed device |
| CN107417534A (en) * | 2017-06-20 | 2017-12-01 | 中国科学院过程工程研究所 | A kind of system and technique of co-producing dimethyl carbonate and ethylene glycol |
| CN112479883A (en) * | 2020-12-16 | 2021-03-12 | 吴剑华 | Production device for dimethyl carbonate by ester exchange method and use method thereof |
| CN113387811A (en) * | 2021-08-02 | 2021-09-14 | 华东理工大学 | Energy-saving consumption-reducing method for producing dimethyl carbonate by ester exchange method |
| CN216419333U (en) * | 2021-09-30 | 2022-05-03 | 沈阳工业大学 | Dimethyl carbonate apparatus for producing based on resource utilization |
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