CN209237968U - A kind of system of continuous preparation high concentration high-quality sodium methyl mercaptide - Google Patents
A kind of system of continuous preparation high concentration high-quality sodium methyl mercaptide Download PDFInfo
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Abstract
The application provides a kind of system of continuous preparation high concentration high-quality sodium methyl mercaptide, the system comprises the first order absorption device (1) being connected and sponge oil units (2), the level-one discharge port (12) is connected to the feed inlet of level-one mixing arrangement (3), the level-one escape vents (14) are connected to the feed inlet of second level mixing arrangement (4), the secondary discharge port (22) is connected to the feed inlet of level-one feed inlet (11) and second level mixing arrangement (4) respectively, the two-phase high concentration raw material for being used to prepare sodium methyl mercaptide is directly sufficiently reacted in multistage reactor, the method is that pre-reaction is carried out in second level mixing arrangement (4), secondary response is carried out in first-stage reactor, so that the raw material fully reacting in liquid-phase system, and and oxygen, carbon dioxide etc. easily causes the substance of side reaction Isolation, to directly prepare high concentration sodium methyl mercaptide solution.
Description
Technical field
The application belongs to sodium methyl mercaptide production technology field, in particular to a kind of continuous preparation high concentration high-quality methyl mercaptan
The system of sodium.
Background technique
Sodium methyl mercaptide is a kind of common industrial chemicals, for convenient for controlling production technology, most of chemical industry is raw
Produce using sodium methyl mercaptide solution as a raw material for production, still, sodium methyl mercaptide chemical property activity is not easy to maintain, easily and air
In oxygen reaction generate dimethyl disulfide impurity.Solid sodium methyl mercaptide contains compared with multi-crystallization water, is not easy to crush, uses Shi Yaojia
Heat could use after melting, and not easy to package, and smell is very big, be easy to cause environmental pollution, therefore, make using sodium methyl mercaptide
Sodium methyl mercaptide solution is typically directly bought for the enterprise of raw material.
Since at normal temperature, the saturated concentration of sodium methyl mercaptide is about 20wt% or so, concentration, which continues growing, is transporting and is storing up
It is easy to precipitate crystal during depositing, result in blockage pipeline and sodium methyl mercaptide solution content inaccuracy, therefore, commercially available sodium methyl mercaptide
The concentration of solution is generally in 20wt%, that is, aqueous 80wt% or so in this sodium methyl mercaptide commodity, this not only causes sodium methyl mercaptide
The industrial water amount of production firm is big, and conevying efficiency is low, and transportation cost is high, moreover, sodium methyl mercaptide solution user is under production
The wastewater flow rate generated when swimming product is also big.
For example, the sodium methyl mercaptide solution of Ningxia methionine company production and sales 20wt%, main sales territory is in Jiangsu and Zhejiang Provinces one
Hundred freight charges of folding of band, northwest client are about 1500 yuan/ton, and hundred freight charges of folding of East China client are about 4000 yuan/ton.
It in addition, some clients need to use the sodium methyl mercaptide solution of high concentration as raw material, but is 20wt% by concentration
Sodium methyl mercaptide be concentrated into the method that aimed concn generallys use vacuum distillation, under condition of negative pressure, sodium methyl mercaptide is water-soluble at its
Decomposing in liquid can accelerate, and be continuously generated gaseous methyl mercaptan, meanwhile, in condition of negative pressure, the methyl mercaptan of generation can constantly escape dense
Compression system promotes decomposition reaction constantly to carry out, and eventually leads to and is unable to reach aimed concn, but also can make in sodium methyl mercaptide solution
Generate the impurity such as a large amount of sodium hydroxides.
Therefore, a kind of method for needing to develop directly preparation high concentration sodium methyl mercaptide solution.
Utility model content
The application provides a kind of system of continuous preparation high concentration sodium methyl mercaptide, uses hydrogen by control preparation process condition
The sodium methyl mercaptide solution that sodium oxide molybdena and methyl mercaptan directly prepare high concentration reduces soft water to reduce the transportation cost of product
It uses, and then reduces discharge of wastewater, with good economic efficiency and environmental benefit.
System provided by the present application includes the first order absorption device 1 and sponge oil unit 2 being connected, and is inhaled in the level-one
The bottom of receiving apparatus 1 offers level-one feed inlet 11, level-one discharge port 12 and outlet for product 13, in the first order absorption device
1 top offers level-one escape vents 14, offers second level feed inlet 21 in the bottom of the sponge oil unit 2 and second level goes out
Material mouth 22 is provided with level-one mixing arrangement 3 in 1 entrance of first order absorption device, is arranged in 2 entrance of sponge oil unit
There is second level mixing arrangement 4, the level-one discharge port 12 is connected to the feed inlet of level-one mixing arrangement 3, the level-one escape vents 14
It is connected to the feed inlet of second level mixing arrangement 4, the secondary discharge port 22 mixes dress with level-one feed inlet 11 and second level respectively
Set 4 feed inlet connection.
System provided by the present application, is provided with insulating layer outside all devices, and all devices include that level-one is inhaled
Receiving apparatus 1, sponge oil unit 2 and the pipeline and valve that are connected to first order absorption device 1 and sponge oil unit 2.
Wherein, the level-one mixing arrangement 3 and second level mixing arrangement 4 are Liqiud-gas mixing device, keep gas-liquid mixed abundant.
In a kind of achievable mode, the system also includes the oxygen content detectors for oxygen content in detection architecture
5, it is preferable that be set on first order absorption device 1.
In another achievable mode, the system also includes the dioxies for carbon dioxide content in detection architecture
Change carbon content detector 6, it is preferable that be set on first order absorption device 1.
In another achievable mode, the system also includes the hydrogen sulfide for hydrogen sulfide content in detection architecture
Content detection instrument 7, it is preferable that be set on first order absorption device 1.
