WO2022110871A1 - 一种草酸酯法制备乙二醇的强化微界面反应系统及方法 - Google Patents

一种草酸酯法制备乙二醇的强化微界面反应系统及方法 Download PDF

Info

Publication number
WO2022110871A1
WO2022110871A1 PCT/CN2021/109739 CN2021109739W WO2022110871A1 WO 2022110871 A1 WO2022110871 A1 WO 2022110871A1 CN 2021109739 W CN2021109739 W CN 2021109739W WO 2022110871 A1 WO2022110871 A1 WO 2022110871A1
Authority
WO
WIPO (PCT)
Prior art keywords
micro
reaction tank
interface generator
interface
generator
Prior art date
Application number
PCT/CN2021/109739
Other languages
English (en)
French (fr)
Inventor
张志炳
周政
李磊
张锋
孟为民
王宝荣
杨高东
罗华勋
田洪舟
杨国强
曹宇
Original Assignee
南京延长反应技术研究院有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 南京延长反应技术研究院有限公司 filed Critical 南京延长反应技术研究院有限公司
Publication of WO2022110871A1 publication Critical patent/WO2022110871A1/zh

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • 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
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to the field of ethylene glycol preparation, in particular to an enhanced micro-interface reaction system and method for preparing ethylene glycol by an oxalate method.
  • Ethylene Glycol also known as glycol
  • glycol is an important petrochemical organic raw material.
  • the chemical reaction of ethylene glycol is similar to that of monohydric alcohol, and it can carry out many typical reactions of alcohols, such as esterification reaction, dehydration reaction, etherification reaction, etc.
  • the reaction products are mainly used in the production of polyester fibers and polyester plastics, etc., and are widely used in It is used in the production of lubricants, plasticizers, non-ionic surfactants and explosives, etc., and can be directly used as antifreeze and formulated engine coolant.
  • the first is a direct synthesis process
  • the second is a synthesis using methanol and formaldehyde
  • the third is an oxalate synthesis process.
  • the production of ethylene glycol by the oxalate method adopts a self-closed circulation method, and the whole reaction process is relatively mild, and the catalyst in it has the characteristics of good stability and low consumption, and has little impact on the environment.
  • Ethylene glycol produced by oxalate method is of higher quality than the other two methods.
  • the technology for preparing ethylene glycol by oxalate method is not mature enough, and there are still some related technical problems.
  • the first object of the present invention is to provide an enhanced micro-interface reaction system for preparing ethylene glycol by oxalate method.
  • the reaction system is provided with a hydraulic micro-interface generator inside the first reaction tank and a micro-interface generator on the top.
  • a micro-interface generator is placed below, and a first split-flow micro-interface generator and a first liquid reciprocal micro-interface generator are arranged in the second reaction tank, so that nitric oxide, oxygen and methanol are broken and dispersed into micro-bubbles, improving the The mass transfer area of the phase boundary between nitric oxide, oxygen and methanol, thus solving the problem that nitric oxide, oxygen and methanol cannot be fully mixed in the first reaction tank in the prior art, resulting in high reaction pressure, high reaction temperature and The problem of low liquid hourly space velocity improves the reaction efficiency.
  • a second liquid reciprocal micro-interface generator is arranged in the first hydrogenation reaction tank, and a second gas split is arranged in the second hydrogenation reaction tank.
  • the micro-interface generator and hydrogenation micro-interface generator break and disperse the incoming hydrogen into micro-bubbles, and disperse into the solvent and catalyst to form a micro-interface system, which increases the gas-liquid interface area in the reaction gas and liquid, and greatly improves the The rate of mass transfer from the gas phase to the liquid phase.
  • the second object of the present invention is to provide a reaction method for preparing ethylene glycol using the above reaction system.
  • the method is easy to operate, the obtained ethylene glycol has high purity and high product quality, and is worthy of widespread application.
  • An enhanced micro-interface reaction system for preparing ethylene glycol by an oxalate method comprising: a first reaction tank, a second reaction tank, a hydraulic micro-interface generator, an upper micro-interface generator, a lower micro-interface generator, The first split-flow type micro-interface generator, the first liquid reciprocal micro-interface generator, the first hydrogenation reaction tank, the second hydrogenation reaction tank, the second liquid reciprocal micro-interface generator, the second split-flow type micro-interface generator generator and hydrogenation micro-interface generator;
  • the first reaction tank and the second reaction tank are connected in parallel, the side wall of the first reaction tank is provided with a nitrogen oxide inlet pipe and an oxygen inlet pipe, and the oxygen inlet pipe is connected with the hydraulic micro-interface
  • the generator and the upper micro-interface generator, the nitric oxide inlet pipe is connected to the lower micro-interface generator through the first reaction tank;
  • the side wall of the second reaction tank is provided with oxygen an intake pipe and a nitric oxide intake pipe, the oxygen intake pipe is connected with the first split-flow micro-interface generator, and the nitric oxide intake pipe is connected with the first liquid reciprocal micro-interface generator
  • the first reaction tank and the second reaction tank are connected with a methanol storage tank, and the methanol storage tank transports methanol to the hydraulic micro-interface generator and the second reaction tank;
  • the first hydrogenation reaction tank and the second hydrogenation reaction tank are connected in parallel, the first hydrogenation reaction tank is provided with a second liquid reciprocal micro-interface generator, and the second liquid reciprocal micro-interface generates
  • the second hydrogenation reaction tank is connected with the hydrogen compressor for breaking and dispersing the hydrogen into microbubbles.
  • the second split-flow micro-interface generator and the hydrogenation micro-interface generator are arranged inside the second hydrogenation reaction tank.
  • the invention provides a new type of reaction system.
  • a hydraulic micro-interface generator is arranged in the first reaction tank to break and disperse the oxygen into micro-bubbles, and the oxygen, methanol and a Phase boundary mass transfer area between nitrogen oxides;
  • the liquid-dynamic micro-interface generator is connected with a gas-liquid separation tank, and the nitric oxide separated from the top of the gas-liquid separation tank returns to the liquid-dynamic micro-interface generator, and nitric oxide and oxygen are in liquid
  • the reaction occurs in the dynamic micro-interface generator and disperses into micro-bubbles, which increases the mass transfer area of the phase boundary between oxygen, methanol and nitric oxide, and at the same time uses the recovered nitric oxide to save costs;
  • the interface generator is connected with a methanol storage tank, and the methanol storage tank delivers methanol to the hydraulic micro-interface generator.
  • the hydraulic micro-interface generator increases the flow rate of methanol, and the methanol carries the micro-bubbles in the hydraulic micro-interface generator downward. Hedges with the oxygen micro-bubbles generated in the upper micro-interface generator and the nitric oxide micro-bubbles generated in the lower micro-interface generator, because the hydraulic micro-interface generator and the upper micro-interface generator are installed in the first reaction tank.
  • the generator and the lower micro-interface generator increase the mass transfer area of the phase boundary between oxygen, methanol and nitric oxide, and speed up the methanol flow rate in the first reaction tank, thereby increasing the reaction of methyl nitrite. rate.
  • a first split-flow micro-interface generator is arranged in the second reaction tank to break up and disperse oxygen into oxygen micro-bubbles, and distribute the oxygen micro-bubbles to all parts of the second reaction tank, so that the oxygen can be dispersed more efficiently. It increases the mass transfer area of the phase boundary between oxygen, methanol and nitric oxide; a first liquid reciprocal micro-interface generator is arranged in the second reaction tank, and the liquid reciprocal micro-interface generator is located in the adjacent micro-interface.
  • Liquid reciprocal channels are arranged between the interfaces, and two liquid reciprocal channels are preferably arranged symmetrically on the left and right, because the mutual flow of liquid between each micro-interface generator can improve the crushing and dispersion of nitric oxide, because Fragmentation requires power.
  • the liquid reciprocal channels also cooperate to provide power. The best way is that the liquid flow directions of the two liquid reciprocal channels are exactly opposite. Therefore, convection can also be generated between the various micro-interface generators, and the effect of crushing can be improved.
  • the flow rate in the second reaction tank increases, and the phase between oxygen, methanol and nitric oxide increases.
  • the mass transfer area increases, which increases the reaction rate of methyl nitrite.
  • the second liquid reciprocal micro-interface generator is arranged in the first hydrogenation reaction tank, because the mutual flow of liquid between each micro-interface generator can improve the fragmentation and dispersion of hydrogen, and increase the The mass transfer area of the phase boundary between hydrogen and dimethyl oxalate makes the reaction between hydrogen and dimethyl oxalate sufficient and improves the reaction efficiency; in this reaction system, a second split-flow micro-channel is set in the second hydrogenation reaction tank. The interface generator is used to break up and disperse the hydrogen.
  • the specific structure of the shunt-type micro-interface generator is that a plurality of shunt channels are arranged on the body of the micro-interface generator, and the shunt channels are preferably curved and arranged at the outlet of the shunt-type micro-interface generator.
  • the generated hydrogen microbubbles are more widely dispersed and the reaction effect is improved, so it can be seen that the invention combines the micro-interface generator with the shunt channel creatively to improve the reaction effect of the shunt-type micro-interface generator.
