CN101693525B - Method for preparing bromine by vapor distillation - Google Patents
Method for preparing bromine by vapor distillation Download PDFInfo
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- CN101693525B CN101693525B CN200910036187XA CN200910036187A CN101693525B CN 101693525 B CN101693525 B CN 101693525B CN 200910036187X A CN200910036187X A CN 200910036187XA CN 200910036187 A CN200910036187 A CN 200910036187A CN 101693525 B CN101693525 B CN 101693525B
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Abstract
The invention relates to a method for preparing bromine by vapor distillation, which is characterized by comprising the following steps: adding raw material brine into a high-level groove, flowing through a preheater for preheating and entering a bromine tower from the top of the bromine tower; introducing chlorine and steam from the bottom of the bromine tower; carrying out oxidation and distillation reaction in the bromine tower, discharging bromine extraction waste liquor from the bottom of the bromine tower, and discharging the mixed steam of bromine, chlorine and water from the upper part of the bromine tower to a condensator; condensing with freshwater to obtain a mixture of bromine and bromine water; enabling the mixture of bromine and bromine water to flow into a separation bottle for natural demixing through a pipeline, wherein the bromine water at the upper layer flows back to the bromine tower through a pipeline, and coarse bromine flows to a rectification column from the lower part of the separation bottle through a pipeline; discharging chlorine, bromine and the like from the top of the rectification column; condensing and back flowing part of the bromine through a reflux condenser; discharging the gas which is not condensed to a recovery tower; recovering with brine and entering the bromine tower; and discharging fine bromine to a cooler by a rectification heating kettle to obtain the fine bromine. The invention has reasonable process, convenient and safe operation and high purity of the prepared bromine, thereby being suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of bromine, particularly a kind of steam distillation legal system bromine.
Background technology
Bromine (Br
2), at first the Ba Laer by France leads to chlorine in the useless sea salt mother liquor, has obtained bromine.Bromine is the red-brown fuming liquid, density 3.119 grams per cubic centimters, fusing point-7.2 ℃, 58.76 ℃ of boiling points.Bittern and seawater are the main sources that extracts bromine.Bromine is mainly used in system bromide, Hydrogen bromide, medicine, dyestuff, fumigant etc.Bromine is the same with other halogens at occurring in nature, does not have the simple substance state to exist.Its compound is usually mixed in together with the compound of chlorine, and just the quantity much less contains bromine in some mineral waters, salt lake saline and seawater.The general direct electrolysis of abraum salt juice from salt industry obtains bromine in the prior art.
Summary of the invention
Technical problem to be solved by this invention is at the deficiencies in the prior art, and the steam distillation legal system that a kind of technology is reasonable, workable, the purity of bromine is high bromine is provided.
Technical problem to be solved by this invention is to realize by following technical scheme.The present invention is a kind of steam distillation method for preparing bromine by, is characterized in, its step is as follows:
(1) oxidation distillation: with pH is that 2.5～3.5 raw brine is squeezed into header tank, bittern flows into preheater from header tank, cat head by the bromine tower after the preheater preheating enters in the bromine tower, feed chlorine and steam from the bromine tower bottom, after carrying out the oxidation distillation reaction in the bromine tower, carry the bromine waste liquid and discharge from the bromine tower bottom, the mixed steam of bromine, chlorine G﹠W then is expelled to the condenser from bromine tower top;
(2) condensation: mixed steam condensation in condenser of bromine, chlorine G﹠W, get bromine and bromine water mixture after the condensation, coagulate gas and discharge by the road;
(3) separate: bromine and bromine water mixture that condensation is obtained flow in the separating bottle by pipeline, because proportion difference, bromine and bromine water mixture natural layering in separating bottle, upper strata bromine water is back in the bromine tower by pipeline, and the lower coarse bromine then flow to still in the rectifying tower by the road from the separating bottle bottom;
(4) rectifying: rectifying is carried out in the rectifying tower still, Heating temperature during rectifying is 58～58.5 ℃, mixed gas is discharged at top from the rectifying tower still during rectifying, mixed gas enters the reflux exchanger condensation by the road, phlegma is back in the rectifying tower still by the road, coagulate gas and discharge by the road, the bromine liquid in the heating kettle of rectifying tower still drains into water cooler, gets smart bromine.
