CN1075297A - Microcorrosion high yield synthetic hydrochloric acid production method and equipment - Google Patents
Microcorrosion high yield synthetic hydrochloric acid production method and equipment Download PDFInfo
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- CN1075297A CN1075297A CN 92113941 CN92113941A CN1075297A CN 1075297 A CN1075297 A CN 1075297A CN 92113941 CN92113941 CN 92113941 CN 92113941 A CN92113941 A CN 92113941A CN 1075297 A CN1075297 A CN 1075297A
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- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/012—Preparation of hydrogen chloride from the elements
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Abstract
A kind of microcorrosion high yield hydrochloric acid production method and equipment are the improvement on the hydrogen chloride synthetic furnace basis that carbon steel is made, and improving the upper and lower body of heater of back synthetic furnace all has water jacket.Coil pipe is arranged in the stove, use water cooling during blow-on, hydrogenchloride is dropped to below 500 ℃ in synthetic furnace exit temperature, pass to the hot water of sufficient temp before the blow-on in the water jacket, or with the burning inflammable gas method preheating synthetic furnace, furnace wall temperature is reached more than 108 ℃, and forced air cooled tube is coated with high temperature resistant anti-oxidation lacquer.
Description
The invention belongs to non-metallic element and compound thereof and make the field, is a kind of microcorrosion high yield synthetic hydrochloric acid production method and equipment.
The production of hydrochloric acid mainly is the synthetic of hydrogenchloride, is to carry out in hydrogen chloride synthetic furnace, and chlorine and hydrogen enter by pipeline separately, mix in burner (lamp holder), carry out combustion reactions in the burner exit, generate hydrogenchloride.This is a kind of thermopositive reaction, produces high temperature, needs tentatively to cool off in synthetic furnace.Through with the heat exchange of synthetic furnace upper furnace body water jacket, after synthetic furnace lower furnace body and forced air cooled tube and the air heat exchange, enter graphite heat exchanger with suitable service temperature, cool off once more, enter graphitic absorber at last, absorbed by water, generation hydrochloric acid enters storage tank.Accompanying drawing 1 is existing hydrochloric acid Production Flow Chart sketch, and [1] is the upper furnace body watercooling jacket, and [2] are the hydrogen pipes, [3] be chlorine tube, [4] be burner, [5] are lower furnace bodies, and [6] are upper furnace bodies, [7] be forced air cooled tube, [8] be graphite heat exchanger, [9] are graphitic absorbers, and [10] are graphite secondary resorbers, [11] be squirt pump, [12] are hydrochloric acid tanks.Synthetic furnace generally adopts the carbon steel manufacturing.Use such material, make easy to process, the heat transfer efficiency height, cost is low, but not corrosion-resistant.For fear of corrosion, the employing graphite that has is as the body of heater material, but makes processing difficulties, cost height, and heat exchange efficiency is not high, and output can not effectively improve, so that manufacturer adopts is few, the carbon steel synthetic furnace is widely used in domestic synthetic hydrochloric acid manufacturing firm.The synthetic furnace body of heater can be considered by two portions up and down to be formed, close in order to make, the hydrogenchloride cooling that becomes, there is watercooling jacket the upper furnace body outside, in fact the synthetic body of heater of a lot of carbon steels is made into integration, here it is divided into, lower furnace body is for the convenience that says something, because lower furnace body and forced air cooled tube directly are exposed in the air, high temperature oxidation and corrosion is very serious, lower furnace body particularly, high temperature oxidation and corrosion is very fast in the air, as using the thick boiler sheet manufacturing of 10mm, use and to produce the local corrosion penetration phenomenon in three months, air cooling pipe temperature is lower, and high temperature oxidation and corrosion than lower furnace body lightly but also can not be ignored.Except lower furnace body and the outside high temperature oxidation and corrosion of air cooling pipe, stove inwall hcl corrosion also is a very important problem.
