CN113731320A - 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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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 130
- 150000002148 esters Chemical group 0.000 claims abstract description 121
- 238000004821 distillation Methods 0.000 claims abstract description 67
- 238000007259 addition reaction Methods 0.000 claims abstract description 41
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 8
- 230000005611 electricity Effects 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 110
- 239000003054 catalyst Substances 0.000 claims description 102
- 238000011084 recovery Methods 0.000 claims description 39
- 239000007789 gas Substances 0.000 claims description 33
- 239000012295 chemical reaction liquid Substances 0.000 claims description 31
- 238000010992 reflux Methods 0.000 claims description 27
- 238000002347 injection Methods 0.000 claims description 23
- 239000007924 injection Substances 0.000 claims description 23
- 230000008878 coupling Effects 0.000 claims description 22
- 238000010168 coupling process Methods 0.000 claims description 22
- 238000005859 coupling reaction Methods 0.000 claims description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 abstract description 190
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 162
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract description 23
- 238000012546 transfer Methods 0.000 abstract description 16
- 229960004063 propylene glycol Drugs 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 57
- 239000012530 fluid Substances 0.000 description 16
- 238000002156 mixing Methods 0.000 description 8
- 238000005809 transesterification reaction Methods 0.000 description 7
- 239000000945 filler Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000016507 interphase Effects 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
- 239000012071 phase Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000007791 liquid 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
- 238000003763 carbonization Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- 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
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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, an ester exchange reaction kettle, and hypergravity rectifying machines I and II; raw materials are Propylene Oxide (PO), methanol and CO generated by light-burned magnesium2Dimethyl carbonate (DMC) is obtained through addition reaction, distillation, ester exchange reaction and separation; a super-gravity reactor, a spray reactor,The hypergravity rectifying machine strengthens heat transfer and mass transfer; the heat recovered by the addition reaction heat provides a heat source for the distillation still, the light component steam separated by rectification provides an auxiliary heat source for the ester exchange reaction, the pressure energy of the addition reaction material flow generates electricity, the energy saving effect of the supergravity rectifier is obvious, and the device is comprehensive and energy-saving by 50%; the PO conversion rate is more than 99.5 percent, and the quality of DMC and 1, 2-propylene glycol is higher than the national standard of industrial products. The invention has mature process, continuous operation, high automation degree, cyclic utilization of resources and environmental protection, and realizes CO2And (5) 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 production methods of dimethyl carbonate are generally phosgene method, methanol oxidation carbonization method and ester exchange method. The phosgene process is basically eliminated because the phosgene with high toxicity is used as the main raw material, and the other two methods become the main methods for synthesizing DMC. The DMC technology synthesized by the ester exchange method for coproducing 1, 2-propylene glycol is rapidly developed in recent years. The process has the key for further development: firstly, ester exchange is considered as a reversible reaction, and the conversion rate is low; secondly, the configuration of the separation and refining tower and the screening of an extracting agent are very important for improving the purity of the product; thirdly, the exothermic heat of the addition reaction is not well utilized, the energy consumption is large in the separation and refining stages, the cost is increased due to the increase of the energy consumption, and the industrial production is not facilitated.
The art is eagerly seeking a process for preparing DMC with low energy consumption, which can overcome the above technical problems.
Disclosure of Invention
Aiming at the engineering problems and the market demand, aiming at overcoming the problems in the prior art, the invention provides a dimethyl carbonate production device and a method based on resource utilization, the process flow is simple, the continuous operation is realized, the automation degree is high, the resources are recycled, the environment is friendly, meanwhile, advanced devices such as a supergravity reactor, a supergravity rectifier, a jet stirring reactor, an MVR and the like are adopted, the DMC adopts the supergravity rectifier to pressurize and directly rectify to replace extraction rectification, the reasonable utilization of the resources in the process of synthesizing the DMC is realized, the heat energy and the pressure energy of addition reaction are recovered, the heat generated in the separation and refining process is recovered by utilizing the MVR technology, and the energy consumption is greatly reduced.
In order to achieve the purpose, the 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 still, an ester exchange reaction still and a hypergravity rectifying machine I which are connected in sequence; hypergravity reactor for raw materials PO (propylene oxide) and CO2The jet reactor is used for continuously carrying out addition reaction on reaction liquid, liquid PC (propylene carbonate) enters an intermediate tank after gas-liquid separation of the addition reaction liquid, a distillation kettle is used for distilling the liquid PC, the distilled PC enters an ester exchange reaction kettle after being cooled, the ester exchange reaction kettle is used for carrying out ester exchange reaction, light components distilled from the ester exchange reaction kettle enter a super-gravity rectifier I, and the rectified DMC (dimethyl carbonate) is obtained after rectification; wherein, the stirrers arranged in the jet reactor and the ester exchange 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 ester exchange reaction kettle, and MA (methanol) vapor and DMC vapor removed from the hypergravity rectifying machine I enter the ester exchange reaction kettle after being boosted and heated by the vapor 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 still includes catalyst I recovery tank, and distillation still, hypergravity reactor 1 are connected respectively to catalyst I recovery tank both ends, catalyst I recovery tank is used for collecting the liquid catalyst I who adopts at the bottom of the distillation still, and the catalyst I who retrieves reentrants hypergravity reactor 1 catalytic addition reaction.
Further, the device also comprises a light component removal tower, a hypergravity rectifying machine II and a catalyst II recovery tank; heavy components at the lower part of the ester exchange reaction kettle enter a light component removal 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 hypergravity rectifying machine II7, the gravity rectifying machine II is used for rectifying 1,2-PG (propylene glycol), the catalyst II extracted at the lower part of the hypergravity rectifying machine II enters a catalyst II recovery tank, and the recovered catalyst II is input into an ester exchange reaction kettle to catalyze the ester exchange reaction.
