CN108946676A - A kind of method that industrial chlorinations salt prepares thionyl chloride - Google Patents
A kind of method that industrial chlorinations salt prepares thionyl chloride Download PDFInfo
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- CN108946676A CN108946676A CN201810146107.5A CN201810146107A CN108946676A CN 108946676 A CN108946676 A CN 108946676A CN 201810146107 A CN201810146107 A CN 201810146107A CN 108946676 A CN108946676 A CN 108946676A
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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
- C01B17/00—Sulfur; Compounds thereof
- C01B17/45—Compounds containing sulfur and halogen, with or without oxygen
- C01B17/4561—Compounds containing sulfur, halogen and oxygen only
- C01B17/4584—Thionyl chloride (SOCl2)
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
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Abstract
The present invention provides a kind of methods that industrial chlorinations salt prepares thionyl chloride, comprising the following steps: S1) industrial chlorinations salt and sulfur trioxide, are reacted at 80~200 DEG C, obtain chlorosulfonate；S2) chlorosulfonate obtains sulfate and chlorine, sulfur dioxide in 300~900 DEG C of progress Pintsch process；S3) the obtained chlorine of S2) and sulfur dioxide and sulfur dichloride are mixed, is reacted under the catalytic action of active carbon, obtains thionyl chloride.The present invention uses sulfur trioxide as strong oxidizer at high temperature, and extends residence time of material, converts chlorosulfonate for abraum salt, while carrying out oxidation processes removing to the organic matter in abraum salt during reaction；Then Pintsch process is carried out, while obtaining equimolar chlorine, sulfur dioxide, can not decomposed again by high-temperature oxydation by the micro-content organism that sulfur trioxide aoxidizes, organic matter processing is more thorough, and thionyl chloride can be prepared by adding equimolar sulfur dichloride.
Description
Technical field
The present invention relates to chemical industrial waste object post-processing technology fields more particularly to a kind of industrial chlorinations salt to prepare thionyl chloride
Method.
Background technique
Major part chemical company can all generate high-salt wastewater in process of production at present, can be obtained by a series of processing
To the by-product industrial chlorinations salt for containing a small amount of organic matter, this part salt is difficult to be effectively addressed and utilize, and can only be used as dangerous waste
It handles, not only not any economic value, but also higher processing cost can be consumed, about 3000-5000 yuan/ton of expense.
The main means of processing dangerous waste are exactly to fill at present, if leakage accidentally, will cause secondary pollution.
Only a small number of chemical companies can further refine the part salt at present, improve the content of salt, but
It is that product that current technique obtains can't be directly as the raw material of downstream product.Such as by hot-blast oxidation method, treated
Its content of industrial chlorinations salt significantly improves, but cannot reach the requirement of chlorine industry, can only be used as snow-melting agent, economic value
It is lower, and exhaust gas generation is had in the process.So how industrial chlorinations salt is converted into other useful chemical products is mesh
Preceding technical problem urgently to be solved.
And conventional chlorate is reacted with sulfur trioxide, the method for generating sulfur dioxide, chlorine and sodium sulphate can generate packet
Problem is wrapped up in, the chlorosulfonate that sodium chloride and sulfur trioxide reaction generate can be wrapped in the surface of sodium chloride, and then hinder three oxidations
Sulphur further with chlorination reactant salt, causes reaction to be not thorough, and yield is lower, can be containing a large amount of not anti-in obtained chlorosulfonate
The chlorate answered causes to generate rejected product, and obtained product is not able to satisfy national standard.And the process for increasing grinding can then produce
Fecula dirt, and increase post-processing difficulty.
Thionyl chloride is mainly used for the chlorinating agent or chlorine acylating agent of organic matter, it can also be used to prepare pharmaceutical intermediate, have
The catalyst of the synthesis such as machine acid anhydrides, dyestuff intermediate is alternatively arranged as the raw material of manufacture battery.Believed according to the market of thionyl chloride
For breath data it is found that the production capacity of China's thionyl chloride is not able to satisfy domestic market needs still at present, insufficiency of supply-demand is very big.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing the side that a kind of industrial chlorinations salt prepares thionyl chloride
Method prepares thionyl chloride, and yield with higher and purity using industrial waste salt.