In a kind of achievable mode, can according to it is following attend school continuously prepared using system provided by the present application it is highly concentrated
It spends sodium methyl mercaptide: preparing the sodium methyl mercaptide solution of the first concentration with sodium hydroxide solution and methyl mercaptan gas；To the first concentration
It is passed through methyl mercaptan gas in sodium methyl mercaptide solution, prepares the sodium methyl mercaptide solution of aimed concn；During the preparation process, described in control
Oxygen content is lower than default oxygen content in preparation system, and keeps the temperature to preparation system；Wherein, the first concentration is lower than or waits
In aimed concn.
In a kind of achievable mode, the concentration of the sodium hydroxide solution is 10wt~50wt%, preferably 30wt%
~50wt%；And/or default oxygen content is the total volume based on gas in the preparation system, oxygen in the preparation system
Volume fraction be 2%, preferably 1%；And/or during the preparation process, hydrogen sulfide and dioxy in preparation system are stated described in control
The total content of change carbon is less than 2%, and preferably smaller than 1%, wherein the total content of the hydrogen sulfide and carbon dioxide is based on the system
The total volume of gas in standby system, the sum of hydrogen sulfide and the volume fraction of carbon dioxide in the preparation system.
In a kind of achievable mode, the sodium methyl mercaptide of the first concentration is prepared with sodium hydroxide solution and methyl mercaptan gas
Solution specifically includes: sodium hydroxide solution is added into second level premixed device, is passed through methyl mercaptan into level-one premixed device, it will be by level-one
The methyl mercaptan that absorption plant 1 escapes is passed through in second level premixed device, mixes the sodium hydroxide solution in the second level premixed device
With methyl mercaptan gas, mixed mixed system is injected in sponge oil unit 2.
In a kind of achievable mode, it is passed through methyl mercaptan gas in the sodium methyl mercaptide solution to the first concentration, is made
The sodium methyl mercaptide solution of standby aimed concn specifically includes: keeping the temperature to sponge oil unit 2, by what is formed in sponge oil unit 2
In sodium methyl mercaptide and sodium hydroxide mixed solution system injection level-one premixed device；In the level-one premixed device mix methyl mercaptan with
The mixed solution system injected by sponge oil unit 2, mixed system is injected in first order absorption device 1, to first order absorption
Device 1 is kept the temperature；Sodium hydrate content in first order absorption device 1 is monitored, when the content of sodium hydroxide in the system is lower than default
After naoh concentration, preparation system is drawn into first order absorption device 1.
In a kind of achievable mode, the holding temperature of sponge oil unit 2 is 30 DEG C~50 DEG C, preferably 35 DEG C~
40℃；And/or the holding temperature of first order absorption device 1 is 35 DEG C~55 DEG C, preferably 40 DEG C~45 DEG C.
In a kind of achievable mode, the default naoh concentration is the total weight based on the system, described
The content of sodium hydroxide is 1wt% in system；And/or the heat preservation closed container of obtained product injection nitrogen envelope；And/or obtained product
Concentration be 20wt%~50wt%.
In a kind of achievable mode, controls oxygen content in the preparation system and be included in out lower than default oxygen content
Before opening reaction, inert gas is passed through into preparation system, and/or, if oxygen content is higher than default oxygen content in preparation system,
Inert gas is then passed through into preparation system.
Specifically, high concentration sodium methyl mercaptide is continuously prepared using system provided by the present application, comprising the following steps:
Step 1, it is passed through inert gas into preparation system from first order absorption device 1, removes the oxygen in preparation system；
Step 2, after the oxygen content in preparation system is lower than default oxygen content, hydrogen-oxygen is added into second level premixed device
Change sodium solution, is passed through methyl mercaptan into level-one premixed device, the methyl mercaptan escaped by first order absorption device 1 is passed through second level premixed device
In, the sodium hydroxide solution and methyl mercaptan gas are mixed in the second level premixed device, mixed mixed system is injected
In sponge oil unit 2；
Step 3, sponge oil unit 2 is kept the temperature, the sodium methyl mercaptide formed in sponge oil unit 2 is mixed with sodium hydroxide
It closes in solution system injection level-one premixed device；
Step 4, the mixed solution body for mixing methyl mercaptan in the level-one premixed device and being injected by sponge oil unit 2
System, mixed system are injected in first order absorption device 1, are kept the temperature to first order absorption device 1；
Step 5, sodium hydrate content in first order absorption device 1 is monitored, when the content of sodium hydroxide in the system is lower than
After default naoh concentration, preparation system is drawn into first order absorption device 1.
Wherein, in step 2, presetting oxygen content is the total volume based on gas in the preparation system, described to prepare body
Oxygen content in system is 2%, preferably 1%；And/or the concentration of the sodium hydroxide solution is 10wt~50wt%, preferably
30wt%~50wt%.In step 3, the holding temperature of sponge oil unit 2 is 30 DEG C~50 DEG C, preferably 35 DEG C~40 DEG C.
In step 4, the holding temperature of first order absorption device 1 is 35 DEG C~55 DEG C, preferably 40 DEG C~45 DEG C.It is described default in step 5
Naoh concentration is the total weight based on the system, and the content of sodium hydroxide is 1wt% in the system；Product note is made
Enter the heat preservation closed container of nitrogen envelope；The concentration that product is made is 20wt%~50wt%.
The concentration of the sodium methyl mercaptide solution prepared using preceding method is 20wt%~50wt%, wherein sodium hydroxide
Content is lower than 1wt%, and the concentration of the by-product dimethyl disulfide is lower than 0.1wt%.
System provided by the present application can be transformed i.e. using equipment used in traditional preparation methods in key position
Can, for example, increasing the pipeline for being passed through inert gas, increases attemperator, increase the lift etc. of mixing pump, it is original without removing
Equipment farthest saves construction cost.