In above-described steam distillation method for preparing bromine by, following optimal technical scheme can also be arranged:
1, it also is provided with recovery tower, is provided with normal temperature bittern in the recovery tower, and the described gas that do not coagulate of step (2) and step (4) is expelled in the recovery tower by the road, enters the bromine tower after bittern reclaims, and all the other are not reclaimed gaseous emission;
2, in step (1), the chlorine rate of joining in the bromine tower is 110～120%, describedly joins the per-cent that the chlorine rate is actual chlorine charge and theoretical chlorine charge;
3, in step (1), the flow in bittern enters the bromine tower is 2～9 meters
3In/time, the preheating temperature of bittern in preheater is 60～75 ℃; In step (1), the feed rate of steam is regulated according to the tower mouth temperature that goes out of the mixed steam of bromine, chlorine G﹠W, and the mixed steam of bromine, chlorine G﹠W goes out tower mouth temperature and is controlled at 80～90 ℃;
4, in step (2), the condensing temperature of condenser is 20～30 ℃;
5, in step (3), bromine water and the line of delimitation of bromine liquid establish for separating the level layer that to separate level layer to the height of bromine water laminar surface be H in the described separating bottle, and separating level layer to the height of liquid bromine center line of discharge is h, then: H=3h;
6, adorn a pressure equalizing pipe in a side of separating bottle;
7, in step (4), the condensing temperature of reflux exchanger is 30～35 ℃ during rectifying;
8, in step (4), rectifying when heating with thick bromine sequential portion be heated to 58.0～58.5 ℃.
Below technical scheme of the present invention is carried out concrete elaboration.
One, production principle.
Steam distillation legal system bromine is through bittern preheating, oxidation displacement and vapor distillation (finishing in the same at one time equipment of oxidation displacement and vapor distillation), and processes such as the condensation of bromine vapour, bromine water are separated, smart stream are finished.Raw brine of the present invention can be salt-making mother liquor, old halogen or other bittern, also can be the seawater through certain evaporation process, as long as wherein contain the raw material that the bittern of the bromine of certain content all can be made bromine do the present invention.
Bromine in the bittern is that the form with bromide exists, and generally regards magnesium bromide (MgBr as
2), bromide ionization is bromide anion Br
-, feed chlorine and just can obtain elemental bromine later, oxidation displacement reaction process below Here it is:
MgBr
2+Cl
2＝MgCl
2+Br
2↑
Perhaps, 2Br
-+ Cl
2=Br
2↑+2Cl
-
But, the bromine that obtains of reflection is also in bittern, according to a main character of bromine: its vapour pressure above the aqueous solution increases with the rising of temperature, Here it is the continuous brine temperature after the rising oxidation, bromine vapor is constantly run out of from bittern, wet distillation process that Here it is.
At normal temperatures and pressures, bromine is liquid, so just can obtain liquid bromine when the bromine vapor of running out is cooled to normal temperature, but after the bittern elevated temperature, the bromine vapor part of running out not only, not having the chlorine and the water vapor of complete reaction also to run out, is the mixture of bromine, chlorine and water so bromine vapor cooling obtains.
Dissolving 3.2 gram bromines in the 100 gram water under the normal temperature, water just becomes saturated bromine water, and proportion is 1.02, all the other bromines (small amounts of chlorine is contained in the inside) limit is not dissolved in the water and Individual existence, and the proportion of bromine is 3.1, so bromine water is on the upper strata, the liquid bromine that contains small amounts of chlorine can obtain the liquid bromine in lower floor by separating bottle.