Hydrochloric acid is because hydrochloric acid and iron reaction generate iron(ic) chloride to the corrosion of body of heater.The existence of hydrochloric acid is owing to contain moisture in the hydrogen in the synthetic furnace, in addition, often contains oxygen and moisture etc. in the chlorine, particularly most of factory that produces hydrochloric acid, and the chlorine of usefulness all is tail chlorine, is unpurified.The impurity of removing in the unstripped gas is the pretty troublesome thing of part, increase equipment, improved production cost, so in the ordinary course of things, the unstripped gas of producing hydrochloric acid all can not be very pure, when hydrogen is produced hydrogenchloride with chlorine reaction, oxygen and hydrogen reaction generate water, hydrogen chloride gas is water-soluble immediately, becomes hydrochloric acid, and hydrochloric acid has serious corrosive nature to the iron furnace body.Be subjected in the synthetic furnace hcl corrosion the most serious be burner, secondly be stove inwall and forced air cooled tube inwall.The muriate of the iron that corrosion generates is attached to the equipment inwall, influence is conducted heat, blocking pipe and equipment, be partially soluble in hydrochloric acid, make in the hydrochloric acid iron ion content permissible value that is above standard, the hydrochloric acid its colour changed into yellow, quality reduces, no matter be high temperature oxidation and corrosion or hcl corrosion, the capital is damaged equipment in advance, repairs or changes, and not only causes the waste of equipment, the idle cost that causes is bigger, blowing out and again blow-on make hcl corrosion aggravation again, there is watercooling jacket synthetic furnace upper furnace body outside commonly used, uses water cooling, the heat exchange efficiency height, and lower furnace body and forced air cooled tube lean on air cooling, and heat exchange efficiency is low, are designed to example with the synthetic furnace of producing 1.5 ten thousand tons of hydrochloric acid per year, upper furnace body and water heat exchange, heat interchanging area are 13 square metres; Lower furnace body and forced air cooled tube and air heat interchanging area are 5+18=23 square metre.That is to say that heat a large amount of in the heat transfer process are distributed by heat exchange efficiency not high lower furnace body and air cooling pipe appearance.With the situation of air heat exchange because of season, round the clock, envrionment temperature is different with wind speed and change.Because salt acid yield and synthetic furnace.The cooling performance of forced air cooled tube is closely related, the salt acid yield often is among the fluctuation, produce unstable, more than all situations, there is not improvement for many years, in order to solve the problem of synthetic furnace inner part hcl corrosion, China utility application 92200426.9(notification number CN2109247U) a kind of protection against corrosion burner that is used for hydrogen chloride synthetic furnace has been proposed, this burner is made by highly corrosion resistant refractory materials, prolong its work-ing life greatly, but this improvement only relates to burner, the synthetic furnace body of heater and and the etching problem of air cooling pipe still do not solve.
Find through test, on the basis of original carbon steel synthetic furnace, do some improvement, in operation, take some measures, the corrosion of synthetic furnace is minimized, shutdown maintenance, the number of times of changing parts significantly reduces, and has improved the output of hydrochloric acid, has saved the equipment of establishing and equipment, the hydrochloric acid quality improves greatly, because the improvement of heat exchange situation, produces more stable, the raising of salt acid yield.The object of the present invention is to provide a kind of synthetic hydrochloric acid production method, according to the method, lower furnace body is all used water cooling on the synthetic furnace, promptly also installs watercooling jacket additional in the lower furnace body outside, strengthen cooling, make the forced air cooled tube contraction in length, the forced air cooled tube appearance is coated with high temperature resistant anti-oxidation lacquer, before blow-on, all pass to hot water up and down in the furnace water jacket, make synthetic furnace give heat, or before blow-on, pass to inflammable gas and ignition in stove, furnace temperature is brought up to more than 108 ℃.Another object of the present invention provides a kind of improved hydrochloric acid synthetic furnace, and its upper and lower body of heater all has watercooling jacket, and the forced air cooled tube outside is coated with high temperature resistant anti-oxidation lacquer.