  • the reason why the present invention sets the first hydrogenation reaction tank and the second hydrogenation reaction tank in parallel and operates at the same time is to increase the processing capacity and correspondingly improve the reaction efficiency.
  • the hydraulic micro-interface generator, the upper micro-interface generator and the lower micro-interface generator are arranged in order from top to bottom in the first reaction tank, and the hydraulic micro-interface generator
  • the generator is arranged on the top of the first reaction tank, the lower micro-interface generator is arranged at the bottom of the first reaction tank, and the upper micro-interface generator is arranged on the lower micro-interface generator
  • the first split-flow micro-interface generator is arranged at the top of the second reaction tank, and the first liquid reciprocal micro-interface generator is arranged at the bottom of the second reaction tank.
  • the reason why the hydraulic micro-interface generator is arranged on the top of the first reaction tank is to entrain the gas remaining at the top of the first reaction tank by using the liquid phase as the power to ensure full utilization of the gas.
  • the micro-interface generator and the bottom micro-interface generator are fully reacted in the first reaction tank after dispersing and breaking through different gas phases.
  • the arrangement from top to bottom also enhances the interaction between the gases, which can not only generate hedging but also Because the distance is closer, the interaction can occur better.
  • the hydraulic micro-interface generator, the upper micro-interface generator and the lower micro-interface generator of the present invention are arranged in sequence from top to bottom with the central axis of the first reaction tank as the center, and the hydraulic micro-interface generator is connected with methanol, Nitric oxide and oxygen are connected, and the oxygen and nitric oxide are broken and dispersed into microbubbles, which improves the mass transfer area of the phase boundary between oxygen, nitric oxide and methanol.
  • the hydraulic micro-interface generator sprays methanol and oxygen micro-bubbles into the solvent from top to bottom by means of pressurization, which speeds up the reaction rate.
  • the interface generator forms nitric oxide microbubbles, which increases the gas-liquid interface area, thereby increasing the production rate of methyl nitrite.
  • the rising speed of oxygen in the solvent is higher than that of nitric oxide.
  • the rising speed of nitric oxide in the solvent is slow, so the oxygen is connected to the upper micro-interface generator, and the nitric oxide is connected to the lower micro-interface generator.
  • the rising speed of oxygen is slower than the rising speed of nitric oxide, which increases oxygen, The reaction time between nitric oxide and methanol, thereby improving the production efficiency of methyl nitrite.
  • the reason why the first split-flow micro-interface generator is arranged on the top of the second reaction tank is firstly to facilitate the collection of nitric oxide returned from the regeneration tower and to break and disperse it into nitric oxide microbubbles, and secondly to facilitate the collection of Nitrogen oxide collides downward with the oxygen and nitric oxide microbubbles generated by the crushing and dispersion of the upper and lower micro-interfaces, and collides with the top of the second reaction tank, so that the unreacted gas at the top is dispersed, so that the first reaction tank can be dispersed.
  • the internal response is more adequate.
  • the second liquid reciprocal micro-interface generator is arranged at the bottom of the first hydrogenation reaction tank; the second split-flow micro-interface generator is arranged at the top of the second hydrogenation reaction tank, The hydrogenation micro-interface generator is arranged at the bottom of the second hydrogenation reaction tank.
  • the reason why the second liquid reciprocal micro-interface generator and the hydrogenation micro-interface generator are respectively arranged at the bottom of the first hydrogenation reaction tank and the second hydrogenation reaction tank is because the density of hydrogen is small and the rising speed in the solvent is fast.
  • the second liquid reciprocal micro-interface generator and hydrogenation micro-interface generator are respectively arranged at the bottom of the first hydrogenation reaction tank and the second hydrogenation reaction tank, The rising distance of hydrogen from the bottom to the top is increased, thereby increasing the reaction time between hydrogen and dimethyl oxalate, and improving the rate of hydrogen catalyzing dimethyl oxalate to generate ethylene glycol.
  • first split-flow micro-interface generators there are two first split-flow micro-interface generators in the second reaction tank.
  • the setting direction of the shunt channel of the first shunt-type micro-interface generator located at the upper part of the second reaction tank is upward, and the setting direction of the shunt channel of the first shunt-type micro-interface generator located at the lower part is upward. face down.
  • the distributive channel of the second split-flow-type micro-interface generator in the second hydrogenation reaction tank is arranged in a downward direction.
  • both the second split-flow micro-interface generator and the hydrogenation micro-interface generator are connected to the hydrogen compressor to break up and disperse the hydrogen into microbubbles.
  • micro-interface generator used in the present invention has been embodied in the inventor's prior patents, such as application numbers CN201610641119.6, CN201610641251.7, CN201710766435.0, CN106187660, CN105903425A, Patents of CN109437390A, CN205833127U and CN207581700U.
  • application numbers CN201610641119.6, CN201610641251.7, CN201710766435.0, CN106187660, CN105903425A, Patents of CN109437390A, CN205833127U and CN207581700U In the previous patent CN201610641119.6, the specific product structure and working principle of the micro-bubble generator (that is, the micro-interface generator) were introduced in detail.
  • the body is provided with an inlet communicating with the cavity, the opposite first and second ends of the cavity are open, wherein the cross-sectional area of the cavity is from the middle of the cavity to the first and second ends of the cavity.
  • the second end is reduced; the secondary crushing piece is arranged at at least one of the first end and the second end of the cavity, a part of the secondary crushing piece is arranged in the cavity, and both ends of the secondary crushing piece and the cavity are open
  • An annular channel is formed between the through holes of the micro-bubble generator.
  • the micro-bubble generator also includes an air inlet pipe and a liquid inlet pipe.” From the specific structure disclosed in the application document, we can know that its specific working principle is: the liquid enters the micron tangentially through the liquid inlet pipe. In the bubble generator, ultra-high-speed rotation and cutting of the gas make the gas bubbles break into micro-bubbles at the micron level, thereby increasing the mass transfer area between the liquid phase and the gas phase, and the micro-bubble generator in this patent belongs to the pneumatic micro-interface generation. device.
  • the previous patent 201610641251.7 records that the primary bubble breaker has a circulating liquid inlet, a circulating gas inlet and a gas-liquid mixture outlet, and the secondary bubble breaker communicates the feed port with the gas-liquid mixture outlet, indicating that the bubble breaker is both It needs to be mixed with gas and liquid.
  • the primary bubble breaker mainly uses circulating liquid as power, so in fact, the primary bubble breaker belongs to the hydraulic micro-interface generator, and the secondary bubble breaker is a gas-liquid breaker. The mixture is simultaneously fed into the elliptical rotating ball for rotation, so that the bubbles are broken during the rotation, so the secondary bubble breaker is actually a gas-liquid linkage type micro-interface generator.
  • both hydraulic micro-interface generators and gas-liquid linkage micro-interface generators belong to a specific form of micro-interface generators.
  • the micro-interface generators used in the present invention are not limited to the above-mentioned forms.
  • the specific structure of the bubble breaker described in the prior patent is only one of the forms that the micro-interface generator of the present invention can take.
  • the previous patent 201710766435.0 records that "the principle of the bubble breaker is to achieve high-speed jets to achieve gas collision", and it is also stated that it can be used in micro-interface enhanced reactors to verify the relationship between the bubble breaker and the micro-interface generator.
  • the prior patent CN106187660 also has related records for the specific structure of the bubble breaker, see the specific description in paragraphs [0031]-[0041], and the accompanying drawings, which are related to the bubble breaker S-2 The specific working principle of the bubble breaker is explained in detail.
  • the top of the bubble breaker is the liquid phase inlet, and the side is the gas phase inlet.
  • the liquid phase entering from the top provides the entrainment power, so as to achieve the effect of crushing into ultra-fine bubbles, which can also be seen in the accompanying drawings.
  • the bubble breaker has a conical structure, and the diameter of the upper part is larger than that of the lower part, so that the liquid phase can provide better entrainment power.
  • micro-interface generator Since the micro-interface generator was just developed in the early stage of the previous patent application, it was named as micro-bubble generator (CN201610641119.6), bubble breaker (201710766435.0), etc., and later changed its name to micro-interface generator with continuous technological improvement.
  • the micro-interface generator in the present invention is equivalent to the previous micro-bubble generator, bubble breaker, etc., but the names are different. To sum up, the micro-interface generator of the present invention belongs to the prior art.
  • the present invention also provides a method for preparing ethylene glycol by an oxalate method, comprising the following steps:
  • Nitric oxide, oxygen and methanol micro-interfaces are broken and dispersed to react to obtain methyl nitrite;
  • Methyl nitrite and carbon monoxide are coupled to form dimethyl oxalate
