CN1164479C - Technology of synthesizing high concentration chlorosulfonic acid using low concentration salfur trioxide - Google Patents
Technology of synthesizing high concentration chlorosulfonic acid using low concentration salfur trioxide Download PDFInfo
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- CN1164479C CN1164479C CNB021386099A CN02138609A CN1164479C CN 1164479 C CN1164479 C CN 1164479C CN B021386099 A CNB021386099 A CN B021386099A CN 02138609 A CN02138609 A CN 02138609A CN 1164479 C CN1164479 C CN 1164479C
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Abstract
The present invention discloses a new technology for synthesizing chlorosulfonic acid with high concentration by using sulfur trioxide with low concentration, which uses sulfur trioxide with low concentration as raw materials for producing chlorosulfonic acid with high purity and adopts sulfuric acid for converting fume for directly resolving sulfur trioxide produced from fuming sulfuric acid, and the sulfur trioxide and hydrogen chloride with various concentrations are synthesized into industrial chlorosulfonic acid. The method overcomes the defects of the original high gas concentrating method and the low gas concentrating method. The present invention has the characteristics of wide concentration ranges of hydrogen chloride, low material energy consumption, high environmental protection level and safe production.
Description
Technical field
The present invention relates to a kind of chlorsulfonic acid synthesis technique.
Background technology
Present domestic chlorsulfonic acid manufacturer is numerous, and chemical combination under 150-230 ℃ temperature forms by sulphur trioxide and exsiccant hydrogen chloride gas, presses the difference of raw material sulphur trioxide concentration, is divided into low concentration gas process and high concentration gas process:
Low concentration gas process with the sulfuric acid apparatus temperature be 200-260 ℃, Sulphur Dioxide rate 90-95%, sulphur trioxide concentration be 7-10% once transform flue gas and from the volume content of chlor-alkali device by-product more than 90% or 20-60 ℃ of dry hydrogen chloride gas of volume content 25-35% temperature of Man Hamufa vitriolate of tartar device by-product be raw material,, refrigerated separation synthetic through major-minor reaction produced chlorsulfonic acid, and quality product reaches GB13549-92 premium grads standard; Tail gas successively passes through qualified discharge after sulfuric acid scrubbing, washing and the soda lye wash.The main drawback of this method is: (1) owing to sulfur dioxide concentration height in the raw material, total utilization efficiency is low.(2) because sulfurous gas is not participated in reaction, sulfur dioxide concentration is higher than the numerical value that national standard allows far away in the tail gas, will consume a large amount of alkali when carrying out soda lye wash, and waste liquid needs could discharge after treatment, and cost increases considerably.As without alkali cleaning, at all can't qualified discharge.(3) after the waste gas washing, gained dilute hydrochloric acid directly advances sewage disposal, do not recycle, and the consumption of alkali when having increased soda lye wash, also increased production cost.
High concentration gas process is mainly to utilize 8-10kg/cm
2Saturation steam or sulfuric acid conversion indirect furnace heating be the oleum of 20-30% from sulfuric acid apparatus concentration, about 150 ℃ of the temperature that evaporates, nearly 100% sulfur trioxide gas of concentration, refrigerated separation production chlorsulfonic acid synthetic through primary first-order equation with temperature 150-180 ℃ the high density dry hydrogen chloride that comes from the chlor-alkali device, quality product reaches GB13549-92 premium grads standard; Tail gas is through qualified discharge after the soda lye wash, and waste water advances Sewage treatment systems.The total utilization efficiency of traditional low concentration gas process is low though this method has overcome, the exhaust emissions amount is big and the big shortcoming of quantity of alkali consumption during soda lye wash, has reduced raw materials cost, but still defectiveness: (1) is with 8-10kg/cm
2Saturation steam or converter gas be the 20-30% oleum for the free sulphur trioxide concentration of thermal source indirect heating, about 150 ℃ of nicotinic acid temperature, although employing non-corrosive metal, equipment and materials still has bigger erosion rate, the major equipment vaporizer life-span generally is no more than 1 year, often cause irregular parking, replacement charge and difficulty are very big.(2) as adopting steam heating, vaporizer is a pressurized vessel, in case steam leakage can produce the danger of exploding in sulfuric acid.(3) as adopting the flue gas indirect heating, heating-surface area is big, and consumption of calorie is big; Liquid film skewness in the tubulation often causes local superheating, seriously corroded.(4) because equipment has bigger erosion rate, make that iron-holder is higher in the nicotinic acid after the desorb, influenced the nicotinic acid quality.(5) from the angle of heat balance, the raw material sulphur trioxide can not satisfy with heat that to adopt the low concentration hydrogen chloride that is similar to Man Hamufa vitriolate of tartar device by-product be the situation of raw material.(6) tail gas adopts alkali lye to absorb the back discharging, and the waste liquid after pickling and the washing can't return the native system recycle.