System provided by the present application makes the preparation of methyl mercaptan be divided into second order reaction, using inert gas as protection gas, with
High-concentration sodium hydroxide solution and methyl mercaptan gas are that initial feed directly prepares high concentration sodium methyl mercaptide solution, and utilizes reaction
Itself release heat product is kept the temperature so that high concentration sodium methyl mercaptide solution do not have solute precipitation, remain compared with
High concentration, meanwhile, control sodium methyl mercaptide solution concentration in the reasonable scope, so that the viscosity for controlling sodium methyl mercaptide solution is suitable for
Downstream user uses.
Detailed description of the invention
Fig. 1 is according to a kind of system that the continuous preparation high concentration high-quality sodium methyl mercaptide exemplified is preferably implemented of the application
Schematic diagram.
Description of symbols
1- first order absorption device, 11- level-one feed inlet, 12- level-one discharge port, 13- outlet for product, 14- level-one ease gas
Mouthful, 2- sponge oil unit, 21- second level feed inlet, 22- secondary discharge port, 3- level-one mixing arrangement, 4- second level mixing arrangement,
5- oxygen content detector, 6- carbon dioxide content detector, 7- hydrogen sulfide content detector.
Specific embodiment
It is described in detail below by the utility model, the characteristics of the utility model and advantage will be with these explanations
And it becomes more apparent from, is clear.
The utility model described below.
Fig. 1 is a kind of process flow chart of preferred embodiment of the application, as shown in Figure 1, continuous preparation provided by the present application
The system of high concentration sodium methyl mercaptide includes the first order absorption device 1 and sponge oil unit 2 being connected.
In the present embodiment, level-one feed inlet 11, level-one discharge port 12 are offered in the bottom of the first order absorption device 1
With outlet for product 13, level-one escape vents 14 are offered in the tower top of the first order absorption device 1, wherein level-one feed inlet 11
Mixed system for injecting methyl mercaptan raw material into first order absorption device 1 and being injected by sponge oil unit 2.
Wherein, the methyl mercaptan raw material can be methyl mercaptan gas, or the gas gas mixture containing methyl mercaptan or
Person's air-liquid combination, for example, can be pure methyl mercaptan gas, or the gaseous mixture for methyl mercaptan and nitrogen.
The mixed system injected by sponge oil unit 2 is sodium methyl mercaptide and sodium hydroxide mixed solution, for two
The system formed after being reacted in the grade reaction of absorption plant 2.
The level-one discharge port 12 is for making the shape in first order absorption device 1 of the mixed system in first order absorption device 1
At self-loopa, that is, first order absorption device 1 is discharged by level-one discharge port 12 in the system in first order absorption device 1, then mixed via level-one
It attaches together and sets 3 by level-one feed inlet 11 into first order absorption device 1, thus, make the system in first order absorption device 1 continuous
In cyclic process, sodium hydroxide molecule in liquid phase sufficiently with methyl mercaptan molecular collision so that the hydrogen-oxygen in mixed system
Change sodium sufficiently to react with methyl mercaptan, to obtain high concentration sodium methyl mercaptide solution.
The outlet for product 13 is for being discharged finished product, when the system in first order absorption device 1 is former with methyl mercaptan
After material sufficiently reacts the sodium methyl mercaptide solution of obtained aimed concn, the outlet for product 13 is opened, collects product.
In the present embodiment, the level-one discharge port 12 can be for by first order absorption device 1 with the outlet for product 13
Two sub- discharge ports that the upper same discharge port branches away install valve on every sub- discharge port, wherein a son goes out respectively
Material mouth is connected to level-one feed inlet 11, as level-one discharge port 12, another sub- discharge port and the reservoir for containing product, i.e.,
For outlet for product 13.
In the present embodiment, the first order absorption device 1 can be that any one is used for gas liquid reaction in the prior art
Absorption plant, such as: column plate type absorption plant, packing material absorbing device, stirring are bubbled absorption plant etc..
In a kind of achievable mode, 1 entrance of first order absorption device is provided with level-one mixing arrangement 3, institute
Level-one mixing arrangement 3 is stated for mixing sufficiently methyl mercaptan raw material with the mixed system injected by sponge oil unit 2.Described one
Grade mixing arrangement 3 can in the prior art any one be used for gas-liquid mixed mixing arrangement, for example, static mixing device,
Steam-water mixing device.
In a kind of achievable mode, the system also includes the oxygen content detectors for oxygen content in detection architecture
5。
In another achievable mode, the system also includes the dioxies for carbon dioxide content in detection architecture
Change carbon content detector 6.
In another achievable mode, the system also includes the hydrogen sulfide for hydrogen sulfide content in detection architecture
Content detection instrument 7.
In the present embodiment, second level feed inlet 21 and secondary discharge port are offered in the bottom of the sponge oil unit 2
22, wherein the second level feed inlet 21 is opened on the side wall of the sponge oil unit 2, for injecting sodium hydroxide raw material,
The sodium hydroxide raw material can be sodium hydroxide solution, and the concentration of the sodium hydroxide solution can be high-concentration sodium hydroxide
Solution, such as weight fraction are the sodium hydroxide solution of 50wt%.
In the present embodiment, the sodium hydroxide raw material does not use sodium hydrate solid, to increase reaction speed and to anti-
The control force answered.
The secondary discharge port 22 is opened in the tower bottom of the sponge oil unit 2, the secondary discharge port 22 respectively with
The feed inlet connection of the feed inlet and first order absorption device 1 of sponge oil unit 2, thus, make the liquid in sponge oil unit 2
Phase system fully absorbs the methyl mercaptan gas escaped by first order absorption device 1, so that realizing tail gas zero-emission in sponge oil unit 2
It puts.In addition, enabling the self-loopa inside and outside sponge oil unit 2 of the mixed system in sponge oil unit 2 that second level to be made to absorb dress
The concentration for setting the methyl mercaptan in 2 in mixed system is improved to reasonable range, when the mixed system in sponge oil unit 2 enters
After first order absorption device 1, remaining sodium hydroxide in the mixed system can be with the methyl mercaptan gas that is passed through first order absorption device 1
Impurity content qualification, target product concentration target product up to standard is made in sufficiently reaction.
