CN116119619B - Preparation process of hydrogen bromide gas - Google Patents
Preparation process of hydrogen bromide gas Download PDFInfo
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- CN116119619B CN116119619B CN202310408944.1A CN202310408944A CN116119619B CN 116119619 B CN116119619 B CN 116119619B CN 202310408944 A CN202310408944 A CN 202310408944A CN 116119619 B CN116119619 B CN 116119619B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/093—Hydrogen bromide
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Abstract
The invention provides a preparation process of hydrogen bromide gas, and relates to the technical field of chemical synthesis. The preparation process comprises the following steps: s1: mixing sulfur and a solvent, and dropwise adding bromine at the temperature of 20-40 ℃ to obtain a first mixed product. S2: and heating the first mixed product to 75-90 ℃ and continuously dropwise adding bromine to obtain a second mixed product. S3: and cooling and discharging residues of the second mixed product to obtain hydrogen bromide gas. Wherein in the step S1, the mol ratio of sulfur to bromine is 1:0.3-0.55, and the dropping rate of bromine is 50-300 g/h. The invention discovers and utilizes the disulfide dibromide as a steady-state intermediate product in the initial reaction stage, no hydrogen bromide gas is generated in the process, a workshop gas delivery pump is not required to be started, and the energy consumption is reduced.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation process of hydrogen bromide gas.
Background
The hydrogen bromide has wide application, can be used in medicine, dye, perfume and other industries, and is also used as raw material for preparing various inorganic bromides and organic bromides, the existing method for preparing the hydrogen bromide gas has high risk, high cost and low efficiency, and the obtained hydrogen bromide gas is impure, so that how to improve the yield of the hydrogen bromide gas is an urgent problem to be solved.
The Chinese patent publication No. CN113401873B, publication No. 2021.09.17, provides a process for preparing high purity hydrogen bromide by reacting metallic bromide with chlorine gas, heating to obtain bromine, adsorbing and drying the evaporated bromine, loading the dried bromine into a fixed bed, reacting with hydrogen gas under the action of catalyst to obtain hydrogen bromide gas, adsorbing and dehydrating, and rectifying in two stages to obtain high purity hydrogen bromide. Solves the problem that the bromine is easy to have leakage risk in the feeding process.
Disclosure of Invention
The inventors found that: the process for preparing hydrogen bromide gas by using sulphur bromine method includes such steps as dropping bromine in five stages, and the purity of hydrogen bromide gas at initial stage is only 30-40%, and the purity of hydrogen bromide gas is up to above 95% for a long time, so that it is not beneficial to downstream production. The inventor researches the stability of intermediate transition products of preparing hydrogen bromide gas by sulfur, and discovers that the disulfide synthesized in the initial stage of the reaction can be used as an intermediate product in a steady state, and the disulfide is relatively stable below 40 ℃, thereby providing necessary conditions for stably outputting the hydrogen bromide gas and improving the purity of the hydrogen bromide gas.
The invention provides a preparation process of hydrogen bromide gas, which comprises the following steps:
s1: mixing sulfur and a solvent, and dropwise adding bromine at the temperature of 20-40 ℃ to obtain a first mixed product.
S2: and heating the first mixed product to 75-90 ℃ and continuously dropwise adding bromine to obtain a second mixed product.
S3: and cooling and discharging residues of the second mixed product to obtain hydrogen bromide gas.
Wherein the mol ratio of sulfur to bromine in the step S1 is 1:0.3-0.55, and the dropping rate of bromine in the step S1 is 50-300 g/h.
Compared with the prior art, the invention has at least one of the following beneficial effects:
(1) Compared with the prior art, the invention discovers and utilizes the disulfide dibromide as a steady-state intermediate product in the initial reaction stage, no hydrogen bromide gas is generated in the process of generating the steady-state intermediate product in the initial reaction stage, a workshop gas delivery pump is not required to be started, and the energy consumption is reduced.
(2) Compared with the prior art, the invention effectively reduces the loss of bromine and improves the conversion rate of bromine and the purity of hydrogen bromide by controlling the ratio of sulfur and bromine and the reaction temperature in the process of generating steady intermediate product dibromide disulfide.