  • Dimethyl oxalate and the hydrogen gas after the micro-interface is broken and dispersed are catalytically reacted to generate ethylene glycol.
  • the reaction temperature of the nitric oxide, oxygen and methanol is 60-110°C.
  • the dimethyl oxalate hydrogenation catalytic reaction temperature is 160-210° C.
  • the reaction pressure is 2-2.5 MPa.
  • a hydraulic micro-interface generator connected to the oxygen inlet pipe and the nitric oxide inlet pipe is arranged inside the first reaction tank, so that the oxygen and nitric oxide are broken into a diameter greater than or equal to 1 ⁇ m before the reaction.
  • the preparation method is to set the upper micro-interface generator and the lower micro-interface generator inside the first reaction tank, so that nitric oxide and oxygen are broken into diameters greater than or equal to 1 ⁇ m, The microbubbles smaller than 1mm increase the mass transfer area of the phase boundary between nitric oxide, oxygen and methanol, thereby improving the reaction efficiency;
  • the preparation method uses a first split-flow micro-interface generator inside the second reaction tank
  • the reciprocal micro-interface generator with the first liquid makes oxygen and nitric oxide broken and dispersed into micro-bubbles, which increases the mass transfer area of the phase boundary between nitric oxide, oxygen and methanol, thereby improving the reaction efficiency.
  • a second split flow type micro-interface generator is arranged inside the first hydrogenation reaction tank, so that the hydrogen is broken and dispersed into hydrogen microbubbles; in the preparation method, a second split flow is arranged inside the second hydrogenation reaction tank.
  • the micro-interface generator and hydrogenation micro-interface generator are used to break the hydrogen into micro-bubbles with a diameter of 1 ⁇ m or more and less than 1 mm, so that the hydrogen contacts with dimethyl oxalate in the state of micro-bubbles, increasing the hydrogen in the hydrogenation reaction process.
  • Phase boundary mass transfer area with dimethyl oxalate, and hydrogenation reaction is carried out after fully mixing, thus solving the problem of reaction pressure caused by hydrogen and dimethyl oxalate cannot be fully mixed in the reactor in the prior art High temperature, high temperature and low liquid hourly space velocity.
  • the ethylene glycol product obtained by the reaction method of the invention has good quality and high yield. Moreover, the preparation method itself has low reaction temperature, greatly reduced pressure, and high space velocity, which is equivalent to increasing the production capacity.
  • the enhanced micro-interface reaction system for preparing ethylene glycol by the oxalate method of the present invention is provided in the first reaction tank by a hydraulic micro-interface generator, an upper micro-interface generator and a lower micro-interface generator.
  • the second reaction tank is equipped with a first split-flow micro-interface generator and a first liquid reciprocal micro-interface generator, so that nitric oxide and oxygen are broken into microbubbles before the reaction, and the phase between nitric oxide, oxygen and methanol is improved.
  • the boundary mass transfer area solves the problem of low production efficiency of methyl nitrite in the prior art; the reaction system of the present invention is provided with a second liquid reciprocal micro-interface generator in the first hydrogenation reaction tank.
  • a hydrogenation micro-interface generator and a second split-flow micro-interface generator are set in the hydrogen reaction tank, so that the hydrogen and dimethyl oxalate are broken into micro-bubbles before the reaction of hydrogen and dimethyl oxalate, and the mass transfer area of the phase boundary between hydrogen and dimethyl oxalate is improved. , thereby solving the problems of high reaction pressure, high reaction temperature and low liquid hourly space velocity in the prior art because hydrogen and dimethyl oxalate cannot be fully mixed inside the reactor.
  • the reaction method of the present invention is easy to operate, the concentration of ethylene glycol obtained by the reaction is high, and the application is widely used, which improves the applicability of ethylene glycol itself, and is worthy of widespread promotion.
  • FIG. 1 is a schematic structural diagram of an enhanced micro-interface reaction system for preparing ethylene glycol by oxalate method according to an embodiment of the present invention.
  • 1711 shunt channel
  • 17 first shunt type micro-interface generator
  • 21 carbon monoxide storage tank
  • 22 cooler
  • 171 Second split-flow micro-interface generator; 32: Hydrogen storage tank;
  • the terms “installed”, “connected” and “connected” should be understood in a broad sense, unless otherwise expressly specified and limited, for example, it may be a fixed connection or a detachable connection Connection, or integral connection; can be mechanical connection, can also be electrical connection; can be directly connected, can also be indirectly connected through an intermediate medium, can be internal communication between two elements.
  • installed should be understood in a broad sense, unless otherwise expressly specified and limited, for example, it may be a fixed connection or a detachable connection Connection, or integral connection; can be mechanical connection, can also be electrical connection; can be directly connected, can also be indirectly connected through an intermediate medium, can be internal communication between two elements.
  • the enhanced micro-interface reaction system for preparing ethylene glycol by oxalate method mainly includes a first reaction tank 10, a second reaction tank 101, and a first hydrogenation reaction tank 30. , the first hydrogenation reaction tank 301 , the rectification tower 40 and the ethylene glycol storage tank 50 .
  • the first reaction tank 10 is connected in parallel with the second reaction tank 101, and the oxygen inlet pipe 11 is connected with the hydraulic micro-interface generator 16 in the first reaction tank 10 and the upper micro-interface generator 14, and is connected with the second reaction tank 101.
  • the first split-flow type micro-interface generator 17 is connected with the nitric oxide inlet pipe 12 and the lower micro-interface generator 15 in the first reaction tank 10 and the first liquid reciprocal micro-interface in the second reaction tank 101.
  • the methanol storage tank 13 is connected with the hydraulic micro-interface generator 16 in the first reaction tank 10 and the second reaction tank 101 for supplying methanol to the first reaction tank 10 and the second reaction tank 101 .
  • Nitric oxide, oxygen and methanol react in the first reaction tank 10 and the second reaction tank 101 to generate methyl nitrite and by-products.
  • the first reaction tank 10 is connected in parallel with the second reaction tank 101, the methyl nitrite and by-products in the two reaction tanks are mixed together into the fixed-bed reactor 20, and the fixed-bed reactor 20 is connected to the carbon monoxide storage tank 21, which stores carbon monoxide.
  • the tank 21 transports carbon monoxide to the fixed bed reactor 20, and the methyl nitrite and carbon monoxide undergo a coupling reaction in the fixed bed reactor 20 to generate dimethyl oxalate and by-products.
  • Dimethyl oxalate and by-products are cooled by cooler 22, and then sent to gas-liquid separation tank 23, which separates unreacted nitric oxide from the top and returns to the hydraulic micro-interface generator 16.
  • the regeneration tower 24 regenerates and purifies the dimethyl oxalate solvent to obtain the methyl nitrite and the dimethyl oxalate solvent in the gas phase, and the methyl nitrite in the gas phase returns to the fixed-bed reactor 20 to continue the coupling reaction with carbon monoxide, and the liquid oxalic acid
  • the dimethyl ester is divided into the first hydrogenation reaction tank and the second hydrogenation reaction tank in parallel.
  • the hydrogen in the hydrogen storage tank 32 is pressurized by the hydrogen compressor 41 and then enters the second liquid reciprocal micro-interface generator 181 in the first hydrogenation reaction tank 30 and the second split-flow microinterface in the second hydrogenation reaction tank.
  • the hydrogenation micro-interface generator After the hydrogen is broken and dispersed, it catalyzes the reaction with dimethyl oxalate to generate ethylene glycol. Because the first hydrogenation reaction tank 30 and the second hydrogenation reaction tank 301 are connected in parallel, the ethylene glycol produced by them respectively enters the high-pressure separator 34 to separate out water after mixing, which increases the concentration of ethylene glycol and sends the ethylene glycol to the high-pressure separator 34.
  • the hydraulic micro-interface generator 16 is arranged on the top of the first reaction tank 10, the upper micro-interface generator 14 and the lower micro-interface generator 15 are arranged at the bottom of the first reaction tank 10;
  • the generator 17 is arranged at the top of the second reaction tank 101 , and the first liquid reciprocal micro-interface generator 18 is arranged at the bottom of the second reaction tank 101 .
  • the second liquid reciprocal micro-interface generator 181 is arranged at the bottom of the first hydrogenation reaction tank 30, and the second split-flow micro-interface generator 171 is arranged at the top of the second hydrogenation reaction tank 301, and the hydrogenation micro-interface generates
  • the vessel 31 is arranged at the bottom of the second hydrogenation reaction tank 301 .
  • the second reaction tank 101 is provided with two first shunt-type micro-interface generators 17, and the two first shunt-type micro-interface generators 17 are arranged on the top of the second reaction tank 101, and the direction of the shunt channels 1711 is opposite. , one toward the top of the second reaction tank 101 , and one toward the bottom of the second reaction tank 101 .
  • the temperature of methanol, nitric oxide and oxygen in the first reaction tank 10 and the second reaction tank 101 is 110°C; dimethyl oxalate is in the first hydrogenation reaction tank 30 and the second hydrogenation reaction tank
  • the reaction temperature when being catalyzed by hydrogen in 301 is 160 ° C
  • the reaction pressure in the first hydrogenation reaction tank 30 and the second hydrogenation reaction tank 301 is 2MPa
  • the ethylene glycol collected is sent to the ethylene glycol storage tank 50 for carrying out. storage.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