In a kind of achievable mode, 2 entrance of sponge oil unit is provided with second level mixing arrangement 4.With it is described
Level-one mixing arrangement 3 is similar, and the second level mixing arrangement 4 is for mixing sufficiently methyl mercaptan gas with sodium hydroxide raw material.Institute
State second level mixing arrangement 4 can in the prior art any one be used for gas-liquid mixed mixer, for example, static mixer,
Steam heater.
System provided by the present application, is provided with insulating layer outside all devices, and all devices include that level-one is inhaled
Receiving apparatus 1, sponge oil unit 2 and the pipeline and valve that are connected to first order absorption device 1 and sponge oil unit 2.
In the present embodiment, the level-one discharge port 12 is connected to the feed inlet of level-one mixing arrangement 3, further, institute
It states secondary discharge port 22 to be connected to the feed inlet of level-one feed inlet 11 and second level mixing arrangement 4 respectively, the level-one escape vents
14 are connected to the feed inlet of second level mixing arrangement 4, enable and are introduced directly into second level suction by the methyl mercaptan in first order absorption device 1
In receiving apparatus 2, harmless treatment can either be carried out to the tail gas that first order absorption device 1 generates, while can also inhale using level-one
Low concentration sodium methyl mercaptide solution is made in exhaust gas in receiving apparatus 1 in sponge oil unit 2, so as in level-one mixing arrangement 3
High concentration sodium methyl mercaptide solution is made more quickly.
High concentration sodium methyl mercaptide is continuously prepared using system provided by the present application, mainly includes following chemical reaction:
Main reaction: CH3SH+NaOH→CH3SNa+H2O
Side reaction: 4CH3SNa+O2+2H2O→2C2H6S2+4NaOH
H2S+2NaOH→Na2S+2H2O
CO2+2NaOH→Na2CO3+H2O
High concentration sodium methyl mercaptide is continuously prepared using system provided by the present application, is mainly comprised the steps that
The sodium methyl mercaptide solution of the first concentration is prepared with sodium hydroxide solution and methyl mercaptan gas；
It is passed through methyl mercaptan gas into the sodium methyl mercaptide solution of the first concentration, prepares the sodium methyl mercaptide solution of aimed concn；
During the preparation process, control in the preparation system oxygen content and be lower than default oxygen content, and to preparation system into
Row heat preservation；Wherein, the first concentration is below or equal to aimed concn.
Wherein, the concentration of raw materials used sodium hydroxide solution is 10wt%~50wt%, preferably 30wt%~50wt%, institute
Stating sodium hydroxide solution can be the solution after deoxygenation, or the solution of non-deoxygenation.
In a kind of achievable mode, the default oxygen content is the totality based on gas in the preparation system
Long-pending, the volume fraction of oxygen is 2%, preferably 1% in the preparation system.
Further, during the preparation process, it is small that the total content of hydrogen sulfide and carbon dioxide in preparation system is stated described in control
In 2%, preferably smaller than 1%, wherein the total content of the hydrogen sulfide and carbon dioxide is based on gas in the preparation system
Total volume, the sum of hydrogen sulfide and the volume fraction of carbon dioxide in the preparation system are miscellaneous to reduce vulcanized sodium, sodium carbonate etc.
Matter, to improve product quality.
In a kind of achievable mode, the sodium methyl mercaptide of the first concentration is prepared with sodium hydroxide solution and methyl mercaptan gas
Solution specifically includes: sodium hydroxide solution is added into second level premixed device, is passed through methyl mercaptan into level-one premixed device, it will be by level-one
The methyl mercaptan that absorption plant 1 escapes is passed through in second level premixed device, mixes the sodium hydroxide solution in the second level premixed device
With methyl mercaptan gas, mixed mixed system is injected in sponge oil unit 2.
In a kind of achievable mode, it is passed through methyl mercaptan gas in the sodium methyl mercaptide solution to the first concentration, is made
The sodium methyl mercaptide solution of standby aimed concn specifically includes: keeping the temperature to sponge oil unit 2, by what is formed in sponge oil unit 2
In sodium methyl mercaptide and sodium hydroxide mixed solution system injection level-one premixed device；In the level-one premixed device mix methyl mercaptan with
The mixed solution system injected by sponge oil unit 2, mixed system is injected in first order absorption device 1, to first order absorption
Device 1 is kept the temperature；Sodium hydrate content in first order absorption device 1 is monitored, when the content of sodium hydroxide in the system is lower than default
After naoh concentration, preparation system is drawn into first order absorption device 1.
In a kind of achievable mode, the holding temperature of sponge oil unit 2 is 30 DEG C~50 DEG C, preferably 35 DEG C~
40℃。
The holding temperature of first order absorption device 1 is 35 DEG C~55 DEG C, preferably 40 DEG C~45 DEG C.
In a kind of achievable mode, the default naoh concentration is the total weight based on the system, described
The content of sodium hydroxide is 1wt% in system；And/or the heat preservation closed container of obtained product injection nitrogen envelope.
The concentration that product is made is 20wt%~50wt%.
It is arranged using the waste water that high concentration sodium methyl mercaptide prepared by method provided by the present application can significantly reduce downstream user
High-volume, it is calculated so that concentration is the sodium methyl mercaptide solution of 20wt% and 40wt% as an example, the sodium methyl mercaptide solution of 1 ton of 20wt%
4 tons of waste water are at least generated, and the sodium methyl mercaptide solution of 1 ton of 40wt% at least generates 1.5 tons of waste water, comparatively, first sulphur per ton
Alcohol sodium solution at least 2.5 tons of waste water of emission reduction.Since a large amount of hydrogen sulfide, and the odor threshold of hydrogen sulfide may be contained in waste water downstream
It is low, that is, the hydrogen sulfide of low content will make one to be clearly felt that stink, and therefore, the pressure of environmental protection can be mitigated by reducing discharge of wastewater.
