CN112717847A - Micro-interface reaction system and method for preparing ethylene glycol by ethylene oxide method - Google Patents
Micro-interface reaction system and method for preparing ethylene glycol by ethylene oxide method Download PDFInfo
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- CN112717847A CN112717847A CN202011492546.5A CN202011492546A CN112717847A CN 112717847 A CN112717847 A CN 112717847A CN 202011492546 A CN202011492546 A CN 202011492546A CN 112717847 A CN112717847 A CN 112717847A
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 160
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims description 54
- 239000002994 raw material Substances 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010406 interfacial reaction Methods 0.000 claims 2
- 230000001965 increasing effect Effects 0.000 abstract description 15
- 239000007789 gas Substances 0.000 description 32
- 239000012071 phase Substances 0.000 description 16
- 239000007791 liquid phase Substances 0.000 description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000005501 phase interface Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 230000002528 anti-freeze Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002146 bilateral effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 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
- B01J19/0053—Details of the reactor
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
- B01F23/29—Mixing systems, i.e. flow charts or diagrams
-
- 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
-
- 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
- B01J19/18—Stationary reactors having moving elements inside
-
- 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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
-
- 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00162—Controlling or regulating processes controlling the pressure
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00164—Controlling or regulating processes controlling the flow
- B01J2219/00166—Controlling or regulating processes controlling the flow controlling the residence time inside the reactor vessel
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Abstract
The invention provides a micro-interface reaction system and a method for preparing ethylene glycol by an ethylene oxide method, wherein the micro-interface reaction system comprises: a reactor and a stirred tank, wherein NaHCO is filled in the stirred tank3Dosing; a micro-interface unit is arranged on the outer side of the stirring kettle and is formed by arranging a plurality of external micro-interface generators;the main pipeline which is led into the micro-interface unit is simultaneously connected with an ethylene oxide feeding pipeline and two branch pipelines of a water source pipeline, the ethylene oxide is led into the micro-interface unit from the gas source conveying pipeline, and the water source enters the interior of the micro-interface unit and is used for crushing ethylene oxide gas into micro-bubbles with micron level; according to the invention, the micro-interface units are arranged outside the stirring kettle and inside the reactor, so that the ethylene oxide is broken into micro bubbles before reacting with a water source, and the phase boundary mass transfer area between the ethylene oxide and the water source is increased.
Description
Technical Field
The invention relates to the field of ethylene glycol preparation, in particular to a micro-interface reaction system and a micro-interface reaction method for preparing ethylene glycol by an ethylene oxide method.
Background
Ethylene Glycol (EG) is the simplest and most important aliphatic diol, a colorless, odorless, sweet liquid, and can be mixed with water in any ratio. Ethylene glycol has a wide industrial use, and can be used for producing polyethylene terephthalate (a raw material for synthetic polyester fibers and polyester plastics), and for producing other polyester resins, unsaturated polyester resins, nonionic surfactants, ethanolamine, explosives, and the like; the high-purity ethylene glycol can be used for preparing antifreeze and antifreeze of cooling systems in the automobile industry, the aviation industry and the instrument industry, and producing solvents, lubricants, softeners, plasticizers and the like; ethylene glycol is also used in hydraulic brakes, tobacco humectants, fur treating agents, inkpads, and inks. The total demand and consumption of EG in China are huge, and EG has good development prospect in China.
Ethylene glycol is prepared by an ethylene oxide method, and then downstream products are developed to form a good industrial chain, so that the method is a very good prospect for chemical enterprises at present. Ethylene oxide is taken as a raw material to carry out hydrolysis reaction in a weak alkaline water source, ethylene glycol is directly synthesized, and pure ethylene glycol is prepared by separation; the ethylene glycol is prepared by the ethylene oxide method, and the reaction temperature must be properly increased for accelerating the reaction speed due to larger reaction activation energy, and the reaction is carried out at 80-100 ℃. However, after the reaction temperature is increased, the corresponding reaction pressure is also increased in order to keep the reaction system in a liquid phase; in the reaction process, the ethylene oxide and the water source can not be fully mixed, so that the reaction needs to be carried out under high ethylene oxide pressure (more than 2.0MPa), and the production capacity of the reactor is limited (liquid hourly space velocity is less than 1.0 h)-1)。
Therefore, there is a need for improved routes to ethylene glycol production.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a reaction system for preparing ethylene glycol by an ethylene oxide method, wherein a micro-interface unit is arranged on the outer side of a stirring kettle and inside a reactor, so that ethylene oxide is broken into micro bubbles before reacting with a water source, and the phase boundary mass transfer area between the ethylene oxide and the water source is increased, thereby solving the problems of high reaction pressure, large hydrogen-ester ratio and low liquid hourly space velocity caused by the fact that the ethylene oxide and the water source cannot be fully mixed in the reactor in the prior art.