The invention also provides a dimethyl carbonate production method based on the device, which comprises the following steps:
(1) raw materials PO, CO2The catalyst I enters a supergravity reactor to carry out addition reaction;
(2) reaction liquid discharged from the hypergravity reactor enters the jet reactor, and gas discharged from the hypergravity reactor is sucked for continuous addition reaction;
(3) liquid PC separated from addition reaction liquid of the injection reactor after gas-liquid separation enters an intermediate tank;
(4) the liquid PC in the intermediate tank enters a distillation kettle, and the distilled PC enters an ester exchange reaction kettle after being cooled;
(5) liquid PC in a PC tank, a catalyst II and a coupling distributor liquid inlet of a jet stirrer entering an ester exchange reaction kettle, MA steam and DMC steam of a steam compressor and fresh vaporized MA enter a gas inlet of the coupling distributor, and ester exchange reaction is carried out in the ester exchange reaction kettle; cooling light components (MA and DMC) distilled from the ester exchange reaction kettle, and then feeding the light components into a crude DMC tank;
(6) crude DMC in the crude DMC tank 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 fine DMC from the lower part of a reboiler I of the hypergravity rectifying machine.
Further, the method also comprises a step (7), heavy components (MA, DMC, propylene glycol, PC and a catalyst II) at the lower part of the ester exchange reaction kettle continuously enter a crude 1,2-PG tank, crude 1,2-PG in the crude 1,2-PG tank continuously enters a lightness-removing tower through a crude 1,2-PG pump, removed light components (MA steam and DMC steam) enter a steam compressor, heavy components at the lower part of a reboiler of the lightness-removing tower continuously enter the top of a hypergravity rectifying machine II, refined 1,2-PG is extracted from the top of the hypergravity rectifying machine II, the refined 1,2-PG is cooled by a condenser and enters a refined 1,2-PG tank, and the refined 1,2-PG is partially extracted through a refined 1,2-PG pump part serving as the top reflux of the hypergravity rectifying machine II; and (3) extracting PC, 1,2-PG and catalyst II from the lower part of a reboiler of the hypergravity rectifying machine II, feeding the obtained product into a catalyst II recovery tank, and returning the obtained product to an ester exchange reaction kettle through a catalyst II recovery pump to perform ester exchange reaction.
Further, raw material CO2Recovered for light-burned magnesia, CO2The volume content is 99.9 percent, PO is industrial product PO, MA is industrial product MA, and the catalyst I, II is an ionic liquid catalyst; the hypergravity reactor, the injection reactor, the ester exchange reaction kettle, the hypergravity rectifying machine I and the hypergravity rectifying machine II adopt jacket heat exchange, and public engineering steam adopted for heat exchange is backpressure steam with the temperature of 230 ℃ and 0.4MPa of a self-contained power plant; the utility steam mainly provides heat sources for the hypergravity rectifying machine I, the hypergravity rectifying machine II and the lightness-removing tower, and also provides auxiliary heat sources for the hypergravity reactor, the jet reactor and the distillation kettle 4 for driving and provides an auxiliary heat source for the ester exchange reaction kettle 5; the hypergravity reactor hot stream can provide a main heat source for the distillation still 4; MA and DMC steam enters a steam compressor, and is subjected to Mechanical Vapor Recompression (MVR), namely, the pressure of the compressor is increased, the temperature is increased, the secondary steam becomes secondary steam, the temperature of the secondary steam is 170 ℃, the pressure of the secondary steam is superheated steam of 0.15MPa, and the secondary steam can provide an auxiliary heat source for the ester exchange reaction kettle.
Further, the temperature of the addition reaction 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 react2The molar ratio of 1: 1.3-1: 1.5, and the amount of the catalyst I is 1-2% (based on the total mass of the raw materials).
Further, the reaction temperature of the injection 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 high-gravity reactor is heated by a discharge pump to a distillation kettle, and continuously enters a jet reactor after being cooled, and simultaneously, PO and CO gases discharged from the high-gravity reactor are sucked2The 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 retention time is 2-2.5 h; continuously feeding the reaction liquid of the injection reactor into a turbine to drive a generator to generate electricity and recover pressure energy; separating PO and CO from the addition reaction liquid from the turbine through a gas-liquid separation tank2Entering an exhaust gas treatment system; and liquid PC separated from the gas-liquid separation tank enters the intermediate tank.
Further, the temperature of the distillation kettle in the step (4) is 150-155 ℃, the vacuum degree is-0.095 MPa-0.098 MPa, and the fraction at 135-140 ℃ is collected; the liquid PC in the intermediate tank continuously enters a distillation kettle, the 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; liquid catalyst I is extracted from the bottom of the distillation kettle and enters a catalyst I recovery tank through a distillation kettle bottom pump, and the recovered catalyst I continuously enters the supergravity reactor through a catalyst I recovery pump.
Further, the temperature of the ester exchange 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 retention 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 distillation 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, fine DMC from a fine DMC pump is arranged at the top of the hypergravity rectifying machine I and serves as reflux, MA and DMC distilled from the top enter a buffer tank, and then enter steam and pass through a compressor.
