CN1830760A - Preparation of high concentration fuming sulfuric acid using residual heat distillation method - Google Patents
Preparation of high concentration fuming sulfuric acid using residual heat distillation method Download PDFInfo
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- CN1830760A CN1830760A CN 200510024270 CN200510024270A CN1830760A CN 1830760 A CN1830760 A CN 1830760A CN 200510024270 CN200510024270 CN 200510024270 CN 200510024270 A CN200510024270 A CN 200510024270A CN 1830760 A CN1830760 A CN 1830760A
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- CN
- China
- Prior art keywords
- sulfuric acid
- oleum
- fuming sulfuric
- high concentration
- manufacture method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000004821 distillation Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 68
- 239000007789 gas Substances 0.000 claims description 25
- 239000006200 vaporizer Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 15
- 238000002407 reforming Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 10
- 239000011552 falling film Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002918 waste heat Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002253 acid Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002826 coolant Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- PWJNDVAKQLOWRZ-UHFFFAOYSA-N 1-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=CC=C2C(O)=C(S(O)(=O)=O)C=CC2=C1 PWJNDVAKQLOWRZ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- -1 this Chemical compound 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
A process for preparing high-concentration fuming sulfuric from ordinary fuming sulfuric acid by afterheat distilling method includes such steps as using the afterheat of converting gas in sulfuric acid system to distill the ordinary fuming sulfuric acid in tube-shell evaporator to obtain gas-state SO3, cooling in condenser to become liquid-state SO3, and mixing with ordinary fuming sulfuric acid.
Description
Technical field
The present invention relates to a kind of basic chemical raw materials, promptly the manufacture method of mineral acid specifically, relates to a kind of manufacture method of high concentration fuming sulfuric acid.
Background technology
High concentration fuming sulfuric acid is meant free sulphur trioxide (SO
3) reach the oleum of 65wt.%, it is a kind of than the more effective sulphonating agent of common oleum (about the about 20wt.% of concentration), be mainly used in organic synthesis industry, can obviously improve sulfonation efficient, for example be used to make sulfonaphthol ,-oil of mirbane butyric acid, naphthene sulfonic acid etc.In addition, this high concentration fuming sulfuric acid also is widely used in the production of dyestuff intermediate and medicine industry.
Temperature in the time of 45 ℃, the SO of 65wt.% oleum
3Vapour pressure is up to 72657.9Pa, and under same temperature, concentration is the SO of the common oleum of 20wt.%
3Vapour pressure is 345.8Pa, and both differ more than 200 times.In the system of common gas washing in SA production, no matter adopt " one changes one inhales " (once transform, once absorb) or " double conversion double absorption " (twice transformation, secondary absorption) technology, the SO after the conversion
3Dividing potential drop is always in 7300～9900Pa scope, with the SO of above-mentioned 65wt.% oleum
3Vapour pressure differs greatly, and therefore, utilizes SO
3The concentration only reforming gas of 7～9.5wt.% can not produce concentration and reaches 65% high concentration fuming sulfuric acid.
Traditional technology that vitriol works adopted in the past is: adopting the 25wt.% oleum of producing in the sulfate system (hereinafter to be referred as " oleum ") is raw material, joins the flat board evaporation pot of heating of making fuel with coal through under meter, the SO in the above-mentioned oleum
3Under the effect of high temperature (≤650 ℃) furnace gas heating, be evaporated out, send into SO then
3Condenser, its heat is taken away by water coolant, when temperature reaches below 45 ℃, gasiform SO
3Promptly be converted into liquid SO
3, this liquid SO
3, content can be mixed in proportion it and 25wt.% oleum in tempering tank near 100wt.%, makes the 65wt.% high concentration fuming sulfuric acid after the stirring.