Summary of the invention
The objective of the invention is: a kind of technology that adopts the synthetic high concentration cl sulfonic acid of lower concentration sulphur trioxide is provided, this method has overcome the deficiency that the present chlorsulfonic acid of China is produced, not only the material concentration scope wide, consume lowly, and total energy approach is good, environmental protection level height, production security height.
Technical scheme of the present invention is: a kind of technology that adopts the synthetic high concentration cl sulfonic acid of lower concentration sulphur trioxide comprises the following steps:
(1) be oleum more than 28% by the free sulphur trioxide concentration of sulfuric acid apparatus production, after preliminary preheating, send into the sulphur trioxide desorption tower, under normal pressure, carry out desorb, the required latent heat of sulphur trioxide desorb is by providing from the flue gas more than 330 ℃ behind the sulfuric acid device twice transformation, behind the enhanced heat exchange mass transfer, the sulfur trioxide content that leaves desorption tower is 15-25%, temperature is that 120-140 ℃ gas mixes again with from the high temperature by-pass flue gas behind the sulfuric acid apparatus twice transformation, temperature reaches 160-230 ℃, sulphur trioxide concentration is sent to the chlorsulfonic acid synthetic tower after reaching 10-15%, and last free sulphur trioxide concentration is 15-20%, temperature be 110-130 ℃ oleum with from enter after the dense smoke of the nicotinic acid absorption system acid heat exchange sulfuric acid apparatus nicotinic acid system absorb carry dense;
(2) flue gas of hydrogen chloride gas after will heating and above-mentioned trioxygen-containing sulphur is in 0.95～1.05: 1 ratio enters synthetic tower, according to the difference of hydrogen cloride concentration, temperature of reaction is controlled between 150-220 ℃, obtains containing the gas mixture of gaseous state chlorsulfonic acid;
(3) gas mixture of synthetic tower outlet is used for heating the hydrogen chloride gas of volume content more than 20% of drying, demist in the step (2), and the hydrogen chloride gas temperature enters synthetic tower after being elevated to more than 110 ℃;
(4) the gaseous state gas mixture after heat exchange enters one subsequently and uses water-cooled cooling separator in the step (3), and cooling separator divides high temperature section and low-temperature zone, and non-condensable gases that leaves and liquid are the chlorsulfonic acid crude product;
(5) chlorsulfonic acid crude product and a part of exsiccant hydrogenchloride secondary response again obtains the chlorsulfonic acid finished product;
(6) non-condensable gases at first enters the sulfuric acid scrubbing tower with sulfuric acid absorption sulphur trioxide wherein, remaining few sulphur trioxide and hydrogenchloride adopts water to absorb the nitration mixture that makes sulfur-bearing acid group and hydrogenchloride again, nitration mixture is delivered to the hydrogenchloride that parses in the hydrogenchloride drying tower wherein in system's internal recycle utilization, hydrogenchloride drying tower and sulfuric acid scrubbing tower keep string acid, and by-product contains sulfuric chlorohydrin on a small quantity and can be used for other devices;
(7) after above-mentioned absorption, tail gas emptying up to standard after efficient mist eliminator demist.
Advantage of the present invention is:
1. in service life of equipment and security,, makes the sulphur trioxide desorption tower of developing owing to adopting the non-metallic material of improvement, low cost of manufacture, and medium contacts enhanced heat exchange and mass transfer under normal pressure.Compare with adopting the indirect falling film type heating of steam heating and flue gas, the temperature that makes nicotinic acid go out desorption tower reduces 15-25 ℃.The working temperature of nicotinic acid interchanger can reduce equally, and the erosion rate of nicotinic acid interchanger reduces significantly, has reduced the amount of iron content oleum; The equipment operation is safer, has reduced the maintenance of equipment expense, has improved economic benefit.