In order to solve the above technical problems, the present invention provides a kind of methods that industrial chlorinations salt prepares thionyl chloride, including
Following steps:
S1) industrial chlorinations salt and sulfur trioxide are reacted at 80~200 DEG C, obtain chlorosulfonate；
S2) chlorosulfonate obtains sulfate and chlorine, sulfur dioxide in 300~900 DEG C of progress Pintsch process；
S3) the obtained chlorine of S2) and sulfur dioxide and sulfur dichloride are mixed, carried out under the catalytic action of active carbon
Reaction, obtains thionyl chloride.
The present invention provides a kind of industrial chlorinations salt generated in process of production using chemical company as raw material, prepares chlorination
The method of sulfoxide is efficiently recycled industrial waste salt by adjusting suitable technique and parameter, can not only disappear
Except the influence to environment, and industrial by-product can be made to obtain secondary use, realize circular economy, generate very big industrial valence
Value.
Above-mentioned S1) reaction equation it is as follows:
SO3(l/q)+Cl-→SO3Cl-
The industrial chlorinations salt includes any one or a few in sodium chloride, potassium chloride, ammonium chloride and magnesium chloride, and
Organic matter.
In the present invention, the organic matter can be aromatic series, aliphatic category organic matter.
Wherein, the content of the organic matter is 0~3%, more preferably 0.1%~2.5%, and the content contains for quality
Amount.
The present invention is to the source of above-mentioned industrial chlorinations salt and is not particularly limited, the content of organics that general chemical company generates
0~3% chlorate.
The sulfur trioxide can be gaseous state or liquid.
Since the reaction of chlorate and sulfur trioxide is that strong exothermal reaction can pass through when using liquid sulphur trioxide
The state of sulfur trioxide changes (liquid to gaseous vaporization) and effectively removes the heat that reaction generates, and can effectively control anti-
The temperature of charge in device is answered, sharply temperature rise is avoided.
When using gaseous sulfur trioxide, heat can effectively be removed by outer circulation mode, it can also be by controlling chlorination
Salt and sulfur trioxide add rate to control the heat generated in the reacton time.
The volumetric concentration of the sulfur trioxide is 50%~100%.
Method provided by the invention is not high to the purity requirement of sulfur trioxide, when sulfur trioxide purity is 50%~100%
It can meet the requirements.When sulfur trioxide concentration is lower, such as the sulphur-containing exhaust gas of enterprise, sulfur trioxide concentration is generally 50%~
60%, also contain a large amount of inert gas impurity, these inert gases can't participate in reacting, can be up to standard after vent gas treatment
Discharge.The vent gas treatment can be the method for water absorption+Alkali absorption well known in the art.Therefore above-mentioned place provided by the invention
Reason method, can be with the sulphur-containing exhaust gas of reuse enterprise, and not only abraum salt has obtained recycling, but also also reduces the row of sulphur-containing gas
It puts, achieves many things at one stroke.
The sulphur-containing exhaust gas may include sulfur trioxide, and sulfur dioxide, air, aqueous vapor etc., reaction is preceding to give up the sulfur-bearing
Gas can be reacted through being dried, and reaction system preferably includes exhaust gas processing device, and the exhaust gas processing device can be
Desulphurization system well known in the art post-processes unreacted gas.When using the sulfur trioxide of low-purity, do not participate in
The inert gas of reaction can all enter exhaust treatment system, the qualified discharge after simple process.The simple process can be with
For water absorption+Alkali absorption well known to those skilled in the art.
The mass ratio of the industrial chlorinations salt and sulfur trioxide is preferably (50~200): (50~100), more preferably more
Preferably (80~100): (80~100).
The temperature of the reaction is preferably 80~200 DEG C, and more preferably 105~180 DEG C.Time is preferably 1~100min,
More preferably 5~50min.
For the present invention by the restriction of above-mentioned parameter, the product chlorosulfonate that reaction can be carried out quickly, while be obtained is liquid
State or molten state solve the problems, such as chlorosulfonate to the package of sodium chloride, therefore to the partial size of abraum salt without specific requirement, also with regard to nothing
Grinding pretreatment need to be carried out to abraum salt, without being ground during the reaction to chlorate, fundamentally solved
Grind a series of vent gas treatments of bring and operating environment, such as dust problem.
Further, the present invention utilizes sulfur trioxide in the strong oxidizing property of the condition of high temperature, during the reaction in abraum salt
Organic matter carry out oxidation processes removing, and then ensure that the quality of chlorosulfonate.