Though above-mentioned technology is simple, shortcoming is obvious:
1, evaporative process needs to adopt in addition the thermal source that adds, and the consumption of fuel is bigger;
2, potential certain danger in the operating process, that is, and when batch operation, since the cooling of gas path pipe when intermittence, the gaseous state 100wt.%SO in the pipeline
3Can be converted into liquid state, and and then be converted into solid-stately, this will cause line clogging, even causes the pan blast;
3, the steel plateform evaporating pan contacts with high temperature heat source, and the bottom of a pan seriously corroded even the bottom of a pan steel plate materials is thickeied 30mm, also has only the work-ing life of half a year;
4, owing to the bottom of a pan heavy corrosion, cause to steam SO
3After in the lower concentration oleum that stays iron level increase, reduced its quality grade.
Summary of the invention
The present invention is intended to overcome many shortcomings that the above traditional technology is made high concentration fuming sulfuric acid, provide a kind of technology rationally, production safety, can make full use of the waste heat in the sulfuric acid production system, and gaseous state SO
3Production and sulfate system in the production of common oleum conspire to create the manufacture method of the high concentration fuming sulfuric acid of one.
The present invention is achieved in that it is a raw material with the common oleum of acid making system production, is characterized in that, utilize the waste heat of the sulfuric acid conversion gas in the sulfate system, adopt countercurrent heat exchange method, the common oleum of distillation therefrom evaporates gaseous sulfur trioxide (SO in shell and tube evaporator
3), it is sent into the condenser internal cooling become liquid sulphur trioxide, again this liquid sulphur trioxide is sent into mixing tank, mix with common oleum in being added in this mixing tank in advance, make high concentration fuming sulfuric acid.
Specifically, whole technological process is as follows: by oleum (the concentration 25wt.%～30wt.%) send into the coil tube type preheater and (steam SO from effusive time acid of sulphur trioxide vaporizer by recycle pump of leading portion sulfate system production
3The sulfuric acid that stays behind the gas) heat exchange, through after the preheating, send into the sulphur trioxide vaporizer, the thermal source system of this vaporizer utilizes the waste heat of four sections air preheater outlets of convertor reforming gas of sulfate system, in the time of this reforming gas reverse flow pervaporation device, to the oleum heating of sending into from preheater, evaporate sulfur trioxide gas, self is also to a certain degree cooled off, and is sent back to the sulfate system absorption tower, finishes a circulation.
The gaseous state 100wt.%SO that steams from the sulphur trioxide vaporizer
3Send into the sulphur trioxide condenser by pipeline, valve system, condensation obtains liquid sulphur trioxide, and it is sent in the tempering tank that adds a certain amount of common oleum in advance continuously, reaches the 65wt.% oleum that just makes high density after the preset proportion.What produce if desired is liquid 100wt.% sulphur trioxide, then will it not mix with common oleum, allows it flow directly into the sulfan storage tank and gets final product.
In above-mentioned technology, should adopt the oleum of concentration 25wt.%～30wt.% as raw material acid, effect is better like this, because along with the concentration of oleum raises, its boiling point reduces gradually, and the sulphur trioxide dividing potential drop raises gradually simultaneously, and the yield of gaseous sulfur trioxide is improved.
In addition, in order to slow down to equipment corrosion free SO in the oleum
3Concentration can not be too low because free in right amount SO
3Existence, help improving oxidisability, can slow down corrosion to equipment,, require steaming gaseous state SO for this reason
3The concentration that the oleum of vaporizer is flowed out in the back is controlled at about 15wt.%～20wt.%.