Discover that hydrochloric acid occurs in below the boiling point of hydrochloric acid the corrosion of iron, under the temperature that is higher than the hydrochloric acid boiling point, corrosive nature does not take place to iron in hydrochloric acid.The hydrochloric acid boiling point changes with contained hydrogenchloride percentage.This variation relation is called boiling point curve, as shown in Figure 2.Under the synthetic furnace working condition, the hydrochloric acid boiling point is near 108 ℃.As long as the synthetic furnace furnace wall temperature is more than 108 ℃, hcl corrosion can not take place in the carbon steel body of heater.In order to eliminate the corrosion of hydrochloric acid to synthetic furnace body, should be when hydrogen and chlorine reaction, furnace wall temperature remains on more than 108 ℃.For this reason, the measure of taking among the present invention is before synthetic furnace reacts, stove is given heat, give the measure that the thermal synthesis stove can be taked two aspects, the one, body of heater to be transformed on structure, body of heater all adds watercooling jacket up and down, before the synthetic furnace reaction, in water jacket, pass to the high as far as possible hot water of temperature, make synthetic furnace give heat.Do like this, synthetic furnace is through giving heat, and the very fast rising of temperature reaches more than 108 ℃ furnace wall temperature after the blow-on, and hydrochloric acid was shortened greatly to the low temperature corrosion time of body of heater, and in operation, this point is easy to realize.Can take from the hot water (general hydrochloric acid factory all is that several synthetic furnaces move simultaneously) that other synthetic furnace chuck is discharged for giving the used hot water of thermal synthesis stove.In accompanying drawing 3, A produces stove, and B treats blow-on, and valve 1.2.6.7.8. is an open mode, 3.4.5. be closing condition, will be with the hot water of discharging in the A stove water jacket before the blow-on of B stove, but valve-off 6.7, after opening valve 5. water jackets and filling it up with hot water, valve-off 8, open valve 7, put stove then, logical unstripped gas.Open valve 4. gradually according to actual conditions after question response is normal, other method of also available usefulness adds hot water, fact proved, if make body of heater give heat with 85 ℃ hot water, can make reaction begin that furnace wall temperature reaches more than 108 ℃ in back 2 minutes.If the water that feeds is 18 ℃ cold water, then to furnace wall temperature could be elevated to more than 108 ℃ through about 20 minutes.In this case, hydrochloric acid can shorten to without hot water the etching time of body of heater and give about 1/10th when hot during blow-on, generally feeds the hot water temperature that water jacket gives the thermal synthesis stove and is at least 70 ℃.
It is to pass to inflammable gas earlier in synthetic furnace before the blow-on that another that take among the present invention gives the measure that improves furnace temperature earlier, and makes it burning, and the heat that sends with burning improves furnace temperature.The inflammable gas that is fed is hydrogen preferably, hydrogen was exactly one of unstripped gas of synthesising hydrogen originally, ready-made steam line is arranged, the heat that burning generates improves temperature in the stove soon, furnace wall temperature is reached more than 108 ℃, and the method that makes inflammable gas-combustion of hydrogen is when feeding hydrogen, enters the oxygen of proper amt, to take measures during operation, avoid blasting.Furnace temperature is elevated to after 108 ℃, cuts off oxygen, feeds chlorine simultaneously, hydrogen and chlorine are reacted under the furnace temperature that improves, carry out ordinary production, this just makes, the synthetic furnace inner wall temperature is in basic no hydrogenchloride generation of time below 108 ℃, also just do not have the corrosion of hydrochloric acid, still, hydrogen and oxygen reaction generate water, condensation is got off in interchanger and the resorber, concentration of hydrochloric acid is reduced,, this problem can be compensated with the way that improves concentration after the ordinary production.Passing to the measure of using two of inflammable gas incendiary to improve furnace temperature before hot water and the blow-on in the watercooling jacket can mutually independently also can complement one another.The measure in front can make shortening to of hydrochloric acid low temperature corrosion original 1/10th, effectively and safety, the measure in back can be eliminated hydrochloric acid low temperature corrosion in the stove fully.But must be noted that safety during operation, do not blast.Two measures are used simultaneously, can eliminate hcl corrosion in the stove fully, can save inflammable gas and oxygen again.