(3) The high-temperature decomposition of the steady-state intermediate product disulfide in the later reaction period provides necessary conditions for the stable output of the subsequent hydrogen bromide gas and the preparation of the hydrogen bromide gas with higher purity.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and do not constitute a limitation on the invention. In the drawings:
fig. 1 shows a flow chart of the preparation process of the hydrogen bromide gas of the present invention.
Detailed Description
In order to more clearly illustrate the general inventive concept, a detailed description is given below by way of example with reference to the accompanying drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
In one exemplary embodiment of the present invention, a process for preparing hydrogen bromide gas comprises the steps of:
s1 synthesis of steady-state intermediate stage: mixing sulfur with a solvent, and dropwise adding bromine at the temperature of 20-40 ℃ to obtain a first mixed product. Wherein the molar ratio of sulfur to bromine in the step S1 is 1:0.3-0.55, and preferably the molar ratio of sulfur to bromine in the step S1 is 1:0.4-0.52. More preferably, in the step S1, the molar ratio of sulfur to bromine is 1:0.4. and (2) in the step S1, the dropping speed of bromine is 50-300 g/h. Preferably, the dropping rate of bromine in the step S1 is 80-120 g/h. The solvent may be water or hydrobromic acid at a concentration of 48%. However, the present invention is not limited thereto. The purpose of the S1 step is to obtain the steady state intermediate disulfide in the initial stages of the reaction. The inventors have found that, when the amount of bromine added in the initial stage of the reaction (step S1) is too low and bromine is added dropwise at a temperature of 20 ℃ or lower, the steady intermediate product, namely, disulfide, is less synthesized. If the amount of bromine added is too high at the initial stage of the reaction and bromine is added dropwise at a temperature of 40 ℃ or lower, a small amount of hydrogen bromide gas is produced, but the purity of the hydrogen bromide gas produced at this time is low. For example, the purity of the hydrogen bromide gas is less than 10%. If the bromine dripping speed is too high in the early reaction period, bromine overflows, and the synthesis yield of steady intermediate products is reduced. If the bromine drop rate is too slow in the initial stage of the reaction, the whole reaction takes too long.
In the invention, the feeding amount and the temperature are controlled in the step S1, so that hydrogen bromide gas is not generated basically at the stage, and mainly the disulfide dibromide is synthesized as a steady-state intermediate product in the initial stage of the reaction.
S2 steady-state intermediate decomposition stage: s1, after synthesizing a steady intermediate product, slowly heating to 75-90 ℃ and continuously dropwise adding bromine, and observing gas generation condition and gas purity. In the step S2, the purity of the hydrogen bromide gas is more than 99 percent. If the temperature is too low in the later reaction stage (S2 step), the steady-state intermediate products can be decomposed slowly; too high a temperature can result in too fast a steady-state intermediate product decomposition rate, and the hydrogen bromide gas flow is not easy to control, which is unfavorable for the use of downstream products.
The molar ratio of sulfur to bromine in the whole reaction process of the S1 and the S2 is 1:2.5-3.0, and preferably the molar ratio of sulfur to bromine in the whole reaction process of the S1 and the S2 is 1:2.9-3.0.
S3, cooling and residue removing stage: and (3) cooling and discharging the gas obtained in the step (S2) to obtain hydrogen bromide gas. Specifically, the temperature is raised to 110-120 ℃ firstly, and then the temperature is kept for 1-2 hours, and the cooling and residue removal are carried out. The conversion rate of synthesizing high-purity hydrogen bromide from bromine is 90-98%. The entire reaction process flow diagram is shown with reference to figure 1.
The reaction process comprises two steps of reactions:
s1, a first step of: the steady state intermediate product is synthesized at a temperature of less than 40 ℃ at the initial stage of the reaction.
Reaction principle: 2 S+Br 2 →S 2 Br 2 。
S2, a second step of: and heating and continuously dropwise adding bromine, and decomposing the steady intermediate product into hydrogen bromide gas.