It is elaborated below in conjunction with a kind of achievable scheme and prepares high concentration high-quality using system provided by the present application
The method of sodium methyl mercaptide:
Step 1, inert gas is passed through into preparation system from first order absorption device 1, for example, nitrogen, helium etc. remove system
Oxygen and carbon dioxide in standby system.In the present embodiment, the oxygen removed in preparation system includes by preparation system
In oxygen content to be reduced to volume fraction be 1% hereinafter, 1% or less carbon dioxide.Since target product sodium methyl mercaptide is easy
The solubility of sodium methyl mercaptide in sodium methyl mercaptide solution product is reduced by the carbon dioxide reaction generation sodium carbonate in air, so that
The concentration of sodium methyl mercaptide reduces at identical temperature, also, can introduce impurity in the product, and therefore, scheme provided by the present application exists
The oxygen and carbon dioxide in preparation system are removed before production, in advance to reduce the Probability of side reaction.
Step 2, after the oxygen content in preparation system is lower than default oxygen content, hydrogen-oxygen is added into second level premixed device
Change sodium solution, is passed through methyl mercaptan into level-one premixed device, the methyl mercaptan escaped by first order absorption device 1 is passed through second level premixed device
In, the sodium hydroxide solution and methyl mercaptan gas are mixed in the second level premixed device, mixed hybrid system is injected
In sponge oil unit 2.
In the present embodiment, it is provided with oxygen content monitoring device in the system, thus the oxygen in real-time monitoring system
Content.After the oxygen content in preparation system is lower than default oxygen content, e.g., the default oxygen content is based on the preparation
The total volume of gas in system, the volume fraction of oxygen is 2%, preferably 1% in the preparation system, the oxygen in system with
Reaction between methyl mercaptan will not have an impact the quality of product, therefore, when the oxygen content in preparation system is lower than default
After oxygen content, starting reaction.
Gas raw material methyl mercaptan is passed through preparation system by first-stage reactor, enters second level via first order absorption device 1 and mixes
Device 4, the solution materials sodium hydroxide solution is passed directly into second level mixing arrangement 4, in second level mixing arrangement 4, first sulphur
Alcohol gas is sufficiently mixed with sodium hydroxide solution, and mixed system is passed through again in sponge oil unit 2, and in sponge oil unit 2
In further mix, the mixed system a part flowed out by sponge oil unit 2 is led back in second level mixing arrangement 4, formed second level
The self-loopa of mixing arrangement 4- sponge oil unit 2, makes the system in sponge oil unit 2 mix more uniformly, hydroxide
Sodium solution mixes more abundant with methyl mercaptan gas, and then realizes the zero-emission of methyl mercaptan.
In a kind of achievable mode, the speed that is passed through of the methyl mercaptan raw material is 1600~2000m3/h。
In the present embodiment, the concentration of the sodium hydroxide solution be 10wt%~50wt%, preferably 30wt%~
50wt%.When the concentration of sodium hydroxide solution is lower than 10wt%, after especially less than 30wt%, sodium methyl mercaptide solution obtained
Concentration is lower than 20wt%, the sodium methyl mercaptide solution of aimed concn can not directly be made, when concentration of sodium hydroxide solution is higher than
After 50wt%, the excessive concentration of sodium methyl mercaptide solution obtained, the viscosity of solution is excessive, downstream client can not normal use, and
And concentration is temperature sensitive higher than the sodium methyl mercaptide solution of 50wt%, temperature i.e. crystallization in a slight decrease, it is high to thermal requirements,
Easy crystallization in transportational process causes the substantial concentration of solution to reduce.
In a kind of achievable mode, the speed that is passed through of the sodium hydroxide raw material is 30m3/h。
Further, applicants have discovered that, the solubility of sodium methyl mercaptide is not only related with temperature, but also produces with sodium methyl mercaptide
The content of sodium carbonate is related in product, as shown in embodiment 1 to 4, under the same conditions, the concentration of sodium carbonate in sodium methyl mercaptide product
Bigger, the solubility of sodium methyl mercaptide is smaller, and the sodium carbonate in sodium methyl mercaptide product mostlys come from sodium methyl mercaptide and titanium dioxide
Carbon reaction, therefore, the carbon dioxide in preparation system can be also replaced using the oxygen in inert gas replacement preparation system, dropped
The concentration of carbon dioxide in low preparation system, to reduce due to asking of reducing of sodium methyl mercaptide solubility caused by carbon dioxide
Topic.
Step 3, sponge oil unit 2 is kept the temperature, the sodium methyl mercaptide formed in sponge oil unit 2 is mixed with sodium hydroxide
It closes in solution system injection level-one premixed device.
Since methyl mercaptan can discharge a large amount of heat during reacting and generating sodium methyl mercaptide with sodium hydroxide, in general,
Manufacturer will discharge these heats, and the applicant utilizes these heats, carry out to the reaction system in sponge oil unit 2
Heat preservation, so that reaction system temperature with higher when entering first order absorption device 1.
In the present embodiment, the holding temperature of the sponge oil unit 2 be 30 DEG C~50 DEG C, preferably 35 DEG C~40
DEG C, so that sodium methyl mercaptide solubility with higher in sponge oil unit 2.
It is imported in second level mixing arrangement 4 by mixed system another part that sponge oil unit 2 is discharged, so that the mixing
System is further reacted in level-one mixing arrangement 3 with methyl mercaptan, and absorption of the remaining sodium hydroxide as methyl mercaptan in system is made
Agent is fully converted into sodium methyl mercaptide.
In a kind of achievable mode, the speed of the injection level-one mixing arrangement 3 of the mixed system is 30m3/h。
Step 4, methyl mercaptan and sodium hydroxide solution are mixed in the level-one premixed device, mixed system injects level-one
In absorption plant 1, first order absorption device 1 is kept the temperature.
In level-one mixing arrangement 3, it is passed directly into the methyl mercaptan gas of level-one mixing arrangement 3 and by sponge oil unit 2
The mixed system of importing mixes, and is passed through in first order absorption device 1 after mixing, the sodium hydroxide in methyl mercaptan raw material and mixed system
Reaction, generates the sodium methyl mercaptide solution of high concentration.