2. aspect energy-conservation, adopting sulfur trioxide content first is the flue gas direct heating of 1.1-1.2%, compare with high concentration gas process, not only made full use of the heat that a sulfuric acid industry part will not reclaim always, also reduced the internal circulating load of the oleum that contains the free sulphur trioxide of 20-30% to greatest extent, this workshop section's power consumption reduces about 15%; The synthetic tower exit gas is used for the hydrogen chloride gas of heat drying, has made full use of the waste heat of system, should also not have any safety problem by place's equipment simultaneously, belongs to domestic initiation.
3. aspect prepared using, adopting content of sulfur dioxide is raw material less than the flue gas of 300ppm, compares with traditional low concentration gas process, and the sulphur overall utilization improves 4.5%; The system of returning nitration mixture after waste gas absorbs continues to utilize, and the hydrogenchloride utilization ratio improves 4%, has reduced production cost.
4. aspect environmental protection, owing to advance the dense raising of synthetic tower sulfur trioxide gas, make the exhaust emissions amount reduce 1/4 than traditional low concentration gas process, content of sulfur dioxide is reduced to below the 200ppm in the tail gas, and tail gas is through demist post chlorization hydrogen 40-50mg/Nm
3, sulfuric acid mist 5-10mg/Nm
3Outstanding feature more: this technology has been saved caustic wash process, and the processing wastewater quantity discharged is zero, is better than state specified standards, belongs to cleaning procedure.
5. on device adaptability, can be fit to the hydrogenchloride that high density arrives lower concentration, be high concentration gas process can't be obtained.
Description of drawings
The invention will be further described below in conjunction with embodiment:
Fig. 1 is a process flow sheet of the present invention;
Embodiment
Embodiment: as shown in Figure 1, a kind of technology that adopts the synthetic high concentration cl sulfonic acid of lower concentration sulphur trioxide comprises the following steps:
(1) be oleum more than 28% by the free sulphur trioxide concentration of sulfuric acid apparatus production, after preliminary preheating, send into the sulphur trioxide desorption tower, under normal pressure, carry out desorb, the required latent heat of sulphur trioxide desorb is by providing from the flue gas more than 330 ℃ behind the sulfuric acid device twice transformation, behind the enhanced heat exchange mass transfer, the sulfur trioxide content that leaves desorption tower is 15-25%, temperature is that 120-140 ℃ gas mixes again with from the high temperature by-pass flue gas behind the sulfuric acid apparatus twice transformation, temperature reaches 160-230 ℃, sulphur trioxide concentration is sent to the chlorsulfonic acid synthetic tower after reaching 10-15%, and last free sulphur trioxide concentration is 15-20%, temperature be 110-130 ℃ oleum with from enter after the dense smoke of the nicotinic acid absorption system acid heat exchange sulfuric acid apparatus nicotinic acid system absorb carry dense;
(2) flue gas of hydrogen chloride gas after will heating and above-mentioned trioxygen-containing sulphur is in 0.95～1.05: 1 ratio enters synthetic tower, according to the difference of hydrogen cloride concentration, temperature of reaction is controlled between 150-220 ℃, obtains containing the gas mixture of gaseous state chlorsulfonic acid;
(3) gas mixture of synthetic tower outlet is used for heating the hydrogen chloride gas of volume content more than 20% of drying, demist in the step (2), and the hydrogen chloride gas temperature enters synthetic tower after being elevated to more than 110 ℃;
(4) the gaseous state gas mixture after heat exchange enters one subsequently and uses water-cooled cooling separator in the step (3), and cooling separator divides high temperature section and low-temperature zone, and non-condensable gases that leaves and liquid are the chlorsulfonic acid crude product;
(5) chlorsulfonic acid crude product and a part of exsiccant hydrogenchloride secondary response again obtains the chlorsulfonic acid finished product;
(6) non-condensable gases at first enters the sulfuric acid scrubbing tower with sulfuric acid absorption sulphur trioxide wherein, remaining few sulphur trioxide and hydrogenchloride adopts water to absorb the nitration mixture that makes sulfur-bearing acid group and hydrogenchloride again, nitration mixture is delivered to the hydrogenchloride that parses in the hydrogenchloride drying tower wherein in system's internal recycle utilization, hydrogenchloride drying tower and sulfuric acid scrubbing tower keep string acid, and by-product contains sulfuric chlorohydrin on a small quantity and can be used for other devices;
(7) after above-mentioned absorption, tail gas emptying up to standard after efficient mist eliminator demist.