Principle of reaction： 2S 2 Br 2 +6Br 2 →4SBr 4 ；
SBr 4 +Br 2 →SBr 6 ；
SBr 6 +4H 2 O→H 2 SO 4 +6HBr。
Example 1
The preparation process of the hydrogen bromide gas comprises the following steps:
s1: 110g of sulfur and 720g of hydrobromic acid with the concentration of 48% are added into a reaction four-mouth bottle and stirred and mixed. Bromine is dropwise added at the temperature of 25 ℃ to generate a steady intermediate product, and the dropping speed of bromine is 50-70 g/h. The drop amount of bromine is 192.5g. The molar ratio of sulfur to bromine is 1:0.35. No hydrogen bromide gas was generated during synthesis of the steady state intermediate, and no substantial change in pH above the reaction evacuation condenser was observed, with a hydrogen bromide gas purity of 0.
S2: after synthesis of the steady state intermediate in step S1, a slow temperature rise to 75 ℃ was started and 1237.6g of bromine was continuously added dropwise.
S3: and (3) heating the gas obtained in the step (S2) to 110-120 ℃, preserving heat for 1h, and then cooling and discharging residues to obtain the hydrogen bromide gas.
Example 2
On the basis of example 1, the difference is that step S1: 110g of sulfur is added into a reaction four-mouth bottle, and bromine is added dropwise at the temperature of 30 ℃ to generate a steady intermediate product. The dropping rate of bromine is 60-90 g/h, and the dropping amount of bromine is 260g. The molar ratio of sulfur to bromine is 1:0.47.
S2, step: the steady intermediate product synthesized in the step S1 is slowly heated to 80 ℃ and bromine is continuously added dropwise.
Example 3
On the basis of example 1, the difference is that step S1: 110g of sulfur is added into a reaction four-mouth bottle, and bromine is added dropwise at the temperature of 40 ℃ to generate a steady intermediate product. The dropping rate of bromine is 80-120 g/h, and the dropping amount of bromine is 220g. The molar ratio of sulfur to bromine is 1:0.4.
S2, step: the steady intermediate product synthesized in the step S1 is slowly heated to 90 ℃ and bromine is continuously added dropwise.
Comparative example 1
On the basis of example 1, the difference is that bromine is added dropwise at 45℃under control of the temperature in step S1.
Comparative example 2
On the basis of example 1, the difference is that 110g of sulfur is added into a four-mouth flask for reaction in the step S1, and bromine is added dropwise at the temperature of 25 ℃. The dropping rate of bromine is 50-70 g/h, and the dropping amount of bromine is 148.5g. The molar ratio of sulfur to bromine is 1:0.27.
Comparative example 3
On the basis of example 1, the difference is that 110g of sulfur is added into a four-mouth flask for reaction in the step S1, and bromine is added dropwise at a temperature of 25 ℃. The dropping rate of bromine is 50-70 g/h, and the dropping amount of bromine is 320g. The molar ratio of sulfur to bromine is 1:0.58.
Comparative example 4
On the basis of example 1, the difference is that 110g of sulfur is added into a four-mouth flask for reaction in the step S1, and bromine is added dropwise at a temperature of 50 ℃. The dropping rate of bromine is 50-70 g/h, and the dropping amount of bromine is 320g. The molar ratio of sulfur to bromine is 1:0.58.
Comparative example 5
On the basis of example 1, the difference is that 110g of sulfur is added into a four-mouth flask for reaction in the step S1, and bromine is added dropwise at a temperature of 50 ℃. The dropping rate of bromine is 50-70 g/h, and the dropping amount of bromine is 148.5g. The molar ratio of sulfur to bromine is 1:0.27.
The main process parameters and effects of examples 1 to 3 and comparative examples 1 to 5 were compared, and are shown in Table 1.
Table 1 table of process parameters and effects
Referring to Table 1, it can be seen from examples 1-3 that the process for preparing hydrogen bromide gas according to the present invention can ensure continuous use of downstream products by controlling the initial drop temperature of bromine and the amount of bromine to achieve a conversion rate of bromine to high purity hydrogen bromide of 90% or more and a time period from 0 to 99% or more for 30min after synthesis of steady intermediate products, wherein the purity of the subsequent gas is greater than 99%.