The second purpose of the invention is to provide a reaction method for preparing ethylene glycol by adopting the micro-interface reaction system, the ethylene glycol obtained by the reaction has high purity and wide application, the application range of the ethylene glycol is improved, and the method is worthy of wide popularization and application.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the invention provides a micro-interface reaction system for preparing ethylene glycol by an ethylene oxide method, which is characterized by comprising the following steps: the device comprises a reactor and a stirring kettle, wherein a NaHCO3 agent is filled in the stirring kettle;
a micro-interface unit is arranged on the outer side of the stirring kettle and is formed by arranging a plurality of external micro-interface generators; the main pipeline which is led into the micro-interface unit is simultaneously connected with an ethylene oxide feeding pipeline and two branch pipelines of a water source pipeline, the ethylene oxide is led into the micro-interface unit from the gas source conveying pipeline, and the water source enters the interior of the micro-interface unit and is used for crushing ethylene oxide gas into micro-bubbles with micron level;
the micro-interface unit is arranged at the outer side of the stirring kettle, a water source and ethylene oxide are gathered and then enter the micro-interface unit through the main pipeline, the fusion effect between raw materials is improved by the way of gathering, the ethylene oxide entering the micro-interface generator in parallel is equivalent to a primary micro-interface system formed in each micro-interface generator, so that the gas phase is fully dispersed and crushed in the micro-interface generator on the premise of taking the liquid phase as a medium, the two micro-interface generators at the middle part are closest to a gas phase feed inlet and are used as main dispersed and crushed micro-interface systems, and then the two micro-interface generators at the upper part and the lower part form a secondary micro-interface system and a tertiary micro-interface system, so that the effect of enhancing the reaction is achieved.
In addition, in order to play a good role in fixing, a connecting rod is specially arranged between the micro-interface generators so as to play a role in strengthening the fixing.
The reactor is characterized in that supports are arranged on two sides of a built-in micro-interface generator and fixed in the reactor in order to enable the built-in micro-interface generator to be more stable.
A reaction material liquid inlet is formed in the bottom of the reactor and is communicated with the stirring kettle through an overflow pipe, a built-in micro-interface generator is arranged in the reactor, and an ethylene oxide feeding hole is formed in the built-in micro-interface generator and is used for dispersing and crushing ethylene oxide into micro bubbles under the condition that the reaction material liquid is used as a medium;
the built-in micro-interface generator breaks ethylene oxide into micro-bubbles with micron scale, and releases the micro-bubbles into the reactor, so as to increase the mass transfer area of the phase boundary between the ethylene oxide and the water source in the reaction process, and the ethylene oxide is fully contacted with the water source in the micro-bubble state and reacts.
And (3) the reaction product reacted from the reactor enters a light component removal tower to remove light components, and then enters a rectifying tower to be rectified to obtain the ethylene glycol.
Furthermore, the number of the external micro-interface generators is 4, and the external micro-interface generators are sequentially arranged from top to bottom, so that the phase interface area between a gas phase and a liquid phase is increased, the mass transfer space is fully satisfied, the retention time of the gas in the liquid phase is increased, and the reaction efficiency is improved; and a liquid reciprocal channel is arranged between every two adjacent micro-interface generators and realizes the circulation of gas and liquid in the micro-interface generators.
