CN109336052A - For producing micro- reaction system of hydrogen chloride and the hydrogen chloride production method based on the system - Google Patents

For producing micro- reaction system of hydrogen chloride and the hydrogen chloride production method based on the system Download PDF

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Publication number
CN109336052A
CN109336052A CN201811404363.6A CN201811404363A CN109336052A CN 109336052 A CN109336052 A CN 109336052A CN 201811404363 A CN201811404363 A CN 201811404363A CN 109336052 A CN109336052 A CN 109336052A
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China
Prior art keywords
hydrogen chloride
micro
hydrogen
reaction
microreactor
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CN201811404363.6A
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Chinese (zh)
Inventor
王政强
文仕敏
谢濠江
佘国华
缑可贞
高在平
王万萍
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Yibin Tianyuan Group Co Ltd
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Yibin Tianyuan Group Co Ltd
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Priority to CN201811404363.6A priority Critical patent/CN109336052A/en
Publication of CN109336052A publication Critical patent/CN109336052A/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00Halogens; Halogen acids
    • C01B7/01Chlorine; Hydrogen chloride
    • C01B7/012Preparation of hydrogen chloride from the elements

Abstract

The invention discloses a kind of for producing micro- reaction system of hydrogen chloride, it is characterized in that substituting synthetic furnace with microreactor.It furthermore include: that a, hydrogen and chlorine are passed through in micro-mixer and are sufficiently mixed the invention also discloses the hydrogen chloride production method based on the system;B mixed gas enters microreactor and reacts;C, the hydrogen chloride gas that reaction generates obtains product after cooling.The invention has the advantages that 1) hydrogen chloride product purity significantly improves compared with prior art, according to an embodiment of the invention, hydrogen chloride product purity can reach 98% or more;2) micro- reaction system structure for using of the present invention is simple, and only needing same unit device to be arranged in juxtaposition can reach scale mass production purpose, produce it is easy to control, using industrially promoting.