In addition, the chlorosulfonic acid sodium formed is liquid, it is not only convenient for the circulation conveying of material, and convenient for insoluble impurities
It removes, the chlorosulfonate of high-quality can be obtained.
Therefore after reaction, it is filtered to remove impurity, is post-processed very simple.
Then to obtained product is reacted in 300~900 DEG C of progress Pintsch process, sulfate and chlorine, titanium dioxide are obtained
Sulphur.
The temperature of the Pintsch process is more preferably 300~600 DEG C.
Obtained chlorine, sulfur dioxide molar ratio are reacted for 1:1, which just meets synthesizing chlorinated sulfoxide pair
The requirement of unstrpped gas is directly reacted there is no need to adjust chlorine, sulfur dioxide molar ratio again, and chlorination is not present
In sulfoxide synthesis process the problem of two kinds of gas input fluctuations.And the chlorine and sulfur dioxide of reaction generation are at output scene
It can be utilized, there is no the high problems of freight, less there are problems that risk in transit.Simultaneously as unstrpped gas
Molar ratio is suitable, and raw material Overdosing problems, the product of preparation purity with higher is not present.
In some embodiments of the invention, a small amount of sulfur trioxide is contained in the chlorine and sulfur dioxide that are prepared
Impurity, the present invention can increase the purified treatment step to mixed gas, such as isolate sulfur trioxide, Huo Zheyong by cooling
The concentrated sulfuric acid of sulfur dioxide absorption to saturation state absorbs sulfur trioxide, makes no longer to contain sulfur trioxide in mixed gas,
To obtain simple sulfur dioxide and chlorine.
The chlorine and sulfur dioxide, then mixed with sulfur dichloride, it is reacted under the catalytic action of active carbon
Obtain thionyl chloride.
The equation of the reaction is as follows:
The temperature of the reaction is preferably 200~250 DEG C.Reaction time is preferably 1~100min.The chlorine, dioxy
The molar ratio for changing sulphur and sulfur dichloride is 1:1:1.
In the present invention, since the combined coefficient of thionyl chloride is not 100%, so in the synthesis process of thionyl chloride not
Evitable to have fixed gas (acid gas impurities) generation, fixed gas is mainly sulfur dioxide, chlorine, a small amount of sulfur trioxide
Deng.It is currently preferred, above-mentioned acid gas impurities, a small amount of sulfur trioxide and part are removed by washing+alkali cleaning method
Sulfur dioxide becomes acidic liquid after being washed, part is not captured by the water the gas to get off, is reacted after Alkali absorption
Fall, sour gas is no longer contained in discharge gas.
It is currently preferred, purification process is carried out to the thionyl chloride being prepared by way of rectifying.
Compared with prior art, the present invention provides a kind of method that industrial chlorinations salt prepares thionyl chloride, including it is following
Step: S1) industrial chlorinations salt and sulfur trioxide, are reacted at 80~200 DEG C, obtain chlorosulfonate；S2) chlorosulfonate exists
300~900 DEG C of progress Pintsch process, obtain sulfate and chlorine, sulfur dioxide；S3) by the obtained chlorine of S2) and titanium dioxide
Sulphur and sulfur dichloride mixing, are reacted under the catalytic action of active carbon, obtain thionyl chloride.The present invention makes at high temperature
It uses sulfur trioxide as strong oxidizer, and extends residence time of material, convert chlorosulfonate for abraum salt, while in reaction
Oxidation processes removing is carried out to the organic matter in abraum salt in the process；Then Pintsch process is carried out, equimolar chlorine, dioxy are obtained
While changing sulphur, it can not decomposed again by high-temperature oxydation by the micro-content organism that sulfur trioxide aoxidizes, organic matter processing is more thorough,
Thionyl chloride can be prepared by adding equimolar sulfur dichloride, to ensure that the product of product sulfate and thionyl chloride
Matter.The technique can not only eliminate influence of the industrial chlorinations salt as solid waste to environment, can also realize industrial chlorinations salt by-product
Recycling, realize circular economy, do not have secondary pollution in production, the production requirement of green chemical industry may be implemented.By work
Industry by-product industrial chlorinations salt is turned waste into wealth, and has highly important realistic meaning and good social benefit and environmental benefit, to building
If resource-efficient and environment friendly society has great strategic significance.