Furthermore, the number of the external micro-interface generators is 4, each 2 is divided into two groups, the two groups are sequentially arranged from top to bottom, 2 of each group of the micro-interface generators are connected in series, the two groups are connected in parallel, the phase interface area between a gas phase and a liquid phase is increased, the retention time of the gas in the liquid phase is increased, meanwhile, each group is connected in series, the breaking rate of the gas phase is more sufficient, micro bubbles generated by the front micro-interface generator enter the rear micro-interface generator, the micro bubbles are further broken into smaller micro bubbles, and the mass transfer effect is fully improved; a liquid reciprocal channel is arranged between the adjacent micro-interface generators, and the liquid reciprocal channel realizes the circulation of gas and liquid in the micro-interface generators;
furthermore, the number of the external micro-interface generators is 3, and the external micro-interface generators are sequentially arranged from top to bottom, so that the phase interface area between a gas phase and a liquid phase is increased, the mass transfer space is more sufficient, and the retention time of the gas in the liquid phase is prolonged; a liquid reciprocal channel is arranged between the adjacent micro-interface generators, and the liquid reciprocal channel realizes the circulation of gas and liquid in the micro-interface generators;
preferably, the liquid reciprocal channels are arranged in two groups and are arranged in bilateral symmetry, and the crushing degree of the gas phase can be improved through the mutual circulation of liquid among all the micro-interface generators; the power required by the broken gas phase is provided by the microporous structure in the micro-interface generator, and the liquid reciprocal channel also provides power correspondingly in an auxiliary way;
preferably, the liquid phase flow directions of the two sets of liquid reciprocal channels are opposite, so that convection is generated between the micro-interface generators, and the crushing effect is improved.
Further, the water source feeding pipeline is connected with a water source storage tank to supply water to the water source entering the external micro-interface generator; the ethylene oxide feeding pipeline is connected with an ethylene oxide external channel so as to provide an ethylene oxide gas source for the ethylene oxide to enter the external micro-interface generator.
Further, a light component outlet is formed in the top of the light component removal tower and used for discharging light components, a heavy component outlet is formed in the bottom of the light component removal tower and communicated with the side wall of the rectifying tower and used for further rectifying the ethylene glycol.
Further, a raw material circulating outlet is formed in the bottom of the rectifying tower, and the water source returns to the reactor from the raw material circulating outlet so as to realize the recycling of the raw materials.
Further, the top of the rectifying tower is provided with an overhead condenser, a part of substances condensed from the overhead condenser is returned to the rectifying tower, and the other part of substances goes to the ethylene glycol storage tank.
The invention also provides a reaction method of the micro-interface reaction system for preparing the ethylene glycol by the ethylene oxide method, which comprises the following steps:
mixing ethylene oxide and a water source, carrying out micro-interface dispersion and crushing, reacting, removing light, rectifying to obtain ethylene glycol, and collecting.
Further, the pressure of the reaction is 0.8-2.0 MPa.
The process conditions for preparing the ethylene glycol by hydrolyzing the ethylene oxide are as follows: the molar ratio of ethylene oxide to NaHCO3 was: 1:1, the reaction temperature is about 78-95 ℃; the reaction time is 2-3 h.
Because the industrial grade ethylene oxide contains more impurities, the yield is low, and in order to improve the yield of the ethylene glycol, a proper catalyst can be selected during hydrolysis and a proper polymerization inhibitor can be selected during separation to prevent the polyethylene glycol from generating by self polymerization.
Specifically, the preparation method comprises the steps of arranging the micro-interface generator connected with the water source feeding pipeline outside the stirring kettle and inside the reactor, enabling the micro-interface generator to crush ethylene oxide into micro-bubbles with the diameter of more than or equal to 1 mu m and less than 1mm before the ethylene oxide reacts with the water source, enabling the ethylene oxide to be in contact with the water source in the micro-bubble state, increasing the phase boundary mass transfer area between the ethylene oxide and the water source in the reaction process, fully mixing and then reacting, and solving the problems that in the prior art, the reaction pressure is high and the liquid hourly space velocity is low due to the fact that the ethylene oxide and the water source cannot be fully mixed in the reactor.
The ethylene glycol product obtained by the reaction method has good quality and high yield. And the preparation method has low reaction temperature, greatly reduced pressure and high liquid hourly space velocity, which is equivalent to improving the productivity.