In the present embodiment, methyl mercaptan is exothermic reaction with reacting for sodium hydroxide, using itself institute's thermal discharge of reaction
So that the temperature of reaction system is constant within a preset range, and such as 30 DEG C~55 DEG C, further, so that the temperature of the reaction system
Degree is constant at 40 DEG C~45 DEG C, is precipitated from solution to avoid sodium methyl mercaptide.
Solution a part that first order absorption device 1 is discharged is back in level-one mixing arrangement 3, is continued anti-with methyl mercaptan gas
It answers, so that the sodium hydroxide in liquid-phase system is sufficiently reacted with methyl mercaptan, to keep the sodium hydrate content in liquid-phase system low
In default naoh concentration, and then obtain the sodium methyl mercaptide solution of low impurity content.
Step 5, sodium hydrate content in first order absorption device 1 is monitored, when the content of sodium hydroxide in the system is up to standard
Afterwards, preparation system is drawn into first order absorption device 1.
The content for monitoring sodium hydroxide in 1 liquid phase feed of first order absorption device, when the content of sodium hydroxide is lower than preset value
Afterwards, it is believed that the sodium hydroxide in system reacts completely, can be used as product outflow preparation system.
In a kind of achievable mode, the rate of outflow of the product is 30m3/h。
In the present embodiment, the default naoh concentration is the total weight based on the system, hydrogen in the system
The content of sodium oxide molybdena is 1wt%.
In the present embodiment, the heat preservation closed container of product injection nitrogen envelope is made, further makes sodium methyl mercaptide product and sky
Air bound is to reduce sodium methyl mercaptide and oxygen or carbon dioxide reaction and decompose, or even causing sodium methyl mercaptide solubility to drop
Low problem.
In the present embodiment, the above method is used the concentration of product to be made as 20wt%~50wt%, sodium hydrate content
Lower than 1wt%, solution state can be remained in a long time, and no crystal is precipitated.
Applicants have discovered that using method provided by the present application prepare sodium methyl mercaptide solution can a step directly prepare it is highly concentrated
Sodium methyl mercaptide solution is spent, preparation method is easy, high concentration sodium methyl mercaptide solution can be efficiently prepared, without passing through low concentration-
The substep preparation method of high concentration, thus, it avoids in concentration process sodium methyl mercaptide and oxygen or carbon dioxide etc. from reacting and leads
Concentration failure is caused, the generation of impurity dimethyl disulfide in system is also avoided, improves the quality of sodium methyl mercaptide solution.Further,
Due to the increase of sodium methyl mercaptide solution concentration, the usage amount of light-water in raw material is reduced, and then reduces the generation of downstream client waste water
Amount, this not only saves the production preparation cost of sodium methyl mercaptide, reduces transportation cost, also the wastewater treatment of reduction downstream client at
This, in summary, method provided by the present application significantly reduces economic cost and Environmental costs.
Embodiment
The preparation of 1 30wt% sodium methyl mercaptide solution of embodiment
(1) it is passed through inert gas into preparation system from sponge oil unit 2, removes the oxygen in preparation system；
(2) it when the oxygen content in preparation system is lower than 1%, is added into the premixed device of sponge oil unit 2
The sodium hydroxide solution of 23wt%, by first order absorption device 1 drainage come methyl mercaptan be passed through sponge oil unit 2 second level premix
In device, the sodium hydroxide solution and methyl mercaptan gas, mixed hybrid system injection are mixed in the second level premixed device
In sponge oil unit 2；
(3) keeping the temperature in sponge oil unit 2 is 35 DEG C~40 DEG C, is fully absorbed methyl mercaptan, no methyl mercaptan
Tail gas discharge, by the sodium methyl mercaptide generated in sponge oil unit 2 and sodium hydroxide mixed solution system injection first order absorption dress
It sets in 1 level-one premixed device；
(4) it is passed through methyl mercaptan into level-one premixed device, mixes methyl mercaptan with the sodium hydroxide in the level-one premixed device,
In mixed system injection first order absorption device 1, keeping the temperature in first order absorption device 1 is 45 DEG C~50 DEG C；
(5) methyl mercaptan gas not reacted completely is introduced into second level premixed device, monitors and prepares system in first order absorption device 1
Preparation system is drawn first order absorption after the content of sodium hydroxide in the system is lower than 1wt% by the sodium hydrate content of system
Device 1, the heat preservation closed container of injection nitrogen envelope.
Particularly, the charging rate and the product rate of outflow for controlling the preparation system, so that in the preparation system
Reaction reaches dynamic equilibrium, realizes the continuous production of 30wt% sodium methyl mercaptide.
In the present embodiment, the sodium methyl mercaptide solution product flowed out by first order absorption device 1 detects the product in kettle out
The weight percent of middle sodium methyl mercaptide is 30wt%, and the weight percent of sodium hydroxide is lower than 1wt%, and kettle temperature degree is 40 out
DEG C -45 DEG C, in the heat preservation closed container (holding temperature is 17 DEG C or more) after transport 20h, sodium methyl mercaptide in the solution
Weight percent is still 30wt%, and the content of impurity dimethyl disulfide is lower than 0.2wt%, does not have solid precipitation in system.
Since sodium methyl mercaptide can generate by-product sodium carbonate with carbon dioxide reaction micro in air, the present inventor exists
The sodium carbonate solid stirring of 0.5wt% (total weight of solution is received based on methyl mercaptan) is added in the sodium methyl mercaptide solution of 30wt%,
When the temperature of system drops to 26 DEG C, a large amount of solids can be precipitated in system, the sodium carbonate solid stirring of 0.1wt% is added, when being
When the temperature of system drops to 20 DEG C, a large amount of solids can be precipitated in system, and the sodium methyl mercaptide solution of the 30wt% of sodium carbonate is not added,
It can be precipitated crystal when the temperature of system is reduced to 17 DEG C, that is, at 26 DEG C hereinafter, the crystallization state of system can be intuitively
The content of sodium carbonate in reflection system.