Further, the temperature of the hypergravity rectifying machine II in the step (7) is 180-185 ℃, the distillation temperature is 130-132 ℃, the vacuum degree is-0.095 MPa to-0.090 MPa, 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. feedstock CO2The recovered content of light-burned magnesia was 99.9% by volume, and the utility steam used was back pressure steam from the power plant; the injection of the 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 Vapor Recompression (MVR), and secondary steam can provide an auxiliary heat source for the ester exchange 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 series-connected addition reactor adopts a supergravity reactor and an injection reactor, so that heat transfer and mass transfer are enhanced, and the gas-liquid mixing effect is improved; the ester exchange reaction kettle adopts a jet stirrer to suck MA steam and DMC steam, so that the ester exchange reaction is strengthened, and the production efficiency is improved;
3. DMC adopts the pressurization direct rectification of the hypergravity rectifying machine to replace the extractive rectification; PG rectification adopts a hypergravity rectifier for rectification, and is safe and energy-saving;
4. the PO conversion rate is more than 99.5 percent, and the quality of DMC and 1,2-PG is superior to the national standard of industrial products; the invention has mature process, continuous operation, high automation degree, resource recycling, environment friendliness, 50 percent of comprehensive energy conservation of the device and realization of CO2And (5) emission reduction.
Drawings
FIG. 1 is a schematic diagram of a dimethyl carbonate production apparatus based on resource utilization according to the present invention;
reference numerals: 1. 1-1 parts of a supergravity reactor, 1-2 parts of a supergravity 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 mechanical sealing; 2. 2-1 of a jet reactor, 2-2 of a jet stirrer coupling distributor, 2-2 of a jet stirrer ejector, 2-3 of a jet stirrer power fluid pump, 2-4 of a turbine, 2-5 of a generator; 3. a middle tank 3-1, a gas-liquid separation tank; 4. 4-1 of a distillation kettle, 4-2 of a condenser, 4-3 of a PC tank, 4-4 of a PC pump, 4-5 of a distillation kettle bottom pump, 4-6 of a catalyst I recovery tank and a catalyst I recovery pump; 5. the method comprises the following steps of (1) a transesterification reaction kettle, 5-1 a jet stirrer coupling distributor, 5-2 a jet stirrer ejector, 5-3 a jet stirrer 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 a light component removal tower reboiler; 6. 6-1 parts of a hypergravity rectifying machine I, 6-2 parts of a hypergravity rectifying machine I jacket, 6-3 parts of a rotor, 6-4 parts of a packing, 6-5 parts of a liquid distributor, 6-6 parts of a vapor compressor, 6-7 parts of a hypergravity rectifying machine 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 system comprises a hypergravity rectifying machine II, 7-1, a hypergravity rectifying machine II jacket, 7-2, a rotor, 7-3, a filler, 7-4, a liquid distributor, 7-5, a fine 1,2-PG condenser, 7-6, a fine 1,2-PG tank, 7-7, a fine 1,2-PG pump, 7-8, a hypergravity rectifying machine II reboiler, 7-9, a catalyst II recovery tank, 7-10 and a catalyst II recovery pump.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit 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, an intermediate tank 3, a distillation kettle 4, an ester exchange reaction kettle 5 and a hypergravity rectifying machine I6 which are connected in sequence; the high gravity reactor 1 is used for raw materials of PO and CO2The method comprises the following steps of (1) performing addition reaction on a catalyst I, wherein a spray reactor 2 is used for continuously performing addition reaction on reaction liquid, liquid PC enters an intermediate tank 3 after gas-liquid separation of the addition reaction liquid, a distillation kettle 4 is used for distilling the liquid PC, the distilled PC enters an ester exchange reaction kettle 5 after being cooled, the ester exchange reaction kettle 5 is used for ester exchange reaction of the PC and the catalyst II, light components distilled from the ester exchange reaction kettle enter a supergravity rectifier I, and the refined DMC is obtained after rectification; wherein, the stirrers arranged in the injection reactor 2 and the ester exchange reaction kettle 5 are injection stirrers;
the device also comprises a vapor compressor 6-5, wherein the input end and the output end of the vapor compressor are respectively connected with the hypergravity rectifying machine I6 and the ester exchange reaction kettle 5, MA (methanol) vapor and DMC vapor removed from the hypergravity rectifying machine I enter the ester exchange reaction kettle for ester exchange reaction after being boosted and heated by the vapor compressor, and an auxiliary heat source is provided for the ester exchange reaction.
The liquid outlet end of the reaction liquid of the hypergravity reactor 1 is connected with the inlet of a heating tube bundle in a distillation still, the outlet end of the heating tube bundle is connected with the injection reactor 2, the distillation still 4 takes the reaction liquid of the hypergravity reactor 1 as a heat source, namely, the reaction liquid in the hypergravity reactor 1 firstly flows through the distillation still 4, and then enters the injection reactor 2 after being cooled; the device further comprises a catalyst I recovery tank 4-5, two ends of the catalyst I recovery tank 4-5 are respectively connected with the distillation still 4 and the supergravity reactor 1, the catalyst I recovery tank is used for collecting the liquid catalyst I extracted from the bottom of the distillation still 4, and the recovered catalyst I enters the supergravity reactor 1 for catalytic addition reaction.
The device also comprises a light component removal tower 5-9, a hypergravity rectifying machine II7 and a catalyst II recovery tank 7-9; the heavy component at the lower part of the ester exchange reaction kettle 5 enters a light component removal tower, the top of the dehydrogenation tower is connected with the input end of a vapor compressor, and the removed light component enters the vapor compressor; the heavy component at the lower part enters a hypergravity rectifying machine II7, a gravity rectifying machine II7 is used for rectifying 1,2-PG, PC, 1,2-PG and catalyst II extracted from the lower part of the hypergravity rectifying machine II enter a catalyst II recovery tank 7-9, and then are input into an ester exchange reaction kettle 5 for catalyzing ester exchange reaction.
The hypergravity rectifying machine I, II is composed of jackets (6-1, 7-1), rotors (6-2, 7-2), fillers (6-3, 7-3) and liquid distributors (6-4, 7-4), and the hypergravity reactor 1, the injection reactor 2, the ester exchange reaction kettle 5, the hypergravity rectifying machine I and the hypergravity rectifying machine 6II7 are all subjected to jacket heat exchange.