一种草酸酯法制备乙二醇的强化微界面反应系统，包括：第一反应罐和第一加氢反应罐；所述第一反应罐和第二反应罐并联，所述第一反应罐内设置有液动式微界面发生器、上置微界面发生器和下置微界面发生器，所述第二反应罐内设置有第一分流型微界面发生器和第一液体互逆微界面发生器；所述第一加氢反应罐和第二加氢反应罐并联，所述第一加氢反应罐内设置有第二液体互逆微界面发生器，所述第二加氢反应罐内设置有第二分流型微界面发生器和加氢微界面发生器。本发明的强化微界面反应系统降低了反应时的压力和温度。

Description

一种草酸酯法制备乙二醇的强化微界面反应系统及方法 技术领域
本发明涉及乙二醇制备领域，具体而言，涉及一种草酸酯法制备乙二醇的强化微界面反应系统及方法。
背景技术
乙二醇(Ethylene Glycol)又名甘醇，是一种重要的石油化工有机原料。乙二醇的化学反应与一元醇相似，能进行许多醇类的典型反应，如酯化反应、脱水反应、醚化反应等，反应产物主要用于生产聚酯纤维和聚酯塑料等，广泛用于生产润滑剂、增塑剂、非离子表面活性剂以及炸药等，并可以直接用作防冻剂和配制发动机的冷却剂。当前，制备乙二醇的工艺路线分三种，第一种是直接合成工艺，第二种是利用甲醇、甲醛合成，第三种是草酸酯法合成工艺。其中草酸酯法生产乙二醇工艺采用了自封闭循环方式进行，整个反应过程较为温和，而且其中的催化剂具有稳定性好，耗量少的特点，对环境影响较小。草酸酯法制备乙二醇比其他两种方法获得的乙二醇产品质量更高。目前草酸酯法制备乙二醇技术还不够成熟，还存在一些相关技术难题，首先一氧化氮的再生技术需要完善，其次乙二醇的纯度不高，缺乏对应的精致技术，最后在制备工艺中反应罐内的温度和压力限制使得生产乙二醇的效率低、成本高。这些技术难题限制了草酸酯法制备乙二醇的效率。
因此，亟需改进草酸酯法制备，通过添加新的技术，提高草酸酯法制备乙二醇的纯度和效率。
有鉴于此，特提出本发明。
发明内容
本发明第一目的在于提供一种草酸酯法制备乙二醇的强化微界面反应系统，该反应系统一方面通过在第一反应罐内部设置液动式微界面发生器、上置 微界面发生器、下置微界面发生器，在第二反应罐内设置有第一分流型微界面发生器和第一液体互逆微界面发生器，使得一氧化氮、氧气和甲醇破碎分散为微气泡，提高了一氧化氮，氧气和甲醇之间的相界传质面积，从而解决了现有技术中一氧化氮、氧气和甲醇在第一反应罐内无法充分混合，导致反应压力高、反应温度高和液时空速低的问题，提高了反应效率，另一方面通过在第一加氢反应罐内设置有第二液体互逆微界面发生器，在第二加氢反应罐内设置有第二气体分流型微界面发生器和加氢微界面发生器，将进入的氢气破碎分散成微气泡，并分散到溶剂、催化剂中形成微界面体系，提高了反应气液内的气液相界面积，大幅提高气相向液相的传质速率。
本发明的第二目的在于提供一种采用上述反应系统进行制乙二醇的反应方法，该方法操作简便，得到的乙二醇纯度高，产品品质高，值得广泛推广进行应用。
为了实现本发明的上述目的，特采用以下技术方案：
一种草酸酯法制备乙二醇的强化微界面反应系统，包括：第一反应罐、第二反应罐、液动式微界面发生器、上置微界面发生器、下置微界面发生器、第一分流型微界面发生器、第一液体互逆微界面发生器、第一加氢反应罐、第二加氢反应罐、第二液体互逆微界面发生器、第二分流型微界面发生器和加氢微界面发生器；
所述第一反应罐和所述第二反应罐并联，所述第一反应罐侧壁设置有一氧化氮进气管道和氧气进气管道，所述氧气进气管道连接有所述液动式微界面发生器和所述上置微界面发生器，所述一氧化氮进气管道穿过所述第一反应罐与所述下置微界面发生器相连；所述第二反应罐侧壁设置有氧气进气管道和一氧化氮进气管道，所述氧气进气管道连接有所述第一分流型微界面发生器，所述一氧化氮进气管道连接有所述第一液体互逆微界面发生器；所述第一反应罐和所述第二反应罐与甲醇存储罐相连，所述甲醇存储罐向所述液动式型微界面 发生器和所述第二反应罐输送甲醇；
所述第一加氢反应罐和所述第二加氢反应罐并联，所述第一加氢反应罐内部设置有第二液体互逆微界面发生器，所述第二液体互逆微界面发生器和氢气压缩机相连以用于将氢气破碎分散成微气泡，所述第二加氢反应罐内部设置有所述第二分流型微界面发生器和所述加氢微界面发生器。
现有技术的乙二醇合成方法中，一方面由于一氧化氮、氧气和甲醇在原有反应罐中反应不充分，导致生成的亚硝酸甲酯效率低，从而降低了整个过程的效率，另一方面由于草酸二甲酯和氢气催化反应需要高温高压作为催化条件，反应过程中草酸二甲酯和氢气反应不充分，导致生产成本大，生产效率低，反应生成的乙二醇纯度不高，本发明为了解决上述技术问题提供了一种新型的反应系统，该反应系统中通过在第一反应罐内设置液动式微界面发生器用以将氧气破碎分散成微气泡，增大了氧气、甲醇和一氧化氮之间相界传质面积；液动式微界面发生器连接有气液分离罐，气液分离罐顶部分离出的一氧化氮返回至液动式微界面发生器，一氧化氮和氧气在液动式微界面发生器里发生反应并分散成微气泡，增大了氧气、甲醇和一氧化氮之间的相界传质面积，同时还利用了回收的一氧化氮，节约了成本；液动式微界面发生器连接有甲醇存储罐，甲醇存储罐向液动式微界面发生器输送甲醇，液动式微界面发生器使得甲醇的流速增快，甲醇带着液动式微界面发生器里的微气泡向下与上置微界面发生器里产生的氧气微气泡和下置微界面发生器里产生的一氧化氮微气泡发生对冲，因为在第一反应罐内设置液动式微界面发生器、上置微界面发生器和下置微界面发生器，增大了氧气、甲醇和一氧化氮之间的相界传质面积，加快了第一反应罐内的甲醇流速，从而增大了亚硝酸甲酯的反应速率。该反应系统中通过在第二反应罐内设置第一分流型微界面发生器用以将氧气破碎分散成氧气微气泡，并将氧气微气泡分流到第二反应罐内部各处，使得氧气分散的更广，增大了氧气与甲醇和一氧化氮之间的相界传质面积；第二反应罐内设置第一液体互逆微界面发生器，液体互逆微界面发生器是在相邻的微界面之间设置液体互逆 通道，液体互逆通道最好为两条，左右对称设置，因为在各个微界面发生器之间通过液体的互相流动，从而更能提高一氧化氮的破碎分散，因为破碎是需要动力的，除了微界面发生器内部的微孔结构提供动力以外，液体互逆通道也相应的配合提供了动力，最好的方式是两个液体互逆通道的液相流向是正好相反的，从而在各个微界面发生器之间也能产生对流，提高破碎的效果。正因为第二反应罐内设置了第一分流型微界面发生器和第一液体互逆微界面发生器，所以第二反应罐内的流速增快，氧气、甲醇和一氧化氮之间的相界传质面积增大，增大了亚硝酸甲酯的反应速率。本发明之所以设置第一反应罐和第二反应罐并将其相互并联同时进行操作，是为了提高处理量，也相应的提高了反应效率。
该反应系统中通过在第一加氢反应罐内设置第二液体互逆微界面发生器，因为在各个微界面发生器之间通过液体的互相流动，从而更能提高氢气的破碎分散，增大氢气与草酸二甲酯之间的相界传质面积，使得氢气与草酸二甲酯之间反应充分，提高反应效率；该反应系统中通过在第二加氢反应罐内设置第二分流型微界面发生器用以将氢气破碎分散。分流型微界面发生器的具体结构为在微界面发生器本体上设置有多个分流通道，分流通道最好成弯曲状，设置在分流型微界面发生器的出口处，这样使分流型微界面出来的氢气微气泡分散更广，提高反应效果，所以可见本发明创造性的将微界面发生器与分流通道进行结合应用，提高了分流型微界面发生器的反应效果。本发明之所以设置第一加氢反应罐和第二加氢反应罐并联且同时进行操作，是为了提高处理量，也相应的提高了反应效率。