Description

For producing micro- reaction system of hydrogen chloride and based on the hydrogen chloride production of the system Method
Technical field
The present invention relates to a kind of hydrogen chloride synthesis technologies.
Background technique
Hydrogen chloride, molecular formula HCl are a kind of gas of colourless irritant smell, are made of chlorine atom and hydrogen atom.Its Aqueous solution is commonly called as hydrochloric acid, relative molecular mass 36.5.Mainly for the preparation of dyestuff, drug, fragrance, organic-inorganic chloride etc..
Usual hydrogen chloride gas is prepared using synthetic furnace, there is steel synthetic furnace, graphitic synthetic furnace, the free air cooling of heat transfer type But formula and two kinds of water-cooling jacket.Steel synthetic furnace holds corrosion-vulnerable at the top and bottom of furnace, and service life is short, few at present Enterprise uses.And graphitic synthetic furnace has many advantages, such as corrosion-resistant, high temperature resistant, is the mainstream synthetic furnace of current synthesising hydrogen.Example As the patent document of the production method of the entitled reagent grade hydrochloric acid of Publication No. CN1640813A describes a kind of compare more typically The method using graphitic synthetic furnace synthesising hydrogen.Using hydrogen chloride gas purity prepared by graphitic synthetic furnace be usually 91~ 94%.
Summary of the invention
For the purity for improving chlorination hydrogen production, the present invention provides a kind of for producing micro- reaction system of hydrogen chloride.
The technical scheme adopted by the invention is that: for producing micro- reaction system of hydrogen chloride, it is characterised in that: including micro- Reactor, synthetic reaction carry out in microreactor.
The gaseous mixture of hydrogen and chlorine is a kind of explosive gaseous mixture, and explosion limit is 5%~87.5% (volume hundred Divide ratio), range is very wide.In prior art, the lamp cap that chlorine and hydrogen are passed through graphite furnace simultaneously mixed after with igniting dress Igniting is set, and since two kinds of gases are there are biggish density variation, it cannot accomplish absolutely to be sufficiently mixed, and graphite furnace volume is big, Hydrogen molecule is more, chlorine molecule is also more, and contact area is big, and the heat that when burning generates is more, while the production of hydrogen chloride at present Journey is continuous production process, and hydrogen and chlorine, which constantly enter graphite furnace also, causes the risk of mixed gas part inhomogeneities to increase Add, if within the scope of explosion limit, the rapid spatial expansion of mixed gas in the confined space is easy to happen explosion.Currently The generation that technical staff is exploded in order to prevent, generally use the hydrogen that is passed through it is much more excessive than chlorine (molar ratio hydrogen: chlorine= 1.1~1.2:1) mode, in practice it has proved that the program can effectively prevent that safety accident occurs, but this scheme causes simultaneously Hydrogen content is high and lead to the reduction of chlorination hydrogen purity in chlorination hydrogen production.
In the present invention, inventor is using microreactor substitution graphitic synthetic furnace as synthesizer, due to microreactor The hydraulic diameter of microchannel is only 0.1~5mm, therefore microreactor device hydrogen is lacked by what pipeline was discharged, with chlorine Contact area very little is scattered and disappeared quickly even if the heat of generation is few within the scope of explosion limit, will not be exploded;Therefore nothing It need to ensure hydrogen much excessive the problem of also there is no security risks, it is only necessary to maintain stable reaction to carry out, make hydrogen slightly mistake Amount, as described above, the reduction of hydrogen ratio is so that therefore product purity is also improved, to realize mesh of the invention 's.Reacting the hydrogen chloride gas generated can be stand-by into hydrogen chloride buffer tank storage after hydrogen chloride cooler is cooling.
In above scheme, since the hydraulic diameter of the microchannel of microreactor is only 0.1~5mm, it is difficult to realize hydrogen Gas and chlorine are passed through microchannel simultaneously and guarantee that the uniformity in microchannel can stablize progress to guarantee to react, because This present invention is also provided with micro-mixer, is carried out in advance by the way that hydrogen and chlorine to be passed through in micro-mixer simultaneously by certain flow ratio Microreactor is entered back into after mixing, to overcome the above problem.
To prevent the temperature of microreactor excessively high, corresponding heat-exchange system can be set, reaction temperature is controlled, hold Intelligible, the common all kinds of heat-exchange systems in this field, such as circulation can be used in heat-exchange system, and specific arragement construction can To be designed according to the structure of microreactor, such as a kind of preferred scheme is inventors herein proposed in the present invention: the present invention Microreactor may include air-tight chamber and the reaction zone that is arranged in air-tight chamber, the reaction zone be provided with to A few microchannel, and hot water cyclesystem is set simultaneously, hot water cyclesystem includes the air-tightness chamber with microreactor The circulating hot water upper hose and circulating hot water return pipe of room connection.In the equipment course of work, circulating hot water passes through hot water circuit The circulating hot water upper hose of system enters in the air-tight chamber of microreactor, the microchannel internal-response object with reaction zone Indirect heat exchange occurs, is controlled reaction temperature at 1500~2500 DEG C by the hot temperature of control loop and flow, in favor of reaction It carries out and ensures safety.Hot water cyclesystem can also further be improved, such as increase liquid vapour separation equipment, heat exchange Circulating hot water afterwards forms steam mixture and passes through hot water cyclesystem recovery section heat as a vapor, and circulating hot water is then Microreactor is returned to by water supply pipeline to continue to take away heat of reaction, what the heat of recycling can be used for that steam is needed to be heated Workshop section.