Specific embodiment
In order to further illustrate the present invention, prepared by protochloride to industrial chlorinations salt provided by the invention below with reference to embodiment
The method of sulfone is described in detail.
Multiple-effect sodium chloride, multiple-effect potassium chloride, multiple-effect magnesium chloride and the multiple-effect ammonium chloride of the following embodiments of the present invention are to adopt
The high-salt wastewater that synthetic workshop generates is concentrated to give with multiple-effect evaporation or MVR equipment.
The quality of following chlorosulfonic acid sodium is to be detected by the way that chlorosulfonic acid sodium is decomposed into sodium sulphate, then be back-calculated to obtain.
The detection method of thionyl chloride are as follows: carry out gas-chromatography point according to the method in professional standard HGB/T3788-2013
Analysis.
Embodiment 1
Multiple-effect sodium chloride (containing 0.12 organic matter) 18.43g is taken into reaction unit, to maintain its temperature with oil bath device
105 DEG C, 99.9% sulfur trioxide is then slowly added into reaction unit, the addition rate of sulfur trioxide is with object in reaction unit
The temperature of material rises subject to unobvious, and the average addition rate of laboratory sulfur trioxide is 0.5g/min, is stirred to react, three oxidations
Sulphur, which is added, just can be obtained qualified intermediate material when finishing, obtain the intermediate material chlorosulfonic acid sodium 43.58g of liquid through weighing.Root
It is 25.17g according to the sulfur trioxide quality that mass balance calculates to be added.
Then obtained intermediate material is heated to 300 DEG C of progress cracking reactions, what is generated into cracking process is mixed
It closes gas and sulfur dichloride 16.20g is added, into thionyl chloride synthesizer (activated carbon catalysis, 200 DEG C of reaction temperature), reaction
It negates after the completion and remaining solid material in thionyl chloride and reaction unit obtained is answered to be analyzed:
Thionyl chloride purity is 98.4%, and yield 92%, remaining substance mainly has sulfur trioxide, hydrogen chloride etc., this batch of chlorine
Change sulfoxide products (the rectifier unit number of plates is 10, reflux ratio 4) after rectifier unit is handled, thionyl chloride purity can reach
99.1%.The molecular results of solid material in reaction unit are: sodium sulphate content 97.8%, sodium chloride content 1.71%,
Sulfur trioxide content is 0.49%.
Embodiment 2
Multiple-effect sodium chloride (containing 0.97% organic matter) 18.71g is taken into reaction unit, to maintain its temperature with oil bath device
At 150 DEG C, 50.6% sulfur trioxide is then slowly added into reaction unit, the addition rate of sulfur trioxide is in reaction unit
The temperature of material rises subject to unobvious, and the average addition rate of laboratory sulfur trioxide is 1.1g/min, is stirred to react, three oxygen
Change sulphur and the intermediate material that qualification just can be obtained when finishing is added, obtains the intermediate material chlorosulfonic acid sodium 43.87g of liquid through weighing.
It is 25.34g that the sulfur trioxide quality being added is calculated according to mass balance.
Then obtained intermediate material is heated to 300 DEG C of progress cracking reactions, the mixing generated in cracking process
Gas is added sulfur dichloride 16.32g and has reacted into thionyl chloride synthesizer (activated carbon catalysis, 220 DEG C of reaction temperature)
It is negated after and remaining solid material in thionyl chloride and reaction unit obtained is answered to be analyzed:
Thionyl chloride purity is 97.9%, and yield 88%, remaining substance mainly has sulfur trioxide, hydrogen chloride etc., this batch of chlorine
Change sulfoxide products (the rectifier unit number of plates is 10, reflux ratio 4) after rectifier unit is handled, thionyl chloride purity can reach
99.4%.The molecular results of solid material in reaction unit are: sodium sulphate content 97.91%, sodium chloride content 0.97%,
Sulfur trioxide content is 1.12%.
Embodiment 3
Multiple-effect sodium chloride (containing 2.1% organic matter) 18.87g is taken into reaction unit, to maintain its temperature with oil bath device
At 180 DEG C, 80% sulfur trioxide is then slowly added into reaction unit, the addition rate of sulfur trioxide is with object in reaction unit
The temperature of material rises subject to unobvious, and the average addition rate of laboratory sulfur trioxide is 0.87g/min, is stirred to react, three oxygen
Change sulphur and the intermediate material that qualification just can be obtained when finishing is added, obtains the intermediate material chlorosulfonic acid sodium 43.75g of liquid through weighing.