优选的，所述液动式微界面发生器、所述上置微界面发生器和所述下置微界面发生器在所述第一反应罐内由上至下依次排列，所述液动式微界面发生器设置在所述第一反应罐的顶部，所述下置微界面发生器设置在所述第一反应罐的底部，所述上置微界面发生器设置在所述下置微界面发生器上边；所述第一分流型微界面发生器设置在所述第二反应罐的顶部，所述第一液体互逆微界面发生器设置在所述第二反应罐的底部。液动式微界面发生器之所以设置在第 一反应罐内顶部，是为了将第一反应罐顶部残留的气体通过以液相为动力进行卷吸，保证气体的充分利用，上置微界面发生器和下置微界面发生器通过通入不同的气相分散破碎后在第一反应罐内进行充分的反应，由上至下依次排列的方式也增强了气体之间的互相作用，不仅可以发生对冲还因为距离比较近能够更好的发生互作用。本发明的液动式微界面发生器、上置微界面发生器和下置微界面发生器，以第一反应罐中轴为中心从上至下依次排布，液动式微界面发生器与甲醇、一氧化氮和氧气相连，氧气和一氧化氮破碎分散成微气泡，提高了氧气与一氧化氮和甲醇之间的相界传质面积。液动式微界面发生器通过加压方式，由上至下向溶剂中喷射甲醇和氧气微气泡，加快了反应速率，氧气通过上置微界面发生器形成氧气微气泡，一氧化氮通过下置微界面发生器形成一氧化氮微气泡，增大了气液相界面积，从而提升亚硝酸甲酯的生产速率，同时氧气因为密度比一氧化氮密度大，所以氧气在溶剂中的上升速度要比一氧化氮在溶剂中的上升速度慢，因此将氧气与上置微界面发生器相连，一氧化氮与下置微界面发生器相连，氧气上升速度慢于一氧化氮上升速度，增长了氧气、一氧化氮和甲醇之间的反应时间，从而提升了亚硝酸甲酯的生产效率。第一分流型微界面发生器之所以设置在第二反应罐顶部，首先是为了方便收集再生塔返回来的一氧化氮并将其破碎分散成一氧化氮微气泡，其次是为了将破碎分散的一氧化氮向下与上置、下置微界面破碎分散产生的氧气和一氧化氮微气泡进行对冲，向上冲撞第二反应罐顶部，使得顶部未反应完全的气体分散开，从而让第一反应罐内的反应更充分。
优选的，所述第二液体互逆微界面发生器设置在所述第一加氢反应罐的底部；所述第二分流型微界面发生器设置在所述第二加氢反应罐的顶部，所述加氢微界面发生器设置在所述第二加氢反应罐的底部。第二液体互逆微界面发生器和加氢微界面发生器之所以分别设置在第一加氢反应罐和第二加氢反应罐底部，是因为氢气密度小，在溶剂中的上升速度快，为了能使草酸二甲酯和氢气充分的发生催化反应，因此第二液体互逆微界面发生器和加氢微界面发生 器分别设置在第一加氢反应罐和第二加氢反应罐底部，增大氢气从底部到顶部的上升距离，从而增加了氢气与草酸二甲酯的反应时间，提升了氢气催化草酸二甲酯生成乙二醇的速率。
优选的，所述第二反应罐内的所述第一分流型微界面发生器有两个。
优选的，所述第二反应罐内的位于上部的所述第一分流型微界面发生器的分流通道设置方向朝上，位于下部的所述第一分流型微界面发生器的分流通道设置方向朝下。
优选的，所述第二加氢反应罐内的所述第二分流型微界面发生器的分流通道设置方向朝下。
优选的，所述第二分流型微界面发生器和所述加氢微界面发生器均与所述氢气压缩机相连用以将氢气破碎分散成微气泡。
本领域所属技术人员可以理解的是，本发明所采用的微界面发生器在本发明人在先专利中已有体现，如申请号CN201610641119.6、CN201610641251.7、CN201710766435.0、CN106187660、CN105903425A、CN109437390A、CN205833127U及CN207581700U的专利。在先专利CN201610641119.6中详细介绍了微米气泡发生器(即微界面发生器)的具体产品结构和工作原理，该申请文件中记载了“微米气泡发生器包括本体和二次破碎件、本体内具有空腔，本体上设有与空腔连通的进口，空腔的相对的第一端和第二端均敞开，其中空腔的横截面积从空腔的中部向空腔的第一端和第二端减小；二次破碎件设在空腔的第一端和第二端中的至少一个处，二次破碎件的一部分设在空腔内，二次破碎件与空腔两端敞开的通孔之间形成一个环形通道。微米气泡发生器还包括进气管和进液管。”从该申请文件中公开的具体结构可以知晓其具体工作原理为：液体通过进液管切向进入微米气泡发生器内，超高速旋转并切割气体，使气体气泡破碎成微米级别的微气泡，从而提高液相与气相之间的传质面积，而且该专利中的微米气泡发生器属于气动式微界面发生器。
另外，在先专利201610641251.7中有记载一次气泡破碎器具有循环液进 口、循环气进口和气液混合物出口，二次气泡破碎器则是将进料口与气液混合物出口连通，说明气泡破碎器都是需要气液混合进入，另外从后面的附图中可知，一次气泡破碎器主要是利用循环液作为动力，所以其实一次气泡破碎器属于液动式微界面发生器，二次气泡破碎器是将气液混合物同时通入到椭圆形的旋转球中进行旋转，从而在旋转的过程中实现气泡破碎，所以二次气泡破碎器实际上是属于气液联动式微界面发生器。其实，无论是液动式微界面发生器，还是气液联动式微界面发生器，都属于微界面发生器的一种具体形式，然而本发明所采用的微界面发生器并不局限于上述几种形式，在先专利中所记载的气泡破碎器的具体结构只是本发明微界面发生器可采用的其中一种形式而已。
此外，在先专利201710766435.0中记载到“气泡破碎器的原理就是高速射流以达到气体相互碰撞”，并且也阐述了其可以用于微界面强化反应器，验证本身气泡破碎器与微界面发生器之间的关联性；而且在先专利CN106187660中对于气泡破碎器的具体结构也有相关的记载，具体见说明书中第[0031]-[0041]段，以及附图部分，其对气泡破碎器S-2的具体工作原理有详细的阐述，气泡破碎器顶部是液相进口，侧面是气相进口，通过从顶部进来的液相提供卷吸动力，从而达到粉碎成超细气泡的效果，附图中也可见气泡破碎器呈锥形的结构，上部的直径比下部的直径要大，也是为了液相能够更好的提供卷吸动力。
由于在先专利申请的初期，微界面发生器才刚研发出来，所以早期命名为微米气泡发生器(CN201610641119.6)、气泡破碎器(201710766435.0)等，随着不断技术改进，后期更名为微界面发生器，现在本发明中的微界面发生器相当于之前的微米气泡发生器、气泡破碎器等，只是名称不一样。综上所述，本发明的微界面发生器属于现有技术。
另外，本发明还提供了一种草酸酯法制备乙二醇的方法，包括如下步骤：
一氧化氮、氧气和甲醇微界面破碎分散后进行反应，得到亚硝酸甲酯；
亚硝酸甲酯和一氧化碳偶联生成草酸二甲酯；
草酸二甲酯和微界面破碎分散后的氢气进行催化反应生成乙二醇。
优选的，所述一氧化氮、氧气和甲醇反应的温度为60-110℃。
优选的，所述草酸二甲酯加氢气催化反应温度为160-210℃，反应压力为2-2.5MPa。
具体的，该制备方法通过在第一反应罐内部设置与氧气进气管道与一氧化氮进气管道连接的液动式微界面发生器，使得氧气和一氧化氮在反应前破碎成直径大于等于1μm、小于1mm的微气泡，并且加快溶剂流速；该制备方法通过在第一反应罐内部设置上置微界面发生器和下置微界面发生器，使得一氧化氮和氧气破碎成直径大于等于1μm、小于1mm的微气泡，提高了一氧化氮、氧气和甲醇之间的的相界传质面积，从而提高了反映效率；该制备方法通过在第二反应罐内部设置第一分流型微界面发生器和第一液体互逆微界面发生器，使得氧气和一氧化氮破碎分散成微气泡，提高了一氧化氮、氧气和甲醇之间的相界传质面积，从而提高了反应效率。
具体的，该制备方法通过在第一加氢反应罐内部设置第二分流型微界面发生器，使得氢气破碎分散成氢气微气泡；该制备方法通过在第二加氢反应罐内部设置第二分流型微界面发生器和加氢微界面发生器用以将氢气破碎成直径大于等于1μm、小于1mm的微气泡，使得氢气以微气泡的状态与草酸二甲酯接触，增大加氢反应过程中氢气与草酸二甲酯之间的相界传质面积，并在充分混合后进行加氢反应，从而解决了现有技术中由于氢气和草酸二甲酯在反应器内部无法得到充分混合，导致反应压力高、温度高、液时空速低的问题。