The boiling point of bromine is 58.8 ℃, the boiling point of chlorine is-34.6 ℃, because bromine is higher 93 ℃ than the boiling point of chlorine, so in the time of will containing the liquid bromine of small amounts of chlorine and be heated to certain temperature, low-boiling chlorine becomes gas rapidly and runs away, and the higher bromine major part of boiling point is liquid and exists, thereby obtains comparatively purified smart bromine, Here it is rectifying.
The above-mentioned system bromine principle that is steam distillation legal system bromine of the present invention.
Two, the concrete technical process of wet distillation legal system bromine.
1, technical process.
Because what the present invention adopted is steam distillation distillation legal system bromine, its technical process can be referring to Fig. 1, characteristics of the present invention be with water vapor with oxidation after free bromine in the bittern separate.
Raw brine is squeezed into header tank, the cat head of flowing through after the preheater preheating by the bromine tower enters in the bromine tower, feed chlorine and steam from the bromine tower bottom, after carrying out the oxidation distillation reaction in the bromine tower, carrying the bromine waste liquid discharges from the bromine tower bottom, bromine, chlorine, the mixed steam of water then is expelled to the condenser from bromine tower top, with getting bromine and bromine water mixture after the fresh water condensation, bromine and bromine water mixture are flowed in the separating bottle by pipeline, because proportion difference, bromine and bromine water mixture natural layering in separating bottle, upper strata bromine water is back in the bromine tower by pipeline, and thick bromine then flow in the rectifying tower by the road from the separating bottle bottom, and rectifying tower top is discharged chlorine and bromine gas etc., through reflux exchanger condensing reflux part bromine, do not coagulate gas and drain into recovery tower, reclaim laggard bromine tower through bittern, all the other do not coagulate gas emptying, smart bromine drains into water cooler by the rectifying heating kettle, gets smart bromine.
2, related process technical qualification.
Steam distillation is put forward the bromine technological process, generally can be divided into: oxidation, distillation, condensation, separation, steps such as rectifying and tail gas recycle.Below several main technique conditions of above steps are set forth.
Keeping in balance between steam, bittern, the chlorine three is that the bromine tower produces the prerequisite normally carry out, and the check mark of tower normal running is that the liquid bromine evenly enters in the separating bottle, and the content of free bromine and chemical combination bromine is no more than standard and plants in the waste liquid.
(1) oxidation
Oxidising process is in order to make the bromine in the bittern be converted into the bromine of unbound state from ionic condition.This conversion is that reduction has taken place chlorine, has carried out the result of oxidation-reduction reaction because after feeding chlorine, oxidation has taken place bromide anion.The following reaction process of following surface analysis.
Bromide anion is converted into bromine, can be represented by the formula:
2Br
--2e→Br
2
Bromide anion loses the oxidation that electronic processes is a bromine.Employing chlorine removes to capture the electronics in the bromide anion, has created the condition that bromide anion transforms, the oxidation of the bromine of facilitating, and chlorine has obtained electronics and has been converted into chlorion, can be expressed as:
Cl
2+2e＝2Cl
-
The process that chlorine obtains electronics is the reduction of chlorine.After feeding chlorine in the bittern, oxidation-reduction reaction takes place immediately.Can get following reaction equation by above-mentioned two reaction formula additions:
2Br
-+ Cl
2=Br
2+ 2Cl
-+ heat release ... ... (1)
This reaction moment has been set up running balance.Br
-Ion (or Cl
-Ion) oxidation and Cl
-(Br
2) reduction, formed a running balance system.Br
-The ionic oxidising process, the oxidation ratio of available bittern is weighed, and oxidation ratio generates free bromine (Br after being meant oxidation
2) amount and oxidation before bromide anion (Br in the bittern
-) amount per-cent.
Oxidation ratio=[C
1-C
2(1+N)]/C
1* 100%
C in the formula
1Br in the-raw brine
-Ion content (grams per liter)
C
2-carry Br in the bromine waste liquid
-Ion content (grams per liter)
The N-thinning ratio refers to carry the percentage ratio that the volume ratio raw brine volume of bromine waste liquid increases, and is generally about 10%.