The present invention is a raw material production high-purity chloro sulfonic acid with the lower concentration sulphur trioxide, adopt the sulfuric acid conversion flue gas directly to resolve the sulphur trioxide of oleum generation and the hydrogenchloride compound probability chlorsulfonic acid of various concentration, this method has overcome the defective of original high concentration gas process and low concentration gas process, have adapt to that the hydrogen cloride concentration scope is wide, thing can consume low, environmental protection level height and produce safer characteristics.
Claims (1)
1. a technology that adopts the synthetic high concentration cl sulfonic acid of lower concentration sulphur trioxide comprises the following steps:
(1) be oleum more than 28% by the free sulphur trioxide concentration of sulfuric acid apparatus production, after preliminary preheating, send into the sulphur trioxide desorption tower, under normal pressure, carry out desorb, the required latent heat of sulphur trioxide desorb is by providing from the flue gas more than 330 ℃ behind the sulfuric acid device twice transformation, behind the enhanced heat exchange mass transfer, the sulfur trioxide content that leaves desorption tower is 15-25%, temperature is that 120-140 ℃ gas mixes again with from the high temperature by-pass flue gas behind the sulfuric acid apparatus twice transformation, temperature reaches 160-230 ℃, sulphur trioxide concentration is sent to the chlorsulfonic acid synthetic tower after reaching 10-15%, and last free sulphur trioxide concentration is 15-20%, temperature be 110-130 ℃ oleum with from enter after the dense smoke of the nicotinic acid absorption system acid heat exchange sulfuric acid apparatus nicotinic acid system absorb carry dense;
(2) flue gas of hydrogen chloride gas after will heating and above-mentioned trioxygen-containing sulphur is in 0.95～1.05: 1 ratio enters synthetic tower, according to the difference of hydrogen cloride concentration, temperature of reaction is controlled between 150-230 ℃, obtains containing the gas mixture of gaseous state chlorsulfonic acid;
(3) gas mixture of synthetic tower outlet is used for heating the hydrogen chloride gas of volume content more than 20% of drying, demist in the step (2), and the hydrogen chloride gas temperature enters synthetic tower after being elevated to more than 110 ℃;
(4) the gaseous state gas mixture after heat exchange enters one subsequently and uses water-cooled cooling separator in the step (3), and cooling separator divides high temperature section and low-temperature zone, and non-condensable gases that leaves and liquid are the chlorsulfonic acid crude product;
(5) chlorsulfonic acid crude product and a part of exsiccant hydrogenchloride secondary response again obtains the chlorsulfonic acid finished product;
(6) non-condensable gases at first enters the sulfuric acid scrubbing tower with sulfuric acid absorption sulphur trioxide wherein, remaining few sulphur trioxide and hydrogenchloride adopts water to absorb the nitration mixture that makes sulfur-bearing acid group and hydrogenchloride again, nitration mixture is delivered to the hydrogenchloride that parses in the hydrogenchloride drying tower wherein in system's internal recycle utilization, hydrogenchloride drying tower and sulfuric acid scrubbing tower keep string acid, and by-product contains sulfuric chlorohydrin on a small quantity and can be used for other devices;
(7) after above-mentioned absorption, tail gas emptying up to standard after efficient mist eliminator demist.
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| CNB021386099A CN1164479C (en) | 2002-11-13 | 2002-11-13 | Technology of synthesizing high concentration chlorosulfonic acid using low concentration salfur trioxide |
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| CNB021386099A CN1164479C (en) | 2002-11-13 | 2002-11-13 | Technology of synthesizing high concentration chlorosulfonic acid using low concentration salfur trioxide |
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| CN1164479C true CN1164479C (en) | 2004-09-01 |
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| CN105111111A (en) * | 2015-09-10 | 2015-12-02 | 泰兴市臻庆化工有限公司 | Preparation method for aryl sulfonyl chloride derivative |
| CN108557775B (en) * | 2018-06-19 | 2020-06-02 | 江苏明盛化工有限公司 | Tail gas treatment method in chlorosulfonic acid preparation process, system for implementing method and chlorosulfonic acid preparation method |
| CN109052332B (en) * | 2018-10-24 | 2022-02-22 | 泰兴锦汇化工有限公司 | Method for preparing chlorosulfonic acid by regenerating high-COD (chemical oxygen demand) saline dilute acid |
| CN112279220B (en) * | 2020-12-29 | 2021-03-23 | 苏州香榭轩表面工程技术咨询有限公司 | Continuous production method of high-purity sulfuric acid |
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