The dimethyl carbonate production method based on the device specifically comprises the following production steps:
(1) CO recovered from PO liquid and light-burned magnesium as raw materials2Continuously feeding gas, fresh liquid catalyst I and recovered liquid catalyst I into the supergravity reactor 1 for addition reaction;
(2) the reaction liquid discharged from the hypergravity reactor 1 passes through a heating distillation kettle 4, is cooled and then continuously enters a jet reactor 2, and meanwhile, the gas discharged from the hypergravity reactor 1 is sucked for continuous addition reaction;
(3) continuously feeding the reaction liquid of the injection reactor 2 into 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 passes through a gas-liquid separation tank 3-1 to separate PO and CO2Entering an exhaust gas treatment system; the liquid PC separated by the gas-liquid separation tank 3-1 enters the intermediate tank 3;
(4) liquid PC in the middle tank 3 continuously enters a distillation kettle 4, the distilled PC is cooled by a condenser 4-1, the liquid enters a PC tank 4-2, and the liquid in the PC tank 4-2 continuously enters an ester exchange reaction kettle 5 by a PC pump 4-3; liquid catalyst I is extracted from the bottom of the distillation kettle 4 and enters a catalyst I recovery tank 4-5 through a distillation kettle bottom pump 4-4, and the recovered catalyst I continuously enters the supergravity reactor 1 through a catalyst I recovery pump 4-6;
(5) liquid PC in a PC tank 4-2, a fresh liquid catalyst II, a catalyst II recovered by a supergravity rectifying machine II7 and liquid in the kettle continuously enter a coupling distributor 5-1 liquid inlet of a jet stirrer of an ester exchange reaction kettle 5, Methanol (MA) steam and DMC steam removed from a supergravity rectifying machine I6, MA steam and DMC steam removed from a light removal tower 5-9, and fresh vaporized MA is continuously sucked into a gas inlet of the coupling distributor 5-1 by a power fluid pump 5-3 of the jet stirrer to enter the ester exchange reaction kettle 5 for ester exchange reaction; the light components (MA, DMC) distilled from the ester exchange 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 and catalyst II) at the lower part of the ester exchange reaction kettle 5 continuously enter a crude 1,2-PG tank 5-7;
(6) the crude DMC passes through a crude DMC pump 5-6, and continuously enters a fractionating column (as reflux) of an ester exchange reaction kettle 5 and a hypergravity rectifying machine I6, the top of the hypergravity rectifying machine I6 is provided with fine DMC from a fine DMC pump 6-8 as reflux, MA steam and DMC steam distilled from the top enter a buffer tank 6-9, the MA steam and the DMC steam are recompressed (MVR) through a compressor 6-5 mechanical steam, namely secondary steam of the pressure increase and the temperature increase of the compressor provides an auxiliary heat source for ester exchange reaction; absorbing the MA steam and the DMC steam after temperature and pressure increase into the ester exchange reaction kettle 5 for ester exchange reaction through a jet stirrer coupling distributor 5-1 of the ester exchange reaction kettle 5; extracting fine DMC from the lower part of a 6-6 reboiler of the supergravity rectifying machine I6 and feeding the fine DMC into a fine DMC tank 6-7;
(7) crude 1,2-PG in a 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 components MA steam and DMC steam enter a compressor 6-5, and secondary steam heated through Mechanical Vapor Recompression (MVR) provides an auxiliary heat source for ester exchange reaction; absorbing the MA and DMC steam after temperature and pressure increase into an ester exchange reaction kettle 5 through an ester exchange reaction kettle 5 jet stirrer coupling distributor 5-1 to perform ester exchange reaction; heavy components at the lower part of a reboiler 5-10 of the light component removal tower continuously enter the top of a supergravity rectifying machine II7, and the top of a supergravity rectifying machine II7 is provided with fine 1,2-PG from a fine 1,2-PG pump 7-7 as reflux; the refined 1,2-PG extracted from the top of the supergravity rectifying machine II7 enters a refined 1,2-PG tank 7-6 after being cooled by a condenser 7-5, and part of the refined 1,2-PG flows through a refined 1,2-PG pump 7-7 to be used as the top reflux of the supergravity rectifying machine II7, and part of the refined 1,2-PG is extracted; PC, 1,2-PG and catalyst II are extracted from the lower part of a reboiler 7-8 of the supergravity rectifying machine II7 and enter a catalyst II recovery tank 7-9, and are returned to the ester exchange reaction kettle 5 through a catalyst II recovery pump 7-10 and are coupled with a distributor 5-1 through a jet stirrer for carrying out ester exchange reaction.
The jet stirrer adopted by the invention consists of jet stirrers (2-2, 5-2) and a jet stirrer coupling distributor (2-1, 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 ejector adopts the 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; when the ejector is in operation, the circulating pump sucks mixed liquid in the tank, 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 by the distribution cavity enters the ejector through the mixed liquid inlet of the ejector. The power fluid passes through the nozzle to form high-speed fluid, at the moment, the kinetic energy of the fluid is the largest, the potential energy of the fluid is the smallest, the sucked gas is rapidly expanded in the negative pressure area and is beaten into tiny bubbles by the power fluid, the gas and the liquid are fully mixed in the mixing cavity, the fluid is intensively mixed and stirred in the mixing area and is accelerated to be discharged due to energy exchange, the potential energy of the mixed liquid is increased to the maximum value through the pressure expansion cavity and is emitted to the bottom of the tank, and the mixing and stirring effects are enhanced due to the dragging effect of the mixed fluid. Gas is sucked into the tank through the jet mixing stirrer, and high-speed jet flow of 300m/s 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 supergravity reactor of the present invention consists of supergravity reactor jacket 1-1, rotor 1-2, stuffing 1-3, liquid distributor 1-4 and mechanical seal 1-6, and the supergravity equipment has rotor with specific structure rotating in the casing at high speed, gas phase entering the casing from the radial gas inlet and entering the rotor from the outer edge of the rotor, liquid phase entering the center of the rotor from the axial liquid inlet and being distributed by the liquid distributor, and gas-liquid two phases forming gas-liquid interface with great specific surface area inside the rotor. Finally, the gas phase leaves the bed body through an axial gas outlet; the liquid phase is collected in the shell and then is led out from the radial liquid outlet.