Vaporizer in the above-mentioned technical process, what pass logical process using is falling film evaporator, it belongs to the tube and shell heat exchanger type.According to requirement of the present invention, can be assigned to equably in the every steel pipe in the vaporizer as the 25wt.%～30wt.% oleum of raw material acid, acid solution forms air film along the steel pipe inwall and evenly flows downward, the reforming gas that contains heat heats from the steel pipe outside, if the acid intake amount that at this moment takes place in certain root steel pipe is few, cause the oleum transition evaporation in this pipe, so that the local area acid concentration is lower than 15wt.%SO
3(dissociating), cause pipe corrosion.Therefore, it is vital making the oleum uniform distribution in vaporizer as raw material acid, for this has made appropriate reconstruction to vaporizer: oleum flows in evaporator tube from bottom to top, reforming gas outside the pipe heats, simultaneously by countercurrent flow, design and installation the reforming gas gas distribution grid, increase the turbulence intensity of gas whereby, improve heat transfer coefficient, the remaining oleum in evaporation back flows in the disc type preheater by potential difference.
Be used for the sulphur trioxide condenser condensing and be generally tube shell type structure, can use air cooling, also can use water cooling, consider from the thermal conduction angle, in view of the inner variation that has phase of pipe, the cooling of pipe exterior-applied liquid medicine, total heat transfer coefficient is than much higher with air, but having relatively high expectations to equipment material, just in case leak, the gasiform sulphur trioxide mixes with water and can set off an explosion, and for this reason, the present invention adopts the design of falling film type shell condenser structure specially, make water coolant can be assigned on the every steel pipe equably, and open-top is in atmospheric pressure state, and water coolant forms liquid film along the steel pipe inwall and flows downward, pipe is outer to be reverse the advancing of gasiform sulphur trioxide (pressure 0.02MPa), progressively being cooled is condensed into liquid sulphur trioxide, like this, even the contingency shell side leaks because of corrosion, the operative liquid sulphur trioxide can only enter tube side, it mixes with water and the heat that produces can be by opening wide the row of place ease, and unlikely setting off an explosion also helps in time to take emergency measures.
As seen by above-mentioned, effect of the present invention is fairly obvious, can simply be summarized as follows:
1, the inventive method conspires to create one to the production of the oleum of the production of gaseous sulfur trioxide and sulfuric acid production system, uncooled oleum is directly sent into the production system of sulphur trioxide, can make full use of the generation heat of oleum in the front end oleum production process.
2, as the oleum of raw material acid before entering vaporizer, earlier by preheater with from the effusive gaseous state SO that steams of vaporizer
3The residual oleum in back (returning acid) heat exchange so as to reclaiming a part of sensible heat, and improves the temperature condition that reforming gas enters the back system.
3, the shared pump of oleum circulation absorption system and high concentration fuming sulfuric acid production system has been saved facility investment and electric energy.
4, the reasonable safety of whole production technology.
Description of drawings
Fig. 1 is a high concentration fuming sulfuric acid technological process of production synoptic diagram of the present invention.Number in the figure is: 1---oleum preheater; 2---the acid seal bucket; 3---the sulphur trioxide vaporizer; 4---the oleum acid tower; 5---the oleum recycle pump; 6---the oleum plate-type heat exchanger; 7---the sulphur trioxide condenser; 8---the sulfan storage tank; 9---the mixed bucket of high concentration fuming sulfuric acid; 10---the high concentration fuming sulfuric acid recycle pump.
Embodiment
The invention will be further described below in conjunction with embodiment, but the present invention is not limited to this embodiment.
Embodiment
Consult Fig. 1,, send into coil tube type oleum preheater [1] by recycle pump [5], and from the effusive SO that steams of sulphur trioxide vaporizer [3] by 25wt.%～30wt.% oleum that sulfate system is produced as raw material acid
3About 160 ℃ 15wt.%～20wt.% oleum (the returning acid) heat exchange of residual temperature behind the gas, this raw material acid is preheating to about 100 ℃, send into sulphur trioxide vaporizer [3], this place be subjected to countercurrent flow from sulfate system in the heat effect of reforming gas of four sections air preheaters of convertor outlet, the SO in the raw material acid (boiling point of 25wt.% oleum is 140.5 ℃)
3Be distilled out, obtain the sulfur trioxide gas of 100wt.%.Meanwhile, the temperature of reforming gas about 200 ℃ when entering vaporizer are cooled to about 130 ℃, are sent back to the absorption tower import of sulfate system.