Behind the synthetic furnace stopped reaction, go back remaining hydrogen chloride gas of lingering section and water vapour in the stove and in the forced air cooled tube, because reaction stops, temperature descends, and when dropping to below 108 ℃, can produce corrosion to synthetic furnace and forced air cooled tube.Though this corrosion is lighter, must take measures to be eliminated.The measure of taking among the present invention is one. strengthens the draft of back squirt pump after the blowing out, makes residual gas enter interchanger and resorber rapidly; Two. nitrogen tube is installed entering on the Hydrogen Line of synthetic furnace, makes a large amount of nitrogen enter synthetic furnace after the blowing out, residual hydrogenchloride in displacement synthetic furnace and the forced air cooled tube.
Problem about body of heater and forced air cooled tube outside surface high temperature oxidation and corrosion, as previously mentioned, add watercooling jacket, eliminated the high temperature oxidation and corrosion of body of heater basically in synthetic furnace lower furnace body outside, during the synthetic furnace blow-on, in the stove temperature up to 1000 ℃ about, the cooling of water in furnace water jacket arrives the forced air cooled tube ingress, temperature is still more than 500 ℃, through the forced air cooled tube cooling, be the graphite heat exchanger temperature in its exit, the rotten corrosion of forced air cooled tube leading portion high temperature oxidation is still more serious.In the present invention, be to solve the high temperature oxidation and corrosion problem of forced air cooled tube, the one, strengthen the cooling effect of synthetic furnace, make the synthetic furnace exit, that is forced air cooled tube ingress hydrogen chloride gas temperature drops to and is no more than 500 ℃; The 2nd, be coated with high temperature resistant anti-oxidation lacquer in the forced air cooled tube appearance.Strengthen the synthetic furnace cooling effect, can take the measure of several respects.The one, the heat interchanging area of increase watercooling jacket: the 2nd, at the inner dress of synthetic furnace spiral coil cooling tube,, just can not be used in and install spiral coil cooling tube in the stove if, synthetic furnace exit hydrogen chloride gas temperature is dropped to below 500 ℃ by the water jacket heat exchange.The hydrogen chloride gas temperature effectively reduces, and just can reduce the length of forced air cooled tube.Forced air cooled tube is by air cooling, and it is indefinite that the cooling situation rises and falls, and influential to producing, its length is short more, influences more little.So, strengthen the cooling effect of synthetic furnace, not only effectively reduce the forced air cooled tube temperature, thereby the high temperature corrosion that alleviates forced air cooled tube can make also production more stable.Reduce in the forced air cooled tube temperature, under the situation of contraction in length, be coated with high temperature resistant anti-oxidation lacquer in its outside, this high temperature resistant anti-oxidation lacquer contains organosilicon, and not only high temperature resistant anti-oxidation but also unlikely influence heat radiation under the temperature below 500 ℃, can be selected trade mark W-61-901 for use.
According to the present invention, the synthetic furnace that the annual production of design hydrochloric acid is 1.5 ten thousand tons, all there is watercooling jacket upper and lower body of heater outside, and the forced air cooled tube leading portion has watercooling jacket, and back segment is coated with high temperature resistant anti-oxidation lacquer; Operating aspect passes to hot water in the water jacket before the blow-on, and in stove burning hydrogen, make synthetic furnace give heat, after the blowing out with residual hydrogenchloride in the nitrogen replacement stove and in the forced air cooled tube.These measures can make body of heater and forced air cooled tube high temperature oxidation and corrosion basically eliminate, the hydrochloric acid low temperature corrosion is reduced to bottom line, the synthetic furnace lower furnace body can only be used half a year when not adding the stove watercooling jacket, take to use the more than ten years after the measure among the present invention, because corrosion is slight, the parking maintenance number of times can be by tens of inferior being reduced to for several times in every year (but reducing blowing out number of times mitigate corrosion again).The synthetic furnace blow-on time prolongs greatly.Body of heater is all used water cooling, and good effect of heat exchange is produced stable.Everything can make the salt acid yield improve 1/4th, and the hydrochloric acid quality also significantly improves.