It is 25.26g according to the sulfur trioxide quality that mass balance calculates to be added.
Then obtained intermediate material is heated to 300 DEG C of progress cracking reactions, what is generated into cracking process is mixed
It closes gas and sulfur dichloride 16.26g is added, into thionyl chloride synthesizer (activated carbon catalysis, 250 DEG C of reaction temperature), reaction
It negates after the completion and remaining solid material in thionyl chloride and reaction unit obtained is answered to be analyzed:
Thionyl chloride purity is 97.4%, and yield 91%, remaining substance mainly has sulfur trioxide, hydrogen chloride etc., this batch of chlorine
Change sulfoxide products (the rectifier unit number of plates is 10, reflux ratio 4) after rectifier unit is handled, thionyl chloride purity can reach
99.4%.The molecular results of solid material in reaction unit are: sodium sulphate content 97.43%, sodium chloride content 1.01%,
Sulfur trioxide content is 1.56%.
Embodiment 4
Multiple-effect sodium chloride (containing 2.8% organic matter) 18.43g is taken into reaction unit, to maintain its temperature with oil bath device
At 150 DEG C, 99.9% sulfur trioxide is then slowly added into reaction unit, the addition rate of sulfur trioxide is in reaction unit
The temperature of material rises subject to unobvious, and the average addition rate of laboratory sulfur trioxide is 0.5g/min, is stirred to react, three oxygen
Change sulphur and the intermediate material that qualification just can be obtained when finishing is added, obtains the intermediate material chlorosulfonic acid sodium 41.41g of liquid through weighing.
It is 24.50g according to the sulfur trioxide quality that mass balance calculates to be added.
Then obtained intermediate material is heated to 600 DEG C of progress cracking reactions, what is generated into cracking process is mixed
It closes and sulfur dichloride 15.77g is added in gas, into thionyl chloride synthesizer (activated carbon catalysis, 220 DEG C of reaction temperature), instead
It should negate after the completion and remaining solid material in thionyl chloride and reaction unit obtained is answered to be analyzed:
Thionyl chloride purity is 97.3%, and yield 93%, remaining substance mainly has sulfur trioxide, hydrogen chloride etc., this batch of chlorine
Change sulfoxide products (the rectifier unit number of plates is 10, reflux ratio 4) after rectifier unit is handled, thionyl chloride purity can reach
99.3%.The molecular results of solid material in reaction unit are: sodium sulphate content 96.1%, sodium chloride content 0.91%,
Sulfur trioxide content is 2.99%.
Embodiment 5
Multiple-effect sodium chloride (containing 0.12% organic matter) 18.98g is taken into reaction unit, to maintain its temperature with oil bath device
At 150 DEG C, 99.9% sulfur trioxide is then slowly added into reaction unit, the addition rate of sulfur trioxide is in reaction unit
The temperature of material rises subject to unobvious, and the average addition rate of laboratory sulfur trioxide is 0.5g/min, is stirred to react, three oxygen
Change sulphur and the intermediate material that qualification just can be obtained when finishing is added, obtains the intermediate material chlorosulfonic acid sodium 44.98g of liquid through weighing.
It is 26g according to the sulfur trioxide quality that mass balance calculates to be added.
Then obtained intermediate material is heated to 850 DEG C of progress cracking reactions, what is generated into cracking process is mixed
It closes gas and sulfur dichloride 16.54g is added after condensation liquefaction, into thionyl chloride synthesizer (activated carbon catalysis, reaction temperature
240 DEG C of degree), it negates remaining solid material in thionyl chloride and reaction unit obtained is answered to be analyzed after the reaction was completed:
Thionyl chloride purity is 96.4%, and yield 91%, remaining substance mainly has sulfur trioxide, hydrogen chloride etc., this batch of chlorine
Change sulfoxide products (the rectifier unit number of plates is 10, reflux ratio 4) after rectifier unit is handled, thionyl chloride purity can reach
99%.The molecular results of solid material in reaction unit are: sodium sulphate content 95.12%, sodium chloride content 1.91%, three
Sulfur oxide content is 4.88%.