The preparation of 2 40wt% sodium methyl mercaptide solution of embodiment
(1) it is passed through inert gas into preparation system from sponge oil unit 2, removes the oxygen in preparation system；
(2) it when the oxygen content in preparation system is lower than 1%, is added into the premixed device of sponge oil unit 2
The sodium hydroxide solution of 33wt%, by first order absorption device 1 drainage come methyl mercaptan be passed through sponge oil unit 2 second level premix
In device, the sodium hydroxide solution and methyl mercaptan gas, mixed hybrid system injection are mixed in the second level premixed device
In sponge oil unit 2；
(3) keeping the temperature in sponge oil unit 2 is 35 DEG C~40 DEG C, is fully absorbed methyl mercaptan, no methyl mercaptan
Tail gas discharge, by the sodium methyl mercaptide generated in sponge oil unit 2 and sodium hydroxide mixed solution system injection first order absorption dress
It sets in 1 level-one premixed device；
(4) it is passed through methyl mercaptan into level-one premixed device, mixes methyl mercaptan with the sodium hydroxide in the level-one premixed device,
In mixed system injection first order absorption device 1, keeping the temperature in first order absorption device 1 is 40 DEG C~45 DEG C；
(5) methyl mercaptan gas not reacted completely is introduced into second level premixed device, monitors and prepares system in first order absorption device 1
Preparation system is drawn first order absorption after the content of sodium hydroxide in the system is lower than 1wt% by the sodium hydrate content of system
Device 1, the heat preservation closed container of injection nitrogen envelope.
Particularly, the charging rate and the product rate of outflow for controlling the preparation system, so that in the preparation system
Reaction reaches dynamic equilibrium, realizes the continuous production of 40wt% sodium methyl mercaptide.
In the present embodiment, the sodium methyl mercaptide solution product flowed out by first order absorption device 1 detects the product in kettle out
The weight percent of middle sodium methyl mercaptide is 40wt%, and the weight percent of sodium hydroxide is lower than 1wt%, and kettle temperature degree is 40 out
DEG C -45 DEG C, in the heat preservation closed container (holding temperature is 32 DEG C or more) after transport 20h, sodium methyl mercaptide in the solution
Weight percent is still 40wt%, and the content of impurity dimethyl disulfide is lower than 0.2wt%, does not have solid precipitation in system.
Since sodium methyl mercaptide can generate by-product sodium carbonate with carbon dioxide reaction micro in air, the present inventor exists
The sodium carbonate solid stirring of 0.5wt% (total weight of solution is received based on methyl mercaptan) is added in the sodium methyl mercaptide solution of 40wt%,
When the temperature of system drops to 38 DEG C, a large amount of solids can be precipitated in system, the sodium carbonate solid stirring of 0.1wt% is added, when being
When the temperature of system drops to 34 DEG C, a large amount of solids can be precipitated in system, and the sodium methyl mercaptide solution of the 40wt% of sodium carbonate is not added,
It can be precipitated crystal when the temperature of system is reduced to 32 DEG C, that is, at 38 DEG C hereinafter, the crystallization state of system can be intuitively
The content of sodium carbonate in reflection system.
The preparation of 3 50wt% sodium methyl mercaptide solution of embodiment
(1) it is passed through inert gas into preparation system from sponge oil unit 2, removes the oxygen in preparation system；
(2) it when the oxygen content in preparation system is lower than 1%, is added into the premixed device of sponge oil unit 2
The sodium hydroxide solution of 45wt%, by first order absorption device 1 drainage come methyl mercaptan be passed through sponge oil unit 2 second level premix
In device, the sodium hydroxide solution and methyl mercaptan gas, mixed hybrid system injection are mixed in the second level premixed device
In sponge oil unit 2；
(3) keeping the temperature in sponge oil unit 2 is 35 DEG C~40 DEG C, is fully absorbed methyl mercaptan, no methyl mercaptan
Tail gas discharge, by the sodium methyl mercaptide generated in sponge oil unit 2 and sodium hydroxide mixed solution system injection first order absorption dress
It sets in 1 level-one premixed device；
(4) it is passed through methyl mercaptan into level-one premixed device, mixes methyl mercaptan with the sodium hydroxide in the level-one premixed device,
In mixed system injection first order absorption device 1, keeping the temperature in first order absorption device 1 is 40 DEG C~45 DEG C；
(5) methyl mercaptan gas not reacted completely is introduced into second level premixed device, monitors and prepares system in first order absorption device 1
Preparation system is drawn first order absorption after the content of sodium hydroxide in the system is lower than 1wt% by the sodium hydrate content of system
Device 1, the heat preservation closed container of injection nitrogen envelope.
Particularly, the charging rate and the product rate of outflow for controlling the preparation system, so that in the preparation system
Reaction reaches dynamic equilibrium, realizes the continuous production of 50wt% sodium methyl mercaptide.
In the present embodiment, the sodium methyl mercaptide solution product flowed out by first order absorption device 1 detects the product in kettle out
The weight percent of middle sodium methyl mercaptide is 40wt%, and the weight percent of sodium hydroxide is lower than 1wt%, and kettle temperature degree is 40 out
DEG C -45 DEG C, in the heat preservation closed container (holding temperature is 38 DEG C or more) after transport 20h, sodium methyl mercaptide in the solution
Weight percent is still 40wt%, and the content of impurity dimethyl disulfide is lower than 0.2wt%, does not have solid precipitation in system.
Since sodium methyl mercaptide can generate by-product sodium carbonate with carbon dioxide reaction micro in air, the present inventor exists
The sodium carbonate solid stirring of 0.5wt% (total weight of solution is received based on methyl mercaptan) is added in the sodium methyl mercaptide solution of 50wt%,
When the temperature of system drops to 45 DEG C, a large amount of solids can be precipitated in system, the sodium carbonate solid stirring of 0.1wt% is added, when being
When the temperature of system drops to 40 DEG C, a large amount of solids can be precipitated in system, and the sodium methyl mercaptide solution of the 50wt% of sodium carbonate is not added,
It can be precipitated crystal when the temperature of system is reduced to 38 DEG C, that is, at 45 DEG C hereinafter, the crystallization state of system can be intuitively
The content of sodium carbonate in reflection system.