In the leaching process of bromine, the height of oxidation ratio is the principal element that influences extraction yield.The chemical equilibrium of reaction equation (1) is temporary transient, relative, with good conditionsi.Create the condition of favourable bromide anion conversion and should note following two problems.
The one, acidity.Suitable acidity is to extract the prerequisite of bromine from bittern, the sour environment of general requirement pH=2.5～3.5 (preferred pH=2.9～3.2), and this is because following reaction easily takes place for bromine and water:
Or be expressed as follows with the ionic reaction formula:
By reaction formula (2), (3) as can be known, in slightly acidic or basic solution, reaction is easily carried out to the right, suppress the reaction of bromine and water, and reaction is carried out left, will make H
+Ionic concn big (the pH value of ie in solution is littler).Generally speaking, the pH=2.5 of bittern～3.5 do not need acidifying, if it is bigger to put forward the pH value of bromine raw brine, then need to carry out acidification.
The 2nd, join the chlorine rate.
By reaction formula (1) as can be seen, the brominated (Br of bittern
-Ion) the high more or logical chlorine (Cl of amount
2) amount increases and all to help Br
-Ion is to generating Br
2Direction carry out.Advance the brominated amount and flow one timing of tower bittern, Br
-The ionic amount is certain, how much just suitable is the amount of chlorine that feeds so in the bittern? calculate 1 kilogram of bromine of every production according to reaction equation in theory, the theoretical consumption of chlorine is 0.445 kilogram.
In order to make the Br in the bittern
-The abundant oxidation of ion considers also that simultaneously part chlorine also will be consumed in impurity in the oxidation bittern and a small amount of chlorine and will enter the loss that causes in the bromine vapor etc., often needs to add some chlorine.This will select the suitable chlorine rate of joining, and join the per-cent that the chlorine rate is actual chlorine charge and theoretical chlorine charge.Its calculating formula is:
Join chlorine rate (%)=actual chlorine charge/theoretical chlorine charge * 100%
Theoretical chlorine dosage is 0.445 kilogram in the formula.
The practice of trial production that carries out through the contriver proves, joins the chlorine rate and will determine according to the brominated amount of bittern, generally can be 100～130%, preferably is controlled at 110～120%.
The feed rate of chlorine also can be regulated according to the content of chemical combination bromine in the waste liquid, as chlorine feed rate deficiency, then can not fully replace the bromide anion in the bittern and cause that the chemical combination bromine content increases in the waste liquid, influence the extraction yield of bromine, if too much, can cause the consumption of chlorine big for chlorine; Influence final product quality; Can reaction take place to pay with bromine and generate halogen compounds, also cause chloride increasing in the emptying tail gas, contaminate environment.
According to selected chlorine rate (every bromine tower the is per hour) chlorine dosage can computer board time of joining:
Chlorine dosage during platform (kilogram)=bittern flow (rice
3/ time) * the brominated amount (kilogram/rice of bittern
3) * 0.445 * join chlorine rate (%)
(2) distillation
Still-process carries out in the bromine tower.Bittern advances tower from cat head, and steam and chlorine advance tower from the bottom respectively, and bromine vapor goes out the bromine mouth from tower top draws, and carries the bromine waste liquid and discharges at the bottom of tower.
Bittern after the oxidation mainly is to contain the aqueous solution such as bromine, small amounts of chlorine and inorganic salt.In operating process, because chlorine (Cl in each component of bittern
2), bromine (Br
2) and water (H
2O) all be the component of easily bringing into play, size of its volatilization ability can be weighed with vapour pressure, and vapour pressure is bigger, and the volatilization ability more greatly.Under same temperature, their vapour pressure is
The contriver utilizes the difference of their capability development, separates fluid bromine (also being thick bromine) and bromine water from the bittern of oxidation, and this operating process is called distillation, extracts bromine, is called steam distillation again owing to utilize water vapor to make termite.Make a concrete analysis of the changing conditions of material in the bromine tower below.