Claims (7)
1, a kind of microcorrosion high yield synthetic hydrochloric acid production method, synthesizing in the synthetic furnace of carbon steel manufacturing of hydrogen chloride gas carried out, synthetic furnace is made of upper and lower body of heater, hydrogen and the chlorine sent into pipeline enter in the synthetic furnace by burner, react, generate hydrogen chloride gas, hydrogen chloride gas tentatively cools off in stove, enter forced air cooled tube then and further cool off, it is characterized in that:
A. on the synthetic furnace. all there is water jacket the lower furnace body outside, cools off with cold water during the synthetic furnace blow-on;
B. before the synthetic furnace blow-on, make synthetic furnace give heat;
C. the forced air cooled tube outside is coated with high temperature resistant anti-oxidation lacquer;
D. squirt pump adds high-power the continuation and bleeds behind the synthetic furnace stopped reaction, and entrap bubble is extracted out fast.
2, by the said synthetic hydrochloric acid production method of claim 1, it is characterized in that, in upper and lower furnace water jacket, pass to hot water before the synthetic furnace blow-on.
3, by the said synthetic hydrochloric acid production method of claim 1, it is characterized in that, feed inflammable gas before the blow-on and make its burning.
By the said synthetic hydrochloric acid production method of claim 2, it is characterized in that 4, the hot water temperature who feeds in the water jacket before the blow-on is at least 70 ℃.
By the said synthetic hydrochloric acid production method of claim 3, it is characterized in that 5, the inflammable gas that feeds before the blow-on is a hydrogen.
6, a kind of microcorrosion high yield hydrochloric acid production unit, the carbon steel manufacturing of hydrogen chloride gas synthetic furnace is made of upper and lower body of heater, and the hydrogenchloride that reaction generates is tentatively cooling in stove, enters forced air cooled tube then and continues cooling, it is characterized in that:
A. all there is watercooling jacket the upper and lower body of heater of synthetic furnace outside;
B. the forced air cooled tube outside is coated with high temperature resistant anti-oxidation.
7, by the said hydrochloric acid production unit of claim 6, it is characterized in that spiral coil cooling tube is arranged in the synthetic furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92113941 CN1031393C (en) | 1992-12-05 | 1992-12-05 | Process for production of synthetic hydrochloric acid at slightly corrosion and high yield and its equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92113941 CN1031393C (en) | 1992-12-05 | 1992-12-05 | Process for production of synthetic hydrochloric acid at slightly corrosion and high yield and its equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1075297A true CN1075297A (en) | 1993-08-18 |
| CN1031393C CN1031393C (en) | 1996-03-27 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92113941 Expired - Fee Related CN1031393C (en) | 1992-12-05 | 1992-12-05 | Process for production of synthetic hydrochloric acid at slightly corrosion and high yield and its equipment |
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| Country | Link |
|---|---|
| CN (1) | CN1031393C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830860B (en) * | 2005-03-03 | 2010-06-16 | 罗门哈斯公司 | Method for reducing corrosion |
| CN102249859A (en) * | 2005-11-08 | 2011-11-23 | 索尔维公司 | Process for the manufacture of dichloropropanol by chlorination of glycerol |
| CN103256818A (en) * | 2012-02-17 | 2013-08-21 | 沈阳铝镁设计研究院有限公司 | Cooling water jacket of pot type calcining furnace |
-
1992
- 1992-12-05 CN CN 92113941 patent/CN1031393C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830860B (en) * | 2005-03-03 | 2010-06-16 | 罗门哈斯公司 | Method for reducing corrosion |
| CN102249859A (en) * | 2005-11-08 | 2011-11-23 | 索尔维公司 | Process for the manufacture of dichloropropanol by chlorination of glycerol |
| CN103256818A (en) * | 2012-02-17 | 2013-08-21 | 沈阳铝镁设计研究院有限公司 | Cooling water jacket of pot type calcining furnace |
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| Publication number | Publication date |
|---|---|
| CN1031393C (en) | 1996-03-27 |
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