As a further improvement of the present invention, temperature is respectively arranged on the inlet duct and outlet conduit of micro-mixer Detector and pressure sensor;On-line detector, temperature monitor and pressure is provided on the microreactor outlet conduit to pass Sensor, the on-line detector include hydrogen chloride purity detecting instrument and free chlorine contents detector;The hydrogen chloride buffer tank is set It is equipped with pressure sensor;In order to be monitored to production process.
The invention also discloses a kind of methods using micro- reaction system production hydrogen chloride, comprising the following steps:
A, by dry hydrogen and chlorine according to the molar ratio hydrogen of flows per unit time: chlorine=1.01~1.05:1 Ratio is passed through in micro-mixer is sufficiently mixed simultaneously, obtains mixed gas;
B, enter microreactor from the mixed gas that micro-mixer comes out, pass through igniter provocative reaction, mixed gas Reaction generates hydrogen chloride gas in microchannel, while circulating hot water passes through the circulating hot water upper hose of hot water cyclesystem Into in the air-tight chamber of microreactor, indirect heat exchange occurs with the microchannel internal-response object of reaction zone, passes through control Circulating hot water temperature processed and flow control reaction temperature at 1500~2500 DEG C;The mixed gas is in microchannel It is 5~20s by the time;
C, the hydrogen chloride gas that reaction generates obtains chlorination hydrogen production after cooling.
The production that hydrogen chloride is carried out based on micro- reaction system of the invention can be realized using this method.
The beneficial effects of the present invention are: 1) hydrogen chloride product purity significantly improves compared with prior art, according to the present invention Embodiment, hydrogen chloride product purity can reach 98% or more;2) micro- reaction system structure that the present invention uses is simple, only needs phase Being arranged in juxtaposition with cell arrangement can reach scale mass production purpose, and production is easy to control, conducive to industrially promoting.
Detailed description of the invention
Fig. 1 is of the invention for producing micro- reaction system structural schematic diagram of hydrogen chloride.
In the figure, it is marked as 1- micro-mixer, 2- microreactor, 201- air-tight chamber, 202- reaction zone, 3- chlorination are hydrogen-cooled But device, 4- hydrogen chloride buffer tank, 5- hot water cyclesystem, 501- circulating hot water upper hose, 502- circulating hot water return pipe, 6- point Fiery device, 7- circulation, 8- hydrogen gas tank, 9- chlorine pot, PI01- hydrogen pressure tank, PI02- chlorine pressure tank, PI03- are micro- Mixer outlet gas pressure, PI04- microreactor outlet gas pressure, PI05- hydrogen chloride buffer tank pressure;TI01- hydrogen Temperature, TI02- chlorine temperature, TI03- micro-mixer Outlet Gas Temperature, TIC04- microreactor Outlet Gas Temperature, TIC05- hydrogen chloride cooler outlet pipe temp;FQIC01- hydrogen flowmeter, FQIC02- cl gas flow meter;FV01- hydrogen stream Adjustable valve, FV02- chlorine flowrate regulating valve, TV01- circulating hot water regulating valve, TV02- hydrogen chloride cooler recirculated water are adjusted Valve;CICR01- on-line checking point.
Specific embodiment
Present invention will be further explained below with reference to the attached drawings and examples.
As shown in Figure 1, of the invention is used to produce micro- reaction system of hydrogen chloride, including it is sequentially connected by process pipe Micro-mixer 1, microreactor 2, hydrogen chloride cooler 3, hydrogen chloride buffer tank 4;It further include hot water cyclesystem 5, igniting dress Set 6, circulation 7, hydrogen gas tank 8 and chlorine pot 9;The hydrogen gas tank 8, chlorine pot 9 are connect with micro-mixer 1, the igniting Device 6, hot water cyclesystem 5 are connect with microreactor 2, and the circulation 7 is connect with hydrogen chloride cooler 4;It is described micro- Reactor 2 is set including air-tight chamber 201 and the reaction zone 202 being arranged in air-tight chamber 201, the reaction zone 202 It is equipped with several microchannels;The hot water cyclesystem 5 includes the circulation being connected to the air-tight chamber 202 of microreactor 2 Hot water upper hose 501 and circulating hot water return pipe 502;It is set respectively on the inlet duct and outlet conduit of the micro-mixer 1 It is equipped with temperature monitor and pressure sensor;On-line detector, temperature monitor are provided on 2 outlet conduit of microreactor And pressure sensor, the on-line detector include hydrogen chloride purity detecting instrument and free chlorine contents detector;The hydrogen chloride Surge tank 4 is provided with pressure sensor.
Embodiment one:
The production of hydrogen chloride is used for using above-mentioned apparatus according to the following steps:
(1) by Jing Guo Gan Zaochuliing hydrogen and chlorine each lead into hydrogen gas tank 8, in chlorine pot 9;Open simultaneously hydrogen and Chlorine intake valve makes hydrogen and chlorine while entering the two entrances of micro-mixer 1, regulates and controls the molar flow ratio of hydrogen and chlorine Hydrogen: chlorine=1.01:1.0 ratio is passed through micro-mixer 1 and is uniformly mixed, and obtains mixed gas;
(2) enter microreactor 2 from the mixed gas that micro-mixer 1 comes out, pass through 6 provocative reaction of igniter, mixing Gas reacts in microchannel generates hydrogen chloride gas, while circulating hot water passes through the circulating hot water of hot water cyclesystem 5 Upper hose 501 enters in the air-tight chamber 201 of microreactor 2, occurs with the microchannel internal-response object of reaction zone 202 Indirect heat exchange, the circulating hot water shape by control loop hot water temperature and flow by reaction temperature control at 1900 DEG C, after heat exchange After recycling heat generation steam by hot water cyclesystem 5 at hot water and vapor mixture, circulating hot water passes through circulating hot water and returns Water pipe 502 returns to the heat for taking away microreactor generation, and the steam pressure is 0.5MPa;The mixed gas is being reacted In microchannel is 10s by the time;
(3) enter hydrogen chloride cooler 3 by the hydrogen chloride gas that the reaction of microreactor 2 generates to store after circulating water It is stored in hydrogen chloride buffer tank 4, measuring gained hydrogen chloride product purity is 98.7%.
Embodiment two:
The production of hydrogen chloride is used for using above-mentioned apparatus according to the following steps:
(1) by Jing Guo Gan Zaochuliing hydrogen and chlorine each lead into hydrogen gas tank 8, in chlorine pot 9;Open simultaneously hydrogen and Chlorine intake valve makes hydrogen and chlorine while entering the two entrances of micro-mixer 1, regulates and controls the molar flow ratio of hydrogen and chlorine Hydrogen: chlorine=1.03:1.0 ratio is passed through micro-mixer 1 and is uniformly mixed, and obtains mixed gas;
(2) enter microreactor 2 from the mixed gas that micro-mixer 1 comes out, pass through 6 provocative reaction of igniter, mixing Gas reacts in microchannel generates hydrogen chloride gas, while circulating hot water passes through the circulating hot water of hot water cyclesystem 5 Upper hose 501 enters in the air-tight chamber 201 of microreactor 2, occurs with the microchannel internal-response object of reaction zone 202 Indirect heat exchange, the circulating hot water shape by control loop hot water temperature and flow by reaction temperature control at 2100 DEG C, after heat exchange After recycling heat generation steam by hot water cyclesystem 5 at hot water and vapor mixture, circulating hot water passes through circulating hot water and returns Water pipe 502 returns to the heat for taking away microreactor generation, and the steam pressure is 1.1MPa;The mixed gas is being reacted In microchannel is 12s by the time;
(3) enter hydrogen chloride cooler 3 by the hydrogen chloride gas that the reaction of microreactor 2 generates to store after circulating water It is stored in hydrogen chloride buffer tank 4, measuring gained hydrogen chloride product purity is 98.5%.
Embodiment three:
The production of hydrogen chloride is used for using above-mentioned apparatus according to the following steps:
(1) by Jing Guo Gan Zaochuliing hydrogen and chlorine each lead into hydrogen gas tank 8, in chlorine pot 9;Open simultaneously hydrogen and Chlorine intake valve makes hydrogen and chlorine while entering the two entrances of micro-mixer 1, regulates and controls the molar flow ratio of hydrogen and chlorine Hydrogen: chlorine=1.05:1.0 ratio is passed through micro-mixer 1 and is uniformly mixed, and obtains mixed gas;
(2) enter microreactor 2 from the mixed gas that micro-mixer 1 comes out, pass through 6 provocative reaction of igniter, mixing Gas reacts in microchannel generates hydrogen chloride gas, while circulating hot water passes through the circulating hot water of hot water cyclesystem 5 Upper hose 501 enters in the air-tight chamber 201 of microreactor 2, occurs with the microchannel internal-response object of reaction zone 202 Indirect heat exchange, the circulating hot water shape by control loop hot water temperature and flow by reaction temperature control at 2100 DEG C, after heat exchange After recycling heat generation steam by hot water cyclesystem 5 at hot water and vapor mixture, circulating hot water passes through circulating hot water and returns Water pipe 502 returns to the heat for taking away microreactor generation, and the steam pressure is 1.9MPa;The mixed gas is being reacted In microchannel is 18s by the time;
(3) enter hydrogen chloride cooler 3 by the hydrogen chloride gas that the reaction of microreactor 2 generates to store after circulating water It is stored in hydrogen chloride buffer tank 4, measuring gained hydrogen chloride product purity is 98.1%.
The above, only of the invention enumerates preferable example, does not make in any form and substantially to the present invention Limitation, it is noted that for those skilled in the art, under the premise of not departing from the method for the present invention, can also do Numerous improvement and supplement out, these are improved and supplement should also be as being considered as protection scope of the present invention.It is all not depart from the present invention Spirit and scope in the case where, when using invent revealed content above and variation, modification and the differentiation made etc. It is equivalent embodiment of the invention with variation;Meanwhile all substantial technologicals according to the present invention are appointed to made by above-described embodiment Variation, modification and the differentiation of what equivalent variations, should all belong to the technical scheme of the invention.