It will be appreciated by those skilled in the art that the micro-interface generator used in the present invention is described in the prior patents of the present inventor, such as the patents of application nos. CN201610641119.6, 201610641251.7, CN201710766435.0, CN106187660, CN105903425A, CN109437390A, CN205833127U and CN 207581700U. The detailed structure and operation principle of the micro bubble generator (i.e. micro interface generator) is described in detail in the prior patent CN201610641119.6, which describes that "the micro bubble generator comprises a body and a secondary crushing member, wherein the body is provided with a cavity, the body is provided with an inlet communicated with the cavity, the opposite first end and second end of the cavity are both open, and the cross-sectional area of the cavity decreases from the middle of the cavity to the first end and second end of the cavity; the secondary crushing member is disposed at least one of the first end and the second end of the cavity, a portion of the secondary crushing member is disposed within the cavity, and an annular passage is formed between the secondary crushing member and the through holes open at both ends of the cavity. The micron bubble generator also comprises an air inlet pipe and a liquid inlet pipe. "the specific working principle of the structure disclosed in the application document is as follows: liquid enters the micro-bubble generator tangentially through the liquid inlet pipe, and gas is rotated at a super high speed and cut to break gas bubbles into micro-bubbles at a micron level, so that the mass transfer area between a liquid phase and a gas phase is increased, and the micro-bubble generator in the patent belongs to a pneumatic micro-interface generator. The micro-bubble generator is used for secondarily breaking the bubbles in the cavity by arranging a secondary breaking piece at the first end and/or the second end of the cavity so as to generate more micro-bubbles with smaller diameter; in other words, the secondary crushing member can crush further the bubbles that have been cut and crushed near the axis on the tapered surface of the secondary crushing member, producing more and smaller bubbles.
In addition, the first patent 201610641251.7 describes that the primary bubble breaker has a circulation liquid inlet, a circulation gas inlet and a gas-liquid mixture outlet, and the secondary bubble breaker communicates the feed inlet with the gas-liquid mixture outlet, which indicates that the bubble breakers all need to be mixed with gas and liquid, and in addition, as can be seen from the following drawings, the primary bubble breaker mainly uses the circulation liquid as power, so that the primary bubble breaker belongs to a hydraulic micro-interface generator, and the secondary bubble breaker simultaneously introduces the gas-liquid mixture into an elliptical rotating ball for rotation, thereby realizing bubble breaking in the rotating process, so that the secondary bubble breaker actually belongs to a gas-liquid linkage micro-interface generator. In fact, the micro-interface generator is a specific form of the micro-interface generator, whether it is a hydraulic micro-interface generator or a gas-liquid linkage micro-interface generator, however, the micro-interface generator adopted in the present invention is not limited to the above forms, and 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 adopt.
Furthermore, the prior patent 201710766435.0 states that the principle of the bubble breaker is that high-speed jet flows are used to achieve mutual collision of gases, and also states that the bubble breaker can be used in a micro-interface strengthening reactor to verify the correlation between the bubble breaker and the micro-interface generator; moreover, in the prior patent CN106187660, there is a related description on the specific structure of the bubble breaker, see paragraphs [0031] to [0041] in the specification, and the accompanying drawings, which illustrate the specific working principle of the bubble breaker S-2 in detail, the top of the bubble breaker is a liquid phase inlet, and the side of the bubble breaker is a gas phase inlet, and the liquid phase coming from the top provides the entrainment power, so as to achieve the effect of breaking into ultra-fine bubbles, and in the accompanying drawings, the bubble breaker is also seen to be of a tapered structure, and the diameter of the upper part is larger than that of the lower part, and also for better providing the entrainment power for the liquid phase.
Since the micro-interface generator was just developed in the early stage of the prior patent application, the micro-interface generator was named as a micro-bubble generator (CN201610641119.6), a bubble breaker (201710766435.0) and the like in the early stage, and is named as a micro-interface generator in the later stage along with the continuous technical improvement, and the micro-interface generator in the present invention is equivalent to the micro-bubble generator, the bubble breaker and the like in the prior art, and has different names.