采用本发明的反应方法得到的乙二醇产品品质好，收率高。且该制备方法本身反应温度低、压力大幅下降、也是空速高，相当于提高了产能。
与现有技术相比，本发明的有益效果在于：
(1)本发明的草酸酯法制备乙二醇的强化微界面反应系统通过在第一反应罐内设置液动式微界面发生器、上置微界面发生器和下置微界面发生器，在第二反应罐设置第一分流型微界面发生器和第一液体互逆微界面发生器，使得 一氧化氮和氧气在反应之前破碎为微气泡，提高一氧化氮、氧气和甲醇之间的相界传质面积，解决了现有技术中亚硝酸甲酯生产效率低的问题；本发明的反应系统通过在第一加氢反应罐内设置第二液体互逆微界面发生器，在第二加氢反应罐中设置加氢微界面发生器和第二分流型微界面发生器，使得氢气与草酸二甲酯反应之前破碎成为微气泡，提高氢气与草酸二甲酯之间的相界传质面积，从而解决了现有技术中由于氢气和草酸二甲酯在反应器内部无法得到充分混合，导致反应压力高、反应温度高、液时空速低的问题。
(2)本发明的反应方法操作简便，反应得到的乙二醇浓度高，应用广发，提高了乙二醇本身的适用面，值得广泛推广。
附图说明
通过阅读下文优选实施方式的详细描述，各种其他的优点和益处对于本领域普通技术人员将变得清楚明了。附图仅用于示出优选实施方式的目的，而并不认为是对本发明的限制。而且在整个附图中，用相同的参考符号表示相同的部件。在附图中：
图1为本发明实施例提供的草酸酯法制乙二醇的强化微界面反应系统的结构示意图。
其中：
10：第一反应罐；                    101：第二反应罐；
11：氧气进气管道；                  12：一氧化氮进气管道；
16：液动式微界面发生器；            13：甲醇存储罐；
14：上置微界面发生器；              15：下置微界面发生器；
1711：分流通道；                    17：第一分流型微界面发生器；
18：第一液体互逆微界面发生器；      20：固定床反应器；
21：一氧化碳存储罐；                 22：冷却器；
23：气液分离罐；                     24：再生塔；
30：第一加氢反应罐；                 301：第二加氢反应罐；
181：第二液体互逆微界面发生器；      31：加氢微界面发生器；
171：第二分流型微界面发生器；        32：氢气存储罐；
34：高压分离器；                     35：低压闪蒸槽；
40：精馏塔；                         41：氢气压缩机；
50：乙二醇存储罐。
具体实施方式
下面将结合附图和具体实施方式对本发明的技术方案进行清楚、完整地描述，但是本领域技术人员将会理解，下列所描述的实施例是本发明一部分实施例，而不是全部的实施例，仅用于说明本发明，而不应视为限制本发明的范围。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
在本发明的描述中，需要说明的是，术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。此外，术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性。
在本发明的描述中，需要说明的是，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可 以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域的普通技术人员而言，可以具体情况理解上述术语在本发明中的具体含义。
为了更加清晰的对本发明中的技术方案进行阐述，下面以具体实施例的形式进行说明。
实施例
参阅图1所示，为本发明实施例提供的草酸酯法制备乙二醇的强化微界面反应系统，其主要包括第一反应罐10、第二反应罐101、第一加氢反应罐30、第一加氢反应罐301、精馏塔40和乙二醇存储罐50。
第一反应罐10与第二反应罐101并联，氧气进气管道11与第一反应罐10中的液动式微界面发生器16和上置微界面发生器14连接，与第二反应罐101中的第一分流型微界面发生器17相连，一氧化氮进气管道12与第一反应罐10中的下置微界面发生器15和第二反应罐101中的第一液体互逆微界面发生器18连接，甲醇存储罐13与第一反应罐10中的液动式微界面发生器16和第二反应罐101相连以用于向第一反应罐10，第二反应罐101中提供甲醇。一氧化氮、氧气和甲醇在第一反应罐10，第二反应罐101中发生反应，生成亚硝酸甲酯和副产物。
因为第一反应罐10与第二反应罐101并联，两个反应罐中的亚硝酸甲酯和副产物混合一起进入固定床反应器20，固定床反应器20连接有一氧化碳存储罐21，一氧化碳存储罐21向固定床反应器20输送一氧化碳，亚硝酸甲酯和一氧化碳在固定床反应器20中发生偶联反应，生成草酸二甲酯和副产物。草酸二甲酯和副产物通过冷却器22进行降温，接着被输送到气液分离罐23中，气液分离罐23将未反应的一氧化氮从顶部分离出并返回至液动式微界面发生器16，将草酸二甲酯从底部分离出进入再生塔24。再生塔24对草酸二甲酯溶剂进行再生提纯得到气相的亚硝酸甲酯和草酸二甲酯溶剂，气相的亚硝酸甲酯 返回至固定床反应器20继续与一氧化碳发生偶联反应，液态的草酸二甲酯分流进入到并联的第一加氢反应罐和第二加氢反应罐。氢气存储罐32里的氢气通过氢气压缩机41加压后进入到第一加氢反应罐30中的第二液体互逆微界面发生器181、第二加氢反应罐中的第二分流型微界面发生器171和加氢微界面发生器中，氢气破碎分散后和草酸二甲酯催化反应生成乙二醇。因为第一加氢反应罐30和第二加氢反应罐301并联，所以其分别生成的乙二醇混合后进入高压分离器34分离出水，增大了乙二醇的浓度，将乙二醇送入低压闪蒸槽35闪蒸得到乙二醇溶解气，再将乙二醇溶解气送入精馏塔40，精馏塔40顶部分离出的氢气进入氢气压缩机41加压后返回至第一加氢反应罐30和第二加氢反应罐301，精馏塔40底部分离出的副产物直接排出并进行安全处理，精馏塔40中部分离出的乙二醇通过管道输送至乙二醇存储罐50用以储存。
其中，液动式微界面发生器16设置在第一反应罐10的顶部，上置微界面发生器14和下置微界面发生器15设置在第一反应罐10的底部；第一分流型微界面发生器17设置在第二反应罐101的顶部，第一液体互逆微界面发生器18设置在第二反应罐101的底部。
其中，第二液体互逆微界面发生器181设置在第一加氢反应罐30的底部，第二分流型微界面发生器171设置在第二加氢反应罐301的顶部，加氢微界面发生器31设置在第二加氢反应罐301的底部。
另外，第二反应罐101设置有两个第一分流型微界面发生器17，这两个第一分流型微界面发生器17设置在第二反应罐101的顶部，其分流通道1711的朝向相反，一个朝向第二反应罐101的顶部，一个朝向第二反应罐101的底部。
具体反应过程中，甲醇、一氧化氮和氧气在第一反应罐10和第二反应罐101反应时温度为110℃；草酸二甲酯在第一加氢反应罐30和第二加氢反应罐301里被氢气催化时的反应温度为160℃，第一加氢反应罐30和第二加氢反应罐301内部反应压力为2MPa，将收集到的乙二醇送至乙二醇存储罐50进行存 储。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (10)