Embodiment 6
Multiple-effect potassium chloride (containing 1.17% organic matter) 18.13g is taken into reaction unit, to maintain its temperature with oil bath device
At 150 DEG C, 99.9% sulfur trioxide is then slowly added into reaction unit, the addition rate of sulfur trioxide is in reaction unit
The temperature of material rises subject to unobvious, and the average addition rate of laboratory sulfur trioxide is 0.5g/min, is stirred to react, three oxygen
Change sulphur and the intermediate material that qualification just can be obtained when finishing is added, obtains the intermediate material chlorosulfonic acid potassium 37.17g of liquid through weighing.
It is 19.25g according to the sulfur trioxide quality that mass balance calculates to be added.
Then obtained intermediate material is heated to 550 DEG C of progress cracking reactions, what is generated into cracking process is mixed
It closes gas and sulfur dichloride 12.39g is added after condensation liquefaction, into thionyl chloride synthesizer (activated carbon catalysis, reaction temperature
210 DEG C of degree), it negates remaining solid material in thionyl chloride and reaction unit obtained is answered to be analyzed after the reaction was completed:
Thionyl chloride purity is 97.4%, and yield 91.3%, remaining substance mainly has sulfur trioxide, hydrogen chloride etc., this batch
Sulphoxide chloride product (the rectifier unit number of plates is 10, reflux ratio 4) after rectifier unit is handled, thionyl chloride purity can reach
99%.The molecular results of solid material in reaction unit are: sulfuric acid potassium content 96.76%, KCE content 1.21%, three
Sulfur oxide content is 2.03%.
Embodiment 7
Multiple-effect magnesium chloride (containing 0.11% organic matter) 22.1g is taken into reaction unit, to make reaction unit using oil bath pan
Temperature maintains 150 DEG C, and the sulfur trioxide that gaseous state 99.9% is then slowly passed through into reaction unit is stirred to react, three oxidations
The rate that is passed through of sulphur is subject to the temperature of material in reaction unit and is increased without significant, the average addition rate of laboratory sulfur trioxide
For 0.5g/min, it is stirred to react.When the quality for being passed through sulfur trioxide is 37.1g, the substance 59.17g of chlorosulfonic acid magnesium is obtained.
Then obtained intermediate material is heated to 550 DEG C of progress cracking reactions, what is generated into cracking process is mixed
It closes gas and sulfur dichloride 23.89g is added after condensation liquefaction, into thionyl chloride synthesizer (activated carbon catalysis, reaction temperature
250 DEG C of degree), it negates remaining solid material in thionyl chloride and reaction unit obtained is answered to be analyzed after the reaction was completed:
Thionyl chloride purity is 98.34%, and yield 91.11%, remaining substance mainly has sulfur trioxide, hydrogen chloride etc., should
Sulphoxide chloride product (the rectifier unit number of plates is 10, reflux ratio 4) after rectifier unit is handled is criticized, thionyl chloride purity is reachable
To 98.76%.The molecular results of solid material in reaction unit are: sulfuric acid content of magnesium 98.13%, content of magnesium chloride are
0.91%, sulfur trioxide content 0.96%.
Embodiment 8
Multiple-effect ammonium chloride (containing 0.47% organic matter) 14.5g is taken into reaction unit, to make reaction unit using oil bath pan
Temperature maintains 95 DEG C (due to starting to decompose when ammonium chloride is heated to 100 DEG C, so the reaction temperature of the present embodiment control is 95
DEG C), the sulfur trioxide that gaseous state 99% is then slowly passed through into reaction unit is stirred to react, sulfur trioxide be passed through rate with
In reaction unit the temperature of material without significant increase subject to, the average addition rate of laboratory sulfur trioxide is 0.5g/min, is stirred
Mix reaction.When the quality for being passed through sulfur trioxide is 21.58g, the substance 36.0g of chlorosulfonic acid ammonium is obtained.
Then obtained intermediate material is heated to 550 DEG C of progress cracking reactions, what is generated into cracking process is mixed
It closes gas and sulfur dichloride 27.92g is added after condensation liquefaction, into thionyl chloride synthesizer (activated carbon catalysis, reaction temperature
220 DEG C of degree), it negates remaining solid material in thionyl chloride and reaction unit obtained is answered to be analyzed after the reaction was completed:
Thionyl chloride purity is 96.57%, and yield 90.97%, remaining substance mainly has sulfur trioxide, hydrogen chloride etc., should
Sulphoxide chloride product (the rectifier unit number of plates is 10, reflux ratio 4) after rectifier unit is handled is criticized, thionyl chloride purity is reachable
To 98.63%.The molecular results of solid material in reaction unit are: ammonium sulphate content 95.42%, chlorination are by content
3.23%, sulfur trioxide content 1.35%.