When the production device is started, the hypergravity reactor 1, the injection reactor 2 and the ester exchange 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 internal heating tube bundle to heat materials until the whole production device normally operates; after normal operation, cooling water is introduced into jackets of the hypergravity reactor 1 and the injection reactor 2 to control the reaction temperature, secondary steam is used as an auxiliary heat source for the ester exchange reaction kettle 5, when the secondary steam is insufficient, the public engineering steam is also used as an auxiliary heat source for the ester exchange reaction kettle 5, and the reaction liquid of the hypergravity reactor 1 is used as a heat source for the distillation kettle 4; the devices of the invention are connected by corresponding pipelines, and the pipelines in the figure 1 are drawn according to the principle of vertical and horizontal intersecting when intersecting on the figure but not actually intersecting.
Example 2
The dimethyl carbonate production method based on the device in the embodiment 1 comprises the following steps:
(1) feedstock CO2Recovered for light-burned magnesia, CO299.9% by volume, 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 PO and CO2The molar ratio of 1:1.3, the amount of catalyst I used is 2% (based on the total mass of the raw materials); 1742.400kg/hPO liquid, 1716.371kg/h CO2The gas, 69.168kg/h fresh liquid catalyst I and recovered liquid catalyst I continuously and axially enter a liquid distributor 1-4 in the hypergravity reactor 1, and CO2The filler 1-3 radially enters the high-gravity reactor 1 through the high-gravity reactor 1, and the liquid and the gas perform addition reaction in the rotor 1-2;
(2) the reaction temperature of the injection reactor 2 is 195 ℃, the pressure is 6.0MPa, and the addition reaction time is 1 h; the reaction liquid discharged from the hypergravity reactor 1 is heated by a discharge pump 1-5 to a distillation kettle 4, continuously enters a jet reactor power fluid pump 2-3 after being cooled, enters a jet stirrer coupling distributor 2-1, and simultaneously sucks in PO and CO gas discharged from the hypergravity reactor 12And the addition reaction is continued through a jet mixer ejector 2-2.
(3) The temperature of the intermediate tank is 140 ℃, the pressure is 0.20MPa, and the retention time is 2 h; continuously feeding the reaction liquid of the injection reactor 2 into 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 passes through a gas-liquid separation tank 3-1 to separate PO and CO2Entering an exhaust gas treatment system; the liquid PC separated from the gas-liquid separation tank 3-1 enters the intermediate tank 3.
(4) The temperature of the distillation kettle 4 is 150 ℃, the vacuum degree is-0.095 MPa, and the fraction at 140 ℃ is collected; liquid PC in the middle tank 3 continuously enters a distillation kettle 4, the distilled PC is cooled by a condenser 4-1 and enters a PC tank 4-2, and the liquid in the PC tank 4-2 continuously enters an ester exchange reaction kettle 5 by a PC pump 4-3; liquid catalyst I is extracted from the bottom of the distillation kettle 4 and enters a catalyst I recovery tank 4-5 through a distillation kettle bottom pump 4-4, and the recovered catalyst I continuously enters the supergravity reactor 1 through a catalyst I recovery pump 4-6.
(5) The temperature of the ester exchange reaction kettle 5 is 75 ℃, the temperature of the top of the distillation tower is 64 ℃, the reflux ratio is 3, the pressure is normal pressure, and the retention time is 2 hours; the molar ratio of MA to PC is 4:1, and the dosage of the catalyst II is 0.1 percent of the total mass of the materials; 2956.322kg/h of liquid PC in a PC tank 4-2, fresh liquid catalyst II, catalyst II recovered by a supergravity rectifying machine II7 and liquid in the kettle continuously enter a liquid inlet of a jet stirrer coupling distributor 5-1 of a transesterification reaction kettle 5, MA steam, DMC steam recovered by a supergravity rectifying machine I6, MA steam and DMC steam recovered by a lightness-removing column 5-9, fresh vaporized MA is driven by a jet stirrer power fluid pump 5-3 to be continuously sucked into a gas inlet of the coupling distributor 5-1 to enter the transesterification reaction kettle 5 for transesterification reaction, the total amount of MA is 3711.257kg/h, and the total amount of catalyst II is 7.668 kg/h; the light components (MA, DMC) distilled from the ester exchange 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 ester exchange 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 distillation temperature is 137 ℃, the pressure is 1.0MPa, the reflux ratio is 2, and the hypergravity factor is 40; the adoption of the supergravity rectification improves the contact specific surface area and the mass transfer and heat transfer rate of vapor-liquid interphase, greatly reduces the size of equipment, has very high mass transfer efficiency, is difficult to flood, resists pressure and saves energy; the crude DMC continuously enters the top of a hypergravity rectifying machine I6 through a crude DMC pump 5-6, fine DMC from a fine DMC pump 6-8 is arranged at the top of the hypergravity rectifying machine I6 and serves as reflux, MA and DMC distilled from the top enter a buffer tank 6-9, vapor is recompressed (MVR) through a compressor 6-5 mechanical vapor, namely secondary vapor with the pressure increased and the temperature increased by the compressor provides an auxiliary heat source for the ester exchange reaction; absorbing the MA steam and the DMC steam after temperature and pressure increase into the ester exchange reaction kettle 5 for ester exchange reaction through a jet stirrer coupling distributor 5-1 of the ester exchange reaction kettle 5; extracting fine DMC from the lower part of a 6-6 reboiler of the supergravity rectifying machine I6;