  1. 一种草酸酯法制备乙二醇的强化微界面反应系统，其特征在于，包括：第一反应罐、第二反应罐、液动式微界面发生器、上置微界面发生器、下置微界面发生器、第一分流型微界面发生器、第一液体互逆微界面发生器、第一加氢反应罐、第二加氢反应罐、第二液体互逆微界面发生器、第二分流型微界面发生器和加氢微界面发生器；
    所述第一反应罐和所述第二反应罐并联，所述第一反应罐侧壁设置有一氧化氮进气管道和氧气进气管道，所述氧气进气管道连接有所述液动式微界面发生器和所述上置微界面发生器，所述一氧化氮进气管道穿过所述第一反应罐与所述下置微界面发生器相连；所述第二反应罐侧壁设置有氧气进气管道和一氧化氮进气管道，所述氧气进气管道连接有所述第一分流型微界面发生器，所述一氧化氮进气管道连接有所述第一液体互逆微界面发生器；所述第一反应罐和所述第二反应罐与甲醇存储罐相连，所述甲醇存储罐向所述液动式型微界面发生器和所述第二反应罐输送甲醇；
    所述第一加氢反应罐和所述第二加氢反应罐并联，所述第一加氢反应罐内部设置有第二液体互逆微界面发生器，所述第二液体互逆微界面发生器和氢气压缩机相连以用于将氢气破碎分散成微气泡，所述第二加氢反应罐内部设置有所述第二分流型微界面发生器和所述加氢微界面发生器。
  2. 根据权利要求1所述的强化微界面反应系统，其特征在于，所述液动式微界面发生器、所述上置微界面发生器和所述下置微界面发生器在所述第一反应罐内由上至下依次排列，所述液动式微界面发生器设置在所述第一反应罐的顶部，所述下置微界面发生器设置在所述第一反应罐的底部，所述上置微界面发生器设置在所述下置微界面发生器上边；所述第一分流型微界面发生器设置在所述第二反应罐的顶部，所述第一液体互逆微界面发生器设置在所述第二反应罐的底部。
  3. 根据权利要求1所述的强化微界面反应系统，其特征在于，所述第二 液体互逆微界面发生器设置在所述第一加氢反应罐的底部；所述第二分流型微界面发生器设置在所述第二加氢反应罐的顶部，所述加氢微界面发生器设置在所述第二加氢反应罐的底部。
  4. 根据权利要求1所述的强化微界面反应系统，其特征在于，所述第二反应罐内的所述第一分流型微界面发生器有两个。
  5. 根据权利要求4所述的强化微界面反应系统，其特征在于，所述第二反应罐内的位于上部的所述第一分流型微界面发生器的分流通道设置方向朝上，位于下部的所述第一分流型微界面发生器的分流通道设置方向朝下。
  6. 根据权利要求1所述的强化微界面反应系统，其特征在于，所述第二加氢反应罐内的所述第二分流型微界面发生器的分流通道设置方向朝下。
  7. 根据权利要求1所述的强化微界面反应系统，其特征在于，所述第二分流型微界面发生器和所述加氢微界面发生器均与所述氢气压缩机相连用以将氢气破碎分散成微气泡。
  8. 采用权利要求1-7任一项所述的草酸酯法制备乙二醇的强化微界面反应系统及方法，其特征在于，包括如下步骤：
    一氧化氮、氧气和甲醇微界面破碎分散后进行反应，得到亚硝酸甲酯；
    亚硝酸甲酯和一氧化碳偶联生成草酸二甲酯；
    草酸二甲酯和微界面破碎分散后的氢气进行催化反应生成乙二醇。
  9. 根据权利要求8所述的反应方法，其特征在于，所述一氧化氮、氧气和甲醇反应的温度为60-110℃。
  10. 根据权利要求8所述的反应方法，其特征在于，所述草酸二甲酯加氢气催化反应温度为160-210℃，反应压力为2-2.5MPa。
PCT/CN2021/109739 2020-11-30 2021-07-30 一种草酸酯法制备乙二醇的强化微界面反应系统及方法 WO2022110871A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202011371932.9A CN112479822A (zh) 2020-11-30 2020-11-30 一种草酸酯法制备乙二醇的强化微界面反应系统及方法
CN202011371932.9 2020-11-30