Comparative example 1 is mainly different from example 1 in that the dropping temperature of bromine is too high at the initial stage of the reaction of comparative example 1, the conversion rate of synthesizing high-purity hydrogen bromide from bromine is reduced by 4.6%, and the gas purity is from 0 to 99% or more for 40min.
Comparative example 2 is mainly different from example 1 in that when the dropwise addition amount of bromine is too low in the initial stage of the reaction, the synthesis content of the intermediate product in the steady state of the reaction is low and the gas purity is long when it is used from 0 to 99% or more.
The main difference between comparative example 3 and example 1 is that when the drop amount of bromine in the initial stage of reaction is too high, excessive free bromine remains in the reaction system in the initial stage of reaction and is unreacted, bromine loss is caused in the subsequent temperature raising process, and the free bromine is higher in the preparation process of hydrogen bromide gas, so that the purity of the gas is reduced, and the use of downstream products is affected.
Comparative example 4 is mainly different from example 1 in that when the amount of bromine in the initial stage of the reaction is too high and the temperature in the initial stage of the reaction is too high, the reaction rate is too high, the safety risk of the reaction exists, and meanwhile, excessive free bromine in the initial stage of the reaction remains unreacted, so that the temperature overflows from the reaction system, the free bromine in the subsequent preparation process of hydrogen bromide is higher, the gas purity is reduced, and the use of downstream products is affected.
Comparative example 5 is mainly different from example 1 in that when the bromine content is low and the reaction initial temperature is too high, the produced steady intermediate product is decomposed at the high temperature at the initial stage of the reaction, a low concentration of hydrogen bromide gas is generated, the use of downstream products is affected, and the conversion rate of bromine is reduced by 6.8%.
The foregoing is merely exemplary of the present invention and is not intended to limit the present invention. Various modifications and variations of the present invention will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are to be included in the scope of the claims of the present invention.
Claims (7)
1. A process for preparing hydrogen bromide gas, comprising the steps of:
s1: mixing sulfur and a solvent, and dropwise adding bromine at the temperature of 20-40 ℃ to obtain a first mixed product; step S1, no hydrogen bromide gas is generated in the stage;
s2: heating the first mixed product to 75-90 ℃ and continuously dropwise adding bromine to obtain a second mixed product; the purity of the hydrogen bromide gas in the second mixed product is more than 99 percent;
s3: cooling and discharging residues of the second mixed product to obtain hydrogen bromide gas;
wherein the mol ratio of sulfur to bromine in the step S1 is 1:0.3-0.55, and the dropping rate of bromine in the step S1 is 50-300 g/h.
2. The preparation process according to claim 1, wherein the temperature of the step S1 is 25-35 ℃.
3. The preparation process according to claim 1, wherein the temperature of the step S2 is 80-85 ℃.
4. The preparation process according to claim 1, wherein the molar ratio of sulfur to bromine in the step S1 is 1:0.4-0.52.
5. The process according to claim 1, wherein the molar ratio of sulfur to bromine in step S1 is 1:0.4.
6. The preparation process according to claim 1, wherein the dropping rate of bromine in the step S1 is 80-120 g/h.
7. The process according to claim 1, wherein the solvent is water or hydrobromic acid having a concentration of 48%.
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB551789A (en) * | 1940-08-10 | 1943-03-10 | Frieda Goldschmidt | Process for preparing hydrobromic acid |
| CN1126174A (en) * | 1995-01-03 | 1996-07-10 | 天津海晶集团盐化总公司 | Method for prepn. of hyrobromic acid |
| JP4362894B2 (en) * | 1999-06-15 | 2009-11-11 | 東ソー株式会社 | How to collect bromine |
| CN201325873Y (en) * | 2008-12-18 | 2009-10-14 | 山东默锐化学有限公司 | Hydrogen bromide easy preparation device |
| JP6887959B2 (en) * | 2015-02-19 | 2021-06-16 | アグロセル インダストリーズ リミテッドＡｇｒｏｃｅｌ Ｉｎｄｕｓｔｒｉｅｓ Ｌｉｍｉｔｅｄ | Process for the preparation of hydrobromic acid |
| CN104891441A (en) * | 2015-05-20 | 2015-09-09 | 山西恒一新材料技术服务有限公司 | Combined hydrogen bromide generating device and technology |
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