(7) the temperature of the hypergravity rectifying machine 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 supergravity rectification improves the contact specific surface area and the mass transfer and heat transfer rate of vapor-liquid interphase, greatly reduces the size of equipment, has very high mass transfer efficiency, is difficult to flood, resists pressure and saves energy; crude 1,2-PG in a 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 components MA steam and DMC steam enter a compressor 6-5, and secondary steam heated through Mechanical Vapor Recompression (MVR) provides an auxiliary heat source for ester exchange reaction; absorbing the MA and DMC steam after temperature and pressure increase into an ester exchange reaction kettle 5 through an ester exchange reaction kettle 5 jet stirrer coupling distributor 5-1 to perform ester exchange reaction; heavy components at the lower part of a reboiler 5-10 of the light component removal tower continuously enter the top of a supergravity rectifying machine II7, and the top of a supergravity rectifying machine II7 is provided with fine 1,2-PG from a fine 1,2-PG pump 7-7 as reflux; the refined 1,2-PG extracted from the top of the supergravity rectifying machine II7 enters a refined 1,2-PG tank 7-6 after being cooled by a condenser 7-5, and part of the refined 1,2-PG flows through a refined 1,2-PG pump 7-7 to be used as the top reflux of the supergravity rectifying machine II7, and part of the refined 1,2-PG is extracted; PC, 1,2-PG and catalyst II are extracted from the lower part of a reboiler 7-8 of the supergravity rectifying machine II7 and enter a catalyst II recovery tank 7-9, and are returned to the ester exchange reaction kettle 5 through a catalyst II recovery pump 7-10 and are coupled with a distributor 5-1 through a jet stirrer for carrying out ester exchange reaction. The dimethyl carbonate and the 1, 2-propylene glycol are packaged and delivered out of a factory after being barreled.
Example 3
The dimethyl carbonate production method based on the device in the embodiment 1 comprises the following steps:
a dimethyl carbonate production method based on resource utilization comprises the following steps:
(1) feedstock CO2Recovered for light-burned magnesia, CO299.9% by volume, 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, PO and CO2The molar ratio of 1:1.5, the amount of the catalyst I is 1% (based on the total mass of the raw materials); 1742.400kg/hPO liquid, 1980.428kg/hCO2The gas, 37.229kg/h fresh liquid catalyst I and recovered liquid catalyst I continuously and axially enter a liquid distributor 1-4 in the hypergravity reactor 1, and CO2The filler 1-3 radially enters the high-gravity reactor 1 through the high-gravity reactor 1, and the liquid and the gas perform addition reaction in the rotor 1-2;
(2) the reaction temperature of the injection reactor 2 is 200 ℃, the pressure is 6.5MPa, and the addition reaction time is 0.9 h; the reaction liquid discharged from the hypergravity reactor 1 is heated by a discharge pump 1-5 to a distillation kettle 4, continuously enters a jet reactor power fluid pump 2-3 after being cooled, enters a jet stirrer coupling distributor 2-1, and simultaneously sucks in PO and CO gas discharged from the hypergravity reactor 12And the addition reaction is continued through a jet mixer ejector 2-2.
(3) The temperature of the intermediate tank is 145 ℃, the pressure is 0.25MPa,the retention time is 2.5 h; continuously feeding the reaction liquid of the injection reactor 2 into 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 passes through a gas-liquid separation tank 3-1 to separate PO and CO2Entering an exhaust gas treatment system; the liquid PC separated from the gas-liquid separation tank 3-1 enters the intermediate tank 3.
(4) The temperature of the distillation kettle 4 is 155 ℃, the vacuum degree is-0.098 MPa, and 135 ℃ fractions are collected; liquid PC in the middle tank 3 continuously enters a distillation kettle 4, the distilled PC is cooled by a condenser 4-1 and enters a PC tank 4-2, and the liquid in the PC tank 4-2 continuously enters an ester exchange reaction kettle 5 by a PC pump 4-3; liquid catalyst I is extracted from the bottom of the distillation kettle 4 and enters a catalyst I recovery tank 4-5 through a distillation kettle bottom pump 4-4, and the recovered catalyst I continuously enters the supergravity reactor 1 through a catalyst I recovery pump 4-6.