The gasiform sulphur trioxide is condensed into liquid sulphur trioxide by sulphur trioxide condenser [7], condensing temperature is controlled to be 30～45 ℃, be condensed into liquid sulphur trioxide, flow into the sulfan storage tank [8] of below, after reaching some amount, sulfan is continuously flowed in the mixed bucket [9] that adds a certain amount of 25wt.% oleum in advance, and mix with it, just obtain high density 65wt.% oleum after reaching certain proportion by pump [10] circulation.The reforming gas gas distribution grid that specialized designs is installed is equipped with in vaporizer wherein [3] inside, has tangible increase gas turbulence intensity, improves the effect of heat transfer coefficient, can reach 8 years work-ing life according to a preliminary estimate.Condenser [7] adopts falling film type shell condenser structure, move fool proofly, moves through for some time in factory any fault does not take place.
Claims (5)
1, a kind of manufacture method of producing high concentration fuming sulfuric acid by common oleum, it is characterized in that, this method is utilized the waste heat of the reforming gas in the sulfate system, adopt countercurrent heat exchange method, the common oleum of distillation therefrom evaporates gaseous sulfur trioxide in shell and tube evaporator, it is sent into the condenser internal cooling become liquid sulphur trioxide, again this liquid sulphur trioxide is sent into mixing tank, mix, make high concentration fuming sulfuric acid with common oleum in being added in this mixing tank in advance.
2, high concentration fuming sulfuric acid manufacture method according to claim 1 is characterized in that, the described concentration that is used to evaporate the common oleum of gaseous sulfur trioxide is 25wt.%～30wt.%.
3, high concentration fuming sulfuric acid manufacture method according to claim 1 is characterized in that, in described distillation procedure, the oleum concentration that flows out vaporizer is controlled to be 15wt.%～20wt.%.
4, high concentration fuming sulfuric acid manufacture method according to claim 1 is characterized in that, specialized designs has been settled the reforming gas gas distribution grid in the described vaporizer.
5, high concentration fuming sulfuric acid manufacture method according to claim 1 is characterized in that, described sulphur trioxide condenser has adopted falling film type shell design of condenser.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100242707A CN100425528C (en) | 2005-03-09 | 2005-03-09 | Preparation of high concentration fuming sulfuric acid using residual heat distillation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100242707A CN100425528C (en) | 2005-03-09 | 2005-03-09 | Preparation of high concentration fuming sulfuric acid using residual heat distillation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1830760A true CN1830760A (en) | 2006-09-13 |
| CN100425528C CN100425528C (en) | 2008-10-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100242707A Expired - Fee Related CN100425528C (en) | 2005-03-09 | 2005-03-09 | Preparation of high concentration fuming sulfuric acid using residual heat distillation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663389A (en) * | 2013-11-28 | 2014-03-26 | 周正勇 | Method and equipment for concentrating waste sulfuric acid in alkylate production conducted through sulfuric acid method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042124C (en) * | 1996-02-14 | 1999-02-17 | 谭先锋 | Continuous production of liquid SO by using waste heat of converted gas3And 65% SO3System of oleum |
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2005
- 2005-03-09 CN CNB2005100242707A patent/CN100425528C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103663389A (en) * | 2013-11-28 | 2014-03-26 | 周正勇 | Method and equipment for concentrating waste sulfuric acid in alkylate production conducted through sulfuric acid method |
| CN103663389B (en) * | 2013-11-28 | 2015-06-17 | 周正勇 | Method and equipment for concentrating waste sulfuric acid in alkylate production conducted through sulfuric acid method |
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| Publication number | Publication date |
|---|---|
| CN100425528C (en) | 2008-10-15 |
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Granted publication date: 20081015 Termination date: 20100309 |