In summary, the micro-interface generator of the present invention belongs to the prior art, although some bubble breakers belong to the type of pneumatic bubble breakers, some bubble breakers belong to the type of hydraulic bubble breakers, and some bubble breakers belong to the type of gas-liquid linkage bubble breakers, the difference between the types is mainly selected according to the different specific working conditions, and in addition, the connection between the micro-interface generator and the reactor and other equipment, including the connection structure and the connection position, is determined according to the structure of the micro-interface generator, which is not limited.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the reaction system for preparing ethylene glycol by using the ethylene oxide method, the micro-interface units are arranged on the outer side of the stirrer and in the reactor, so that ethylene oxide is crushed into micro-bubbles before reacting with a water source, the phase boundary mass transfer area between ethylene oxide and the water source is increased, and the problems of high reaction pressure and low liquid hourly space velocity caused by the fact that ethylene oxide and the water source cannot be fully mixed in the reactor in the prior art are solved;
(2) the reaction method is simple and convenient to operate, the ethylene glycol obtained by the reaction has high purity and wide application, the application range of the ethylene glycol is improved, and the method is worthy of wide popularization and application.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1 is a schematic structural view of a reaction system provided in example 1 of the present invention;
FIG. 2 is a schematic structural view of a reaction system provided in example 2 of the present invention;
fig. 3 is a schematic structural diagram of a reaction system provided in example 3 of the present invention.
Description of the drawings:
11-a water source storage tank; 12-ethylene oxide external channel;
13-a reactor; 131-a built-in micro-interface generator;
132-liquid reciprocal channel; 14-a light component removal tower;
141-light fraction outlet; 142-a heavy ends outlet;
15-a rectification column; 151-overhead condenser;
152-a raw material recycle outlet; 16-a glycol storage tank;
17-a first delivery pump; 18-a second delivery pump;
19-external micro-interface generator; 20-stirring kettle.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In order to more clearly illustrate the technical solution of the present invention, the following description is made in the form of specific embodiments.
Example 1
Referring to fig. 1, a reaction system for preparing ethylene glycol by an ethylene oxide process according to an embodiment of the present invention mainly includes a stirred tank 20 and a reactor 13, an external micro-interface unit is disposed on a side surface of the stirred tank 20, the micro-interface unit is composed of a plurality of external micro-interface generators 19, the external micro-interface generators 19 are sequentially disposed from top to bottom, a connecting rod for fixing is connected between a bottom surface and a top surface between adjacent external micro-interface generators 19, and the number of the external micro-interface generators 19 is preferably 4.
A main pipeline leading into the external micro-interface unit is simultaneously connected with an ethylene oxide feeding pipeline and two branch pipelines of a water source feeding pipeline, and the water source feeding pipeline is connected with the external micro-interface generator through a first delivery pump 17; ethylene oxide and a water source enter the micro-interface generator to be used for crushing ethylene oxide gas into micro-bubbles at a micron level;
the ethylene oxide feeding pipeline is connected with an ethylene oxide external channel 12 to provide a raw material source for the ethylene oxide to enter the external micro-interface unit 19, and the water source feeding pipeline is connected with a water source storage tank 11 to provide a raw material source for the water source entering the external micro-interface unit 19;
50kg of NaHCO3 dosage is filled into the stirring kettle 20 in advance, and is conveyed into the reactor 13, the system is started, the temperature of the reactor 13 is set to 78 ℃, and the pressure is set to 0.8 MPa;
the external micro-interface generator breaks ethylene oxide into micro-bubbles with micron-scale, so that the ethylene oxide is fully contacted with a water source in a micro-bubble state and is conveyed to the stirring kettle 20, NaHCO3 agent pre-filled in the stirring kettle 20 is stirred with the water source and the ethylene oxide micro-bubbles, a reaction liquid after being stirred from the stirring kettle 20 enters the reactor 13 from a reaction liquid inlet through a pipeline from an overflow pipe after reaching the kettle top, the reaction is further carried out in the reactor 13, an ethylene oxide feeding hole is formed in the side face of the internal micro-interface generator 131 in the reactor 13, and in order to enable the internal micro-interface generator 131 to be more stable, supports are specially arranged on two sides of the internal micro-interface generator 131 and are fixed in the reactor.
The reaction produces ethylene glycol and also produces byproducts such as methanol, acetaldehyde and the like.
The reacted reaction product is conveyed to a light component removal tower 14 to remove light components, the light components and heavy components are separated, light components such as methanol and acetaldehyde are distilled out from a light component outlet 141 at the top of the tower, heavy components such as water source and ethylene glycol are left at the bottom of the tower, the heavy components are conveyed out from a heavy component outlet 142 to a rectifying tower 15, the water source is left at the bottom of the rectifying tower 15 and is conveyed out from a raw material circulating outlet 152 arranged at the bottom of the rectifying tower 15 and is conveyed back to the reactor 13 through a second conveying pump 18 to realize recycling, the ethylene glycol is distilled out from the top of the rectifying tower 15, one part of the ethylene glycol flows back through a tower top condenser 151, and the other part of the ethylene glycol is directly extracted to an ethylene glycol storage tank 16 to be stored.