(5) The temperature of the ester exchange reaction kettle 5 is 78 ℃, the temperature of the top of the distillation tower is 66 ℃, the reflux ratio is 4, the pressure is normal pressure, and the retention time is 1.5 h; the molar ratio of MA to PC is 4.4:1, and the dosage of the catalyst II is 0.05 percent of the total mass of the materials; 2956.322kg/h of liquid PC in a PC tank 4-2, fresh liquid catalyst II, catalyst II recovered by a supergravity rectifying machine II7 and liquid in the kettle continuously enter a liquid inlet of a jet stirrer coupling distributor 5-1 of a transesterification reaction kettle 5, MA steam, DMC steam recovered by a supergravity rectifying machine I6, MA steam and DMC steam recovered by a lightness-removing column 5-9, fresh vaporized MA is driven by a jet stirrer power fluid pump 5-3 to be continuously sucked into a gas inlet of the coupling distributor 5-1 to enter the transesterification reaction kettle 5 for transesterification reaction, the total amount of MA is 3711.257kg/h, and the total amount of catalyst II is 3.834 kg/h; the light components (MA, DMC) distilled from the ester exchange 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 ester exchange 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 distillation temperature is 139 ℃, the pressure is 1.02MPa, the reflux ratio is 2.2, and the hypergravity factor is 41; the adoption of the supergravity rectification improves the contact specific surface area and the mass transfer and heat transfer rate of vapor-liquid interphase, greatly reduces the size of equipment, has very high mass transfer efficiency, is difficult to flood, resists pressure and saves energy; the crude DMC continuously enters the top of a hypergravity rectifying machine I6 through a crude DMC pump 5-6, fine DMC from a fine DMC pump 6-8 is arranged at the top of the hypergravity rectifying machine I6 and serves as reflux, MA and DMC distilled from the top enter a buffer tank 6-9, vapor is recompressed (MVR) through a compressor 6-5 mechanical vapor, namely secondary vapor with the pressure increased and the temperature increased by the compressor provides an auxiliary heat source for the ester exchange reaction; absorbing the MA steam and the DMC steam after temperature and pressure increase into the ester exchange reaction kettle 5 for ester exchange reaction through a jet stirrer coupling distributor 5-1 of the ester exchange reaction kettle 5; extracting fine DMC from the lower part of a 6-6 reboiler of the supergravity rectifying machine I6;
(7) the temperature of the hypergravity rectifying machine 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 supergravity rectification improves the contact specific surface area and the mass transfer and heat transfer rate of vapor-liquid interphase, greatly reduces the size of equipment, has very high mass transfer efficiency, is difficult to flood, resists pressure and saves energy; crude 1,2-PG in a 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 components MA steam and DMC steam enter a compressor 6-5, and secondary steam heated through Mechanical Vapor Recompression (MVR) provides an auxiliary heat source for ester exchange reaction; absorbing the MA and DMC steam after temperature and pressure increase into an ester exchange reaction kettle 5 through an ester exchange reaction kettle 5 jet stirrer coupling distributor 5-1 to perform ester exchange reaction; heavy components at the lower part of a reboiler 5-10 of the light component removal tower continuously enter the top of a supergravity rectifying machine II7, and the top of a supergravity rectifying machine II7 is provided with fine 1,2-PG from a fine 1,2-PG pump 7-7 as reflux; the refined 1,2-PG extracted from the top of the supergravity rectifying machine II7 enters a refined 1,2-PG tank 7-6 after being cooled by a condenser 7-5, and part of the refined 1,2-PG flows through a refined 1,2-PG pump 7-7 to be used as the top reflux of the supergravity rectifying machine II7, and part of the refined 1,2-PG is extracted; PC, 1,2-PG and catalyst II are extracted from the lower part of a reboiler 7-8 of the supergravity rectifying machine II7 and enter a catalyst II recovery tank 7-9, and are returned to the ester exchange reaction kettle 5 through a catalyst II recovery pump 7-10 and are coupled with a distributor 5-1 through a jet stirrer for carrying out ester exchange reaction. The dimethyl carbonate and the 1, 2-propylene glycol are packaged and delivered out of a factory after being barreled.
In the dimethyl carbonate production method based on resource utilization, the device can save energy by 50% comprehensively; the quality of the dimethyl carbonate is higher than the standard of GB/T33107-2016 premium grade products, and the quality of the 1, 2-propylene glycol is higher than the standard of HG/T5392-2018 premium grade products.
The technical idea of the present invention is described in the above technical solutions, and the protection scope of the present invention is not limited thereto, and any changes and modifications made to the above technical solutions according to the technical essence of the present invention belong to the protection scope of the technical solutions of the present invention.
Claims (10)
1. The utility model provides a dimethyl carbonate apparatus for producing based on resource utilization which characterized in that: a dimethyl carbonate production device based on resource utilization comprises a hypergravity reactor, a jet reactor, a middle tank, a distillation still, an ester exchange reaction still and a hypergravity rectifying machine I which are connected in sequence; high gravity reactor for raw materials PO and CO2The jet reactor is used for continuously carrying out addition reaction on reaction liquid, liquid PC enters an intermediate tank after gas-liquid separation of the addition reaction liquid, a distillation kettle is used for distilling the liquid PC, the distilled PC enters an ester exchange reaction kettle after being cooled, the ester exchange reaction kettle is used for carrying out ester exchange reaction, light components distilled from the ester exchange reaction kettle enter a hypergravity rectifying machine I, and the rectified DMC is obtained after rectification; wherein, the stirrers arranged in the jet reactor and the ester exchange 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 ester exchange reaction kettle, and MA vapor and DMC vapor removed from the hypergravity rectifying machine I enter the ester exchange reaction kettle after being boosted and heated by the vapor compressor.
2. The dimethyl carbonate production device based on resource utilization according to claim 1, characterized in that: 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 injection reactor; the device still includes catalyst I recovery tank, and distillation still, hypergravity reactor 1 are connected respectively to catalyst I recovery tank both ends, catalyst I recovery tank is used for collecting the liquid catalyst I who adopts at the bottom of the distillation still, and the catalyst I who retrieves reentrants hypergravity reactor 1 catalytic addition reaction.
3. The dimethyl carbonate production device based on resource utilization according to claim 1, characterized in that: the device also comprises a light component removal tower, a hypergravity rectifying machine II and a catalyst II recovery tank; heavy components at the lower part of the ester exchange reaction kettle enter a light component removal 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 hypergravity rectifying machine II7 for rectifying 1,2-PG, the catalyst II extracted at the lower part of the hypergravity rectifying machine II enters a catalyst II recovery tank, and the recovered catalyst II is input into an ester exchange reaction kettle for catalyzing ester exchange reaction.