First is absorbed using the sodium hydroxide solution of various concentration it can be seen from the data of above embodiments 1 to embodiment 3
Mercaptan, available various concentration, as the sodium methyl mercaptide solution of the sodium methyl mercaptide solution of 30wt%-50wt%, various concentration needs
It can be precipitated in guarantee system without crystal under different heat-retaining conditions.Further, applicants have discovered that, carbonic acid in system
The content of sodium has bigger influence to the saturated concentration of sodium methyl mercaptide, moreover, because sodium methyl mercaptide may be with the oxygen in air
Solid/liquid/gas reactions generate impurity dimethyl disulfide, so needing to carry out preparation system before methyl mercaptan is passed through sodium hydroxide solution
Deoxygenation, for example, the air in inert gas replacement system is passed through into preparation system, thus, prevent sodium hydroxide from absorbing excessive
Carbon dioxide production sodium carbonate, influence the solubility of sodium methyl mercaptide, moreover, prevent preparation sodium methyl mercaptide life is reacted with oxygen
At impurity dimethyl disulfide.
Using traditional preparation method as control, the applicant carries out economic benefit estimation to scheme provided by the present application,
As a result as follows:
In July, 2017 in June, 2018 sodium methyl mercaptide total sales volume is 42705t (percentage amount: 8541t), wherein northwest
19180t is sold in area, and 11231t is sold in Jiangsu Anhui section, and 12294t is sold in Shandong Henan Hebei section；According to freight charges northwest
Area 200 yuan/t of member meter, Jiangsu, the 850 yuan/t in Anhui province meter, Shandong, the 850 yuan/t in Henan Hebei Province meter；8 yuan/t of soft water, no
With under sodium methyl mercaptide content transportation cost and soft water cost, results of comparison it is as shown in table 1 below:
The economic benefit results of comparison of the scheme provided by the present application of table 1 and traditional scheme
Wherein, gross freight be calculated so that the weight of solute sodium methyl mercaptide in each concentration sodium methyl mercaptide solution is identical, for example,
The gross freight of the 20wt% sodium methyl mercaptide solution of the 1t containing sodium methyl mercaptide is 2383.2 ten thousand yuan/year, the 30wt% of the 1t containing sodium methyl mercaptide
The gross freight of sodium methyl mercaptide solution is 1588.8 ten thousand yuan/year, the gross freight of the 40wt% sodium methyl mercaptide solution of the 1t containing sodium methyl mercaptide
For 1191.6 ten thousand yuan/year, the gross freight of the 50wt% sodium methyl mercaptide solution of the 1t containing sodium methyl mercaptide is 953.3 ten thousand yuan/year, due under
Swimming purchaser's payment is that clearing payment is carried out on the basis of the weight of solute sodium methyl mercaptide, therefore, it will be apparent that, is used by table 1
High concentration sodium methyl mercaptide solution provided by the present application can greatly save freight charges when producing the sodium methyl mercaptide of identical weight.
Secondly, be commercially available and obtain preparing sodium hydroxide solution used in sodium methyl mercaptide, the generally hydrogen of high concentration
Sodium hydroxide solution needs to be diluted to the sodium hydroxide solution of high concentration using soft water the hydrogen-oxygen of low concentration according to traditional scheme
Change sodium solution, not only increases the cost of purchase soft water, but also waste water can be brought for downstream purchaser.Using side provided by the present application
Case not only reduces the usage amount of soft water, moreover, reducing wastewater treatment pressure for downstream purchaser.
Combine detailed description and exemplary example that the application is described in detail above, but these explanations are simultaneously
It should not be understood as the limitation to the application.It will be appreciated by those skilled in the art that without departing from the application spirit and scope,
A variety of equivalent substitution, modification or improvements can be carried out to technical scheme and embodiments thereof, these each fall within the application
In the range of.The protection scope of the application is determined by the appended claims.
Claims (6)
1. a kind of system of continuous preparation high concentration high-quality sodium methyl mercaptide, which is characterized in that the system comprises what is be connected
First order absorption device (1) and sponge oil unit (2) offer level-one feed inlet in the bottom of the first order absorption device (1)
(11), level-one discharge port (12) and outlet for product (13) offer level-one ease gas at the top of the first order absorption device (1)
Mouth (14), offers second level feed inlet (21) and secondary discharge port (22) in the bottom of the sponge oil unit (2), described
It is provided with level-one mixing arrangement (3) at level-one feed inlet (11), it is mixed that second level is provided at the feed inlet of sponge oil unit (2)
It attaches together and sets (4), the level-one discharge port (12) is connected to the feed inlet of level-one mixing arrangement (3), the level-one escape vents (14)
Be connected to the feed inlet of second level mixing arrangement (4), the secondary discharge port (22) respectively with level-one feed inlet (11) and second level
The feed inlet of mixing arrangement (4) is connected to.
2. system according to claim 1, which is characterized in that be provided with insulating layer, the institute outside all devices
Having equipment includes that first order absorption device (1), sponge oil unit (2) and connection first order absorption device (1) and second level are absorbed and filled
Set the pipeline and valve of (2).
3. system according to claim 1, which is characterized in that the level-one mixing arrangement (3) and second level mixing arrangement (4)
It is Liqiud-gas mixing device.
4. system according to claim 1, which is characterized in that the system also includes for oxygen content in detection architecture
Oxygen content detector (5).
5. system according to claim 1, which is characterized in that the system also includes for carbon dioxide in detection architecture
The carbon dioxide content detector (6) of content.
6. system according to claim 1, which is characterized in that the system also includes contain for hydrogen sulfide in detection architecture
The hydrogen sulfide content detector (7) of amount.
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