In the above embodiment, the micro-interface generator converts the pressure energy of the gas and/or the kinetic energy of the liquid into the surface energy of the bubbles and transmits the surface energy of the bubbles to the bubbles, so that the bubbles are broken into micro-bubbles with a diameter of more than or equal to 1 μm and less than 1mm, and the micro-bubbles are divided into a pneumatic micro-interface generator, a hydraulic micro-interface generator and a gas-liquid linkage micro-interface generator according to an energy input mode or a gas-liquid ratio, wherein the pneumatic micro-interface generator is driven by gas, and the input gas amount is far greater than the liquid amount; the hydraulic micro-interface generator is driven by liquid, and the input air quantity is generally smaller than the liquid quantity; the gas-liquid linkage type micro-interface generator is driven by gas and liquid at the same time, and the input gas amount is close to the liquid amount. The micro-interface generator 131 is one or more of a pneumatic micro-interface generator, a hydraulic micro-interface generator and a gas-liquid linkage micro-interface generator.
In order to increase the dispersion and mass transfer effects, additional micro-interface generators can be additionally arranged, the installation position is not limited actually, the micro-interface generators can be arranged externally or internally, and the micro-interface generators can be arranged on the side wall in the reactor in a relative mode when the micro-interface generators are arranged internally, so that micro-bubbles discharged from the outlet of each micro-interface generator can be subjected to opposite impact.
In the above embodiment, the number of the pump bodies is not specifically required, and the pump bodies may be arranged at corresponding positions as required.
Finally, the yield of ethylene glycol is detected, and the conversion rate of ethylene oxide is calculated to be 98%.
Example 2
Referring to fig. 2, in this embodiment, the number of the external micro-interface generators 19, the temperature of the system, and the pressure are different from those in embodiment 1, the number of the micro-interface generators in this embodiment is 4, each 2 is divided into two groups, the two groups are sequentially arranged from top to bottom, 2 of each group of the micro-interface generators 131 are connected in series, the two groups are connected in parallel, the temperature of the system is set to 95 ℃, and the pressure is set to 2.0 MPa. Ethylene glycol production was monitored and ethylene oxide conversion was calculated to be 97%.
Example 3
Referring to fig. 3, the number of the external micro-interface generators 19, the temperature of the system, and the pressure are different in this embodiment from those in embodiment 1, the number of the micro-interface generators in this embodiment is 3, and the micro-interface generators are sequentially arranged from top to bottom, the micro-interface generators are connected in parallel, the temperature of the system is 86 ℃, and the pressure is 1.4 MPa. Ethylene glycol production was monitored and ethylene oxide conversion was calculated to be 97%.
Comparative example 1
The specific operation steps are the same as those of the example 1, but the micro-interface generator 131 is not arranged, and the ethylene oxide and the water source are directly introduced into the reactor 1 to react. Ethylene glycol production was monitored and ethylene oxide conversion was calculated to be 88%.
Comparative example 2
The specific operation steps are the same as those of the example 2, except that the micro-interface generator 131 is not arranged, and the ethylene oxide and the water source are directly introduced into the reactor 1 to react. Ethylene glycol production was monitored and ethylene oxide conversion was calculated to be 86%.
Comparative example 3
The specific operation steps are the same as those of the example 3, except that the micro-interface generator 131 is not arranged, and the ethylene oxide and the water source are directly introduced into the reactor 1 to react. Ethylene glycol production was monitored and ethylene oxide conversion was calculated to be 83%.
Obviously, comparing the above examples 1 to 3 with the comparative examples 1 to 3, it can be seen that the use of the micro-interface generator outside the stirred tank and inside the reactor 13 in the examples increases the mass transfer area of the phase boundary between the ethylene oxide and the water source during the reaction, so that the ethylene oxide is reacted after being sufficiently contacted with the water source in the micro-bubble state, and the yield of the product ethylene glycol is significantly higher than that of the comparative examples.