4. A method for producing dimethyl carbonate based on the apparatus of any one of claims 1 to 3, characterized in that: the method specifically comprises the following steps:
(1) raw materials PO, CO2The catalyst I enters a supergravity reactor to carry out addition reaction;
(2) reaction liquid discharged from the hypergravity reactor enters the jet reactor, and gas discharged from the hypergravity reactor is sucked for continuous addition reaction;
(3) liquid PC separated from addition reaction liquid of the injection reactor after gas-liquid separation enters an intermediate tank;
(4) the liquid PC in the intermediate tank enters a distillation kettle, and the distilled PC enters an ester exchange reaction kettle after being cooled;
(5) liquid PC in a PC tank, a catalyst II and a coupling distributor liquid inlet of a jet stirrer entering an ester exchange reaction kettle, MA steam and DMC steam of a steam compressor and fresh vaporized MA enter a gas inlet of the coupling distributor, and ester exchange reaction is carried out in the ester exchange reaction kettle; cooling the light component distilled from the ester exchange reaction kettle, and then feeding the light component into a crude DMC tank;
(6) feeding the crude DMC in the crude DMC tank into a fractionating column of an ester exchange reaction kettle and a hypergravity rectifying machine I, and feeding MA steam and DMC steam distilled from the top of the hypergravity rectifying machine I into a steam compressor; and extracting fine DMC from the lower part of a reboiler I of the hypergravity rectifying machine.
5. The process for producing dimethyl carbonate according to claim 4, wherein: the method also comprises a step (7), heavy components at the lower part of the ester exchange reaction kettle continuously enter a crude 1,2-PG tank, crude 1,2-PG in the crude 1,2-PG tank continuously enters a light component removal tower through a crude 1,2-PG pump, removed light component MA steam and DMC steam enter a steam compressor, heavy components at the lower part of a reboiler of the light component removal tower continuously enter the top of a supergravity rectifying machine II, refined 1 is extracted from the top of the supergravity rectifying machine II, 2-PG is cooled by a condenser and enters a refined 1,2-PG tank, and refined 1,2-PG is partially taken as the top reflux of the supergravity rectifying machine II through a refined 1,2-PG pump and is partially extracted; and (3) extracting PC, 1,2-PG and catalyst II from the lower part of a reboiler of the hypergravity rectifying machine II, feeding the obtained product into a catalyst II recovery tank, and returning the obtained product to an ester exchange reaction kettle through a catalyst II recovery pump to perform ester exchange reaction.
6. The process for producing dimethyl carbonate according to claim 5, wherein: feedstock CO2Recovered for light-burned magnesia, CO2The volume content is 99.9 percent, PO is industrial product PO, MA is industrial product MA, and the catalyst I, II is an ionic liquid catalyst; the hypergravity reactor, the injection reactor, the ester exchange reaction kettle, the hypergravity rectifying machine I and the hypergravity rectifying machine II adopt jacket heat exchange, and public engineering steam adopted for heat exchange is backpressure steam with the temperature of 230 ℃ and 0.4MPa of a self-contained power plant; the utility steam mainly provides heat sources for the hypergravity rectifying machine I, the hypergravity rectifying machine II and the lightness-removing tower, and also provides auxiliary heat sources for the hypergravity reactor, the jet reactor and the distillation kettle 4 for driving and provides an auxiliary heat source for the ester exchange reaction kettle 5; the hypergravity reactor hot stream can provide a main heat source for the distillation still 4; MA and DMC steam enters a steam compressor, and is subjected to Mechanical Vapor Recompression (MVR), namely, the pressure of the compressor is increased, the temperature is increased, the secondary steam becomes secondary steam, the temperature of the secondary steam is 170 ℃, the pressure of the secondary steam is superheated steam of 0.15MPa, and the secondary steam can provide an auxiliary heat source for the ester exchange reaction kettle.
7. The process for producing dimethyl carbonate according to claim 4, wherein: the addition of the supergravity reactor in the step (1)The reaction temperature is 190-195 ℃, the pressure is 6.5-7.0 MPa, the reaction time is 0.1-0.2 h, and PO and CO2The molar ratio of the catalyst I to the reaction solution is 1: 1.3-1: 1.5, and the amount of the catalyst I is 1-2% of the total mass of the raw materials; the reaction temperature of the injection reactor 2 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 high-gravity reactor is heated by a discharge pump to a distillation kettle, and continuously enters a jet reactor after being cooled, and simultaneously, PO and CO gases discharged from the high-gravity reactor are sucked2The addition reaction was continued.
8. The process 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 retention time is 2-2.5 h; continuously feeding the reaction liquid of the injection reactor into a turbine to drive a generator to generate electricity and recover pressure energy; separating PO and CO from the addition reaction liquid from the turbine through a gas-liquid separation tank2Entering an exhaust gas treatment system; liquid PC separated by the gas-liquid separation tank enters an intermediate tank; the temperature of the distillation kettle in the step (4) is 150-155 ℃, the vacuum degree is-0.095 MPa-0.098 MPa, and the fraction at 135-140 ℃ is collected; the liquid PC in the intermediate tank continuously enters a distillation kettle, the 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; liquid catalyst I is extracted from the bottom of the distillation kettle and enters a catalyst I recovery tank through a distillation kettle bottom pump, and the recovered catalyst I continuously enters the supergravity reactor through a catalyst I recovery pump.
9. The process for producing dimethyl carbonate according to claim 4, wherein: the temperature of the ester exchange reaction kettle 5 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 retention 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 distillation 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, fine DMC from a fine DMC pump is arranged at the top of the hypergravity rectifying machine I and serves as reflux, MA and DMC distilled from the top enter a buffer tank, and then enter steam and pass through a compressor.
10. The process for producing dimethyl carbonate according to claim 4, wherein: the temperature of the hypergravity rectifying machine II in the step (7) is 180-185 ℃, the distillation temperature is 130-132 ℃, the vacuum degree is-0.095 MPa-0.090 MPa, the reflux ratio is 1.5-1.6, and the hypergravity 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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| CN202111163590.6A CN113731320B (en) | 2021-09-30 | 2021-09-30 | Dimethyl carbonate production device and method based on resource utilization |
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