Publications (1)

Publication Number Publication Date
WO2022110871A1 true WO2022110871A1 (zh) 2022-06-02

Family

ID=74937283

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/109739 WO2022110871A1 (zh) 2020-11-30 2021-07-30 一种草酸酯法制备乙二醇的强化微界面反应系统及方法

Country Status (2)

Country Link
CN (1) CN112479822A (zh)
WO (1) WO2022110871A1 (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112479822A (zh) * 2020-11-30 2021-03-12 南京延长反应技术研究院有限公司 一种草酸酯法制备乙二醇的强化微界面反应系统及方法
CN114507133A (zh) * 2022-03-03 2022-05-17 南京延长反应技术研究院有限公司 一种制备顺丁烯二酸二甲酯的强化微界面系统及方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104098441A (zh) * 2014-06-05 2014-10-15 上海戊正工程技术有限公司 工业合成气高压羰化生产草酸二甲酯并加氢制乙二醇的工艺和装置系统
CN106316788A (zh) * 2016-08-19 2017-01-11 中石化上海工程有限公司 合成气制乙二醇生产中降低酸性腐蚀的方法
CN106748785A (zh) * 2016-12-14 2017-05-31 上海华谊能源化工有限公司 一种合成气制乙二醇工艺中废水处理工艺和系统
CN106866363A (zh) * 2017-02-10 2017-06-20 南京敦先化工科技有限公司 一种大型化合成气制备乙二醇的系统及方法
CN111686644A (zh) * 2019-03-15 2020-09-22 南京延长反应技术研究院有限公司 一种下行式固定床油品加氢微界面强化反应系统
CN112479822A (zh) * 2020-11-30 2021-03-12 南京延长反应技术研究院有限公司 一种草酸酯法制备乙二醇的强化微界面反应系统及方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IN154274B (zh) * 1980-09-02 1984-10-13 Ube Industries
WO2009153123A1 (de) * 2008-05-27 2009-12-23 Basf Se Kontinuierliches verfahren und reaktor zur hydrierung organischer verbindungen
CN102649707A (zh) * 2011-02-25 2012-08-29 中国石油化工股份有限公司 草酸酯通过气相加氢反应制备乙二醇的方法
US10017438B2 (en) * 2014-06-05 2018-07-10 Shanghai Wuzheng Engineering Technology Co., Ltd. Method and device system for producing dimethyl oxalate through carbonylation of industrial synthesis gas and producing ethylene glycol through dimethyl oxalate hydrogenation
CN104841339A (zh) * 2015-04-16 2015-08-19 中国五环工程有限公司 一种用于合成气制乙二醇工艺的新型加氢反应器
CN106928021B (zh) * 2017-02-20 2020-04-24 宁波中科远东催化工程技术有限公司 一种草酸二甲酯加氢制乙二醇的方法
CN109865493A (zh) * 2019-01-31 2019-06-11 浙江大学 一种用于对二甲苯氧化的双鼓泡塔反应装置及反应工艺
CN111359556A (zh) * 2019-03-15 2020-07-03 南京延长反应技术研究院有限公司 一种微界面强化加氢反应系统

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104098441A (zh) * 2014-06-05 2014-10-15 上海戊正工程技术有限公司 工业合成气高压羰化生产草酸二甲酯并加氢制乙二醇的工艺和装置系统
CN106316788A (zh) * 2016-08-19 2017-01-11 中石化上海工程有限公司 合成气制乙二醇生产中降低酸性腐蚀的方法
CN106748785A (zh) * 2016-12-14 2017-05-31 上海华谊能源化工有限公司 一种合成气制乙二醇工艺中废水处理工艺和系统
CN106866363A (zh) * 2017-02-10 2017-06-20 南京敦先化工科技有限公司 一种大型化合成气制备乙二醇的系统及方法
CN111686644A (zh) * 2019-03-15 2020-09-22 南京延长反应技术研究院有限公司 一种下行式固定床油品加氢微界面强化反应系统
CN112479822A (zh) * 2020-11-30 2021-03-12 南京延长反应技术研究院有限公司 一种草酸酯法制备乙二醇的强化微界面反应系统及方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHANG ZHIBING; TIAN HONGZHOU; ZHANG FENG; ZHOU ZHENG: "Overview of Microinterface Intensification in Multiphase Reaction Systems", CIESC JOURNAL, HUAXUE GONGYE CHUBANSHE, CN, vol. 69, no. 1, 6 November 2017 (2017-11-06), CN , pages 44 - 49, XP009526633, ISSN: 0438-1157, DOI: 10.11949/j.issn.0438-1157.20171400 *

Also Published As

Publication number Publication date
CN112479822A (zh) 2021-03-12

Similar Documents

Publication Publication Date Title
WO2022110871A1 (zh) 一种草酸酯法制备乙二醇的强化微界面反应系统及方法
WO2022041425A1 (zh) 一种环状碳酸酯的强化微界面制备系统及方法
WO2022011870A1 (zh) 一种煤制乙醇的反应系统及方法
WO2023138074A1 (zh) 一种催化二氧化碳环加成制备环状碳酸酯的方法及系统
WO2022036837A1 (zh) 一种石油树脂加氢的反应系统及方法
EP4316642A1 (en) Reaction system and method for preparing butyraldehyde by propylene carbonylation
CN113061080A (zh) 一种丙烯羰基化制丁醛的微界面反应系统及方法
CN113061081A (zh) 一种丙烯羰基化制丁醛的微界面强化反应系统及方法
CN111777491A (zh) 一种煤制乙醇的微界面反应系统及方法
CN112452268A (zh) 一种草酸酯法制备乙二醇的微界面反应系统及方法
CN112479852A (zh) 一种甲酸的制备系统及方法
CN111848344A (zh) 一种采用合成气制乙醇的反应系统及方法
WO2022052222A1 (zh) 一种草酸酯加氢制备乙醇酸酯的反应系统及方法
WO2022127127A1 (zh) 一种氯乙醇法制备乙二醇的微界面反应系统及方法
WO2022110872A1 (zh) 一种气相催化水合法制备乙二醇的强化反应系统及方法
CN113546589A (zh) 一种微界面强化制备dmc的系统及制备方法
CN112457169A (zh) 一种草酸酯法制备乙二醇的反应系统及方法
CN112403006A (zh) 一种二氧化碳加氢制甲酸的强化微界面反应系统及方法
CN216024781U (zh) 一种基于微界面的正丁醛缩合反应系统
WO2023284024A1 (zh) 正丁醛缩合制辛烯醛的微界面强化系统及制备方法
CN214612318U (zh) 一种柴油加氢的微界面反应系统
CN216024790U (zh) 一种正丁醛缩合制辛烯醛的微界面强化系统
WO2022036838A1 (zh) 一种石油树脂加氢的微界面反应系统及方法
CN113680286A (zh) 一种催化剂可循环使用的丙烯羰基化反应系统及方法
CN210045216U (zh) 上置式渣油加氢乳化床微界面强化反应装置

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21896378

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21896378

Country of ref document: EP

Kind code of ref document: A1