In a word, after the micro-interface generators are arranged on the outer side of the stirring kettle and in the reactor, on one hand, the reaction system can disperse and crush materials into micro bubbles, so that the phase interface area between a gas phase and a liquid phase is increased, the mass transfer space is fully satisfied, the retention time of gas in the liquid phase is increased, the energy consumption is reduced, and the reaction efficiency is improved; on the other hand, the operation temperature and pressure in the reactor are reduced, and the safety and stability of the whole reaction system are improved.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A micro-interface reaction system for preparing ethylene glycol by an ethylene oxide method is characterized by comprising the following steps: a reactor and a stirred tank, wherein NaHCO is filled in the stirred tank3Dosing;
a micro-interface unit is arranged on the outer side of the stirring kettle and is formed by arranging a plurality of external micro-interface generators; the main pipeline which is led into the micro-interface unit is simultaneously connected with an ethylene oxide feeding pipeline and two branch pipelines of a water source pipeline, the ethylene oxide is led into the micro-interface unit from the gas source conveying pipeline, and the water source enters the interior of the micro-interface unit and is used for crushing ethylene oxide gas into micro-bubbles with micron level;
a reaction material liquid inlet is formed in the bottom of the reactor and is communicated with the stirring kettle through an overflow pipe, a built-in micro-interface generator is arranged in the reactor, and an ethylene oxide feeding hole is formed in the built-in micro-interface generator and is used for dispersing and crushing ethylene oxide into micro bubbles under the condition that the reaction material liquid is used as a medium;
and (3) the reaction product reacted from the reactor enters a light component removal tower to remove light components, and then enters a rectifying tower to be rectified to obtain the ethylene glycol.
2. The micro-interface reaction system according to claim 1, wherein the number of the external micro-interface generators is 4, the external micro-interface generators are arranged from top to bottom, a liquid reciprocal channel is arranged between the adjacent micro-interface generators, and the liquid reciprocal channel realizes the circulation of gas and liquid in the micro-interface generators.
3. The micro-interface reaction system according to claim 1, wherein the number of the external micro-interface generators is 4, each 2 of the external micro-interface generators is divided into two groups, and the two groups are arranged in sequence from top to bottom, 2 of each group of the micro-interface generators are connected in series, the two groups are connected in parallel, a liquid reciprocal channel is arranged between the adjacent micro-interface generators, and the liquid reciprocal channel realizes the circulation of gas and liquid in the micro-interface generators.
4. The micro-interface reaction system according to claim 1, wherein the number of the external micro-interface generators is 3, the external micro-interface generators are arranged from top to bottom, a liquid reciprocal channel is arranged between the adjacent micro-interface generators, and the liquid reciprocal channel realizes the circulation of gas and liquid in the micro-interface generators.
5. The micro-interface reaction system of claim 1, wherein the water source feed line is connected to a water source storage tank to provide a water source for the water source entering the external micro-interface generator; the ethylene oxide feeding pipeline is connected with an ethylene oxide external channel so as to provide an ethylene oxide gas source for the ethylene oxide to enter the external micro-interface generator.
6. The micro-interface reaction system according to any one of claims 1 to 5, wherein the top of the light component removal column is provided with a light component outlet for discharging light components, and the bottom of the light component removal column is provided with a heavy component outlet communicated with the side wall of the rectification column for further rectifying the ethylene glycol.
7. The micro-interface reaction system according to any one of claims 1 to 5, wherein a raw material recycling outlet is arranged at the bottom of the rectifying tower, and the water source is returned to the reactor from the raw material recycling outlet to realize recycling of raw materials.
8. The micro-interface reaction system according to any one of claims 1 to 5, wherein the top of the rectifying tower is provided with an overhead condenser, and a part of the substance condensed from the overhead condenser is returned to the rectifying tower, and the other part of the substance goes to a glycol storage tank.
9. The reaction method of the micro-interfacial reaction system for preparing ethylene glycol by using the ethylene oxide process according to any one of claims 1 to 8, comprising the steps of:
mixing ethylene oxide and a water source, carrying out micro-interface dispersion and crushing, reacting, removing light, rectifying to obtain ethylene glycol, and collecting.
10. The reaction method of a micro-interfacial reaction system according to claim 9, wherein the temperature of the reaction is 78 to 95 ℃ and the pressure of the reaction is 0.8 to 2.0 MPa.
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