As can be seen from the above embodiments, method provided by the invention, industrial waste salt is turned waste into wealth, and the thionyl chloride prepared
Yield with higher and purity.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (9)
1. a kind of method that industrial chlorinations salt prepares thionyl chloride, comprising the following steps:
S1) industrial chlorinations salt and sulfur trioxide are reacted at 80~200 DEG C, obtain chlorosulfonate；
S2) chlorosulfonate obtains sulfate and chlorine, sulfur dioxide in 300~900 DEG C of progress Pintsch process；
S3 chlorine, sulfur dioxide and the sulfur dichloride mixing for) obtaining S2), are reacted under the catalytic action of active carbon,
Obtain thionyl chloride.
2. the method according to claim 1, wherein the industrial chlorinations salt includes sodium chloride, potassium chloride, chlorination
Any one or a few and organic matter in ammonium and magnesium chloride.
3. according to the method described in claim 2, it is characterized in that, the content of the organic matter is 0~3%.
4. the method according to claim 1, wherein the sulfur trioxide is gaseous state or liquid.
5. the method according to claim 1, wherein the volumetric concentration of the sulfur trioxide is 50%~100%.
6. the method according to claim 1, wherein the mass ratio of the industrial chlorinations salt and sulfur trioxide is
(50~200): (50~100).
7. the method according to claim 1, wherein the S1) in, the time of reaction is 1~100min.
8. the method according to claim 1, wherein the S2) in, the molar ratio of chlorine and sulfur dioxide is 1:
1。
9. the method according to claim 1, wherein the S3) in, the temperature of reaction is 200~250 DEG C.
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| CN111434398A (en) * | 2019-01-14 | 2020-07-21 | 光大绿色环保管理（深圳）有限公司 | Industrial waste salt treatment device and method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2430631A1 (en) * | 1974-06-26 | 1976-01-15 | Basf Ag | Purifying crude gaseous thionyl chloride - by contact with molten sulphur or polysulphur chlorides |
| US4388290A (en) * | 1980-06-19 | 1983-06-14 | Bayer Aktiengesellschaft | Purifying thionyl chloride with AlCl3 catalyst |
| CN1132199A (en) * | 1995-03-25 | 1996-10-02 | 山东淄川双凤化工厂 | Method for prodn. of sulfoxide chloride |
| CN106315519A (en) * | 2016-08-29 | 2017-01-11 | 山东凯盛新材料股份有限公司 | Method for preparing thionyl chloride |
-
2018
- 2018-02-12 CN CN201810146107.5A patent/CN108946676A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2430631A1 (en) * | 1974-06-26 | 1976-01-15 | Basf Ag | Purifying crude gaseous thionyl chloride - by contact with molten sulphur or polysulphur chlorides |
| US4388290A (en) * | 1980-06-19 | 1983-06-14 | Bayer Aktiengesellschaft | Purifying thionyl chloride with AlCl3 catalyst |
| CN1132199A (en) * | 1995-03-25 | 1996-10-02 | 山东淄川双凤化工厂 | Method for prodn. of sulfoxide chloride |
| CN106315519A (en) * | 2016-08-29 | 2017-01-11 | 山东凯盛新材料股份有限公司 | Method for preparing thionyl chloride |
Non-Patent Citations (5)
| Title |
|---|
| M.C.斯尼特，等: "《无机化学大纲》", 30 November 1963 * |
| W. L. FIELDER，等: "Reactions of NaCI with Gaseous SO3 , SO2 , and O2", 《JOURNAL OF THE ELECTROCHEMICAL SOCIETY》 * |
| 佟玉衡: "《实用废水处理技术》", 30 November 1998 * |
| 刘少武，等: "《硫酸工作手册》", 30 April 2001 * |
| 辽宁省石油化学工业厅: "《辽宁化工产品大全》", 31 December 1991 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111434398A (en) * | 2019-01-14 | 2020-07-21 | 光大绿色环保管理（深圳）有限公司 | Industrial waste salt treatment device and method |
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