Claims (6)

1. micro- reaction system for producing hydrogen chloride, it is characterised in that: including microreactor (2), synthetic reaction is in micro- reaction It is carried out in device (2).
2. according to claim 1 for producing micro- reaction system of hydrogen chloride, it is characterised in that: described for producing chlorine The micro- reaction system for changing hydrogen includes by the sequentially connected micro-mixer of process pipe (1), microreactor (2), and hydrogen chloride is cooling Device (3), hydrogen chloride buffer tank (4);It further include the igniter (6) for provocative reaction.
3. according to claim 2 for producing micro- reaction system of hydrogen chloride, it is characterised in that: the microreactor (2) reaction zone (202) for including air-tight chamber (201) and being arranged in air-tight chamber (201), the reaction zone (202) it is provided at least one microchannel.
4. according to claim 3 for producing micro- reaction system of hydrogen chloride, it is characterised in that: described for producing chlorine The micro- reaction system for changing hydrogen further includes hot water cyclesystem (5), and the hot water cyclesystem (5) includes and microreactor (2) The circulating hot water upper hose (501) and circulating hot water return pipe (502) of air-tight chamber (201) connection.
5. for producing micro- reaction system of hydrogen chloride according to any claim in claim 2~4, feature exists In: temperature monitor and pressure sensor are respectively arranged on the inlet duct and outlet conduit of the micro-mixer (1);Institute It states and is provided with on-line detector, temperature monitor and pressure sensor, the on-line detector on microreactor (2) outlet conduit Including hydrogen chloride purity detecting instrument and free chlorine contents detector;The hydrogen chloride buffer tank (4) is provided with pressure sensor.
6. utilizing the method for micro- reaction system production hydrogen chloride, comprising the following steps:
A, by dry hydrogen and chlorine according to the molar ratio hydrogen of flows per unit time: chlorine=1.01~1.05:1 ratio It is passed through in micro-mixer (1) and is sufficiently mixed simultaneously, obtain mixed gas;
B, enter microreactor (2) from the mixed gas that micro-mixer (1) comes out, pass through igniter (6) provocative reaction, mixing Gas reacts in microchannel generates hydrogen chloride gas, while circulating hot water passes through the cycling hot of hot water cyclesystem (5) Water pipe (501) waterborne enters in the air-tight chamber (201) of microreactor (2), inside the microchannel of reaction zone (202) Indirect heat exchange occurs for reactant, and reaction temperature is controlled at 1500~2500 DEG C;The mixed gas is in microchannel It is 5~20s by the time;
C, the hydrogen chloride gas that reaction generates obtains chlorination hydrogen production after cooling.
CN201811404363.6A 2018-11-23 2018-11-23 For producing micro- reaction system of hydrogen chloride and the hydrogen chloride production method based on the system Pending CN109336052A (en)

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