Water vapor, chlorine, bromine vapor move upward along tower in the bromine tower, and bittern enters continuously from cat head, and balance old between gas-liquid is constantly broken, and new balance is constantly set up.In the arbitrary zone of inner-tower filling material, chlorine constantly dissolves, spreads and reacts, and bromine constantly generates, and dissolves and overflow, with the same successive vaporization of water and condensation.The mixed gas of chlorine, bromine, water keeps in touch with solution all the time, is in relative balance state between the gas-liquid.
From top to bottom, bromine is more and more in the gas phase, and the vapour pressure of bromine is increasing.Otherwise water vapour constantly enters liquid phase, and water vapor pressure is more and more littler.At the composition content that goes out bromine mouth place gas phase is based on bromine vapor, and contains water vapor and a small amount of chlorine etc.
The bromine tower equals the dividing potential drop sum of each gas with the total pressure of the gaseous mixture of bromine, chlorine, water.
In the formula: P
AlwaysBe total gas pressure,
Be respectively the partial pressure of chlorine, bromine, water.As can be seen from the above equation, expect more bromine, just must improve the dividing potential drop of bromine vapor
When the dissolution rate of bromine equals steam effusion speed from solution, when promptly reaching running balance,
Relevant with the content of bromine in the liquid phase, relevant with the content of bromine in the gas phase again.
The relation of bromine concentration can be represented by the formula in bromine vapor dividing potential drop and the solution:
In the formula: E---Henry'S coefficient (normal atmosphere or mmhg), its value increases with the rising of temperature;
In the formula: P
Always---the total pressure (normal atmosphere or millimeter) of mixed gas;
When being in equilibrium state:
As can be seen from the above equation: work as P
AlwaysOne regularly, the mole number of bromine vapor
The mole fraction in solution along with Henry'S coefficient E and bromine
Increase, the bromine vapor amount also increases along with the rising of temperature in the ordinary course of things.The mole fraction of bromine in solution reflected the size of bromine concentration in solution, and the amount of bromine vapor is along with the concentration of bromine in the solution increases and increases, and therefore, will control following condition aborning well:
The one, the bromine vapor mixture goes out tower mouth temperature and steam delivery volume.
The feed rate of steam goes out tower mouth temperature according to the bromine vapor mixture and regulates, generally be controlled in 75～95 ℃ of scopes, preferably be controlled in 80～90 ℃ of scopes, if feed the steam deficiency, then the tower Outlet Gas Temperature reduces, the bittern that the bromine vapor that has steamed has newly been gone into tower absorbs, and the liquid bromine of collecting in bromine water-separating bottle will reduce, and proposes free bromine content increase in the bromine waste liquid simultaneously.If quantity of steam is excessive, then Outlet Gas Temperature rises, and along with the fierce distillation of bromine, a large amount of steam enters in the condenser, and the bromine water amount is increased, and not only influences the output of bromine, can cause bursting of water cooler when serious.
It is to contact later temperature by the bromine vapor mixture that rises in the tower with the raw brine that just advances tower basically that the bromine vapor mixture goes out tower mouth temperature, so it is to be decided by the quantity of steam that feeds and the preheating temperature of bittern, is mainly fed the influence of quantity of steam.
The purpose that feeds steam is that the bromine that oxidation in the bittern is come out is distilled, and when the bittern flow was big, steam consumption just increased, bittern flow hour, and steam consumption is just less.
The 2nd, bittern preheating temperature and bittern flow.
The purpose of bittern preheating is that indirect heating bittern makes it reach certain temperature, the desorb that helps bromine with separate, guarantee normally carrying out of bromine tower work, the bittern flow is decided according to producing needs, preheating temperature during with platform flow relevant, be generally:
Flow during platform: 2-4 rice
3In/time,, preheating temperature was about 60 ℃;
4-6 rice
3In/time,, preheating temperature was about 65-70 ℃;
6-9 rice
3In/time,, preheating temperature was about 75 ℃;
Preheating temperature was answered corresponding raising when the bittern flow was big, mainly was the interior temperature of tower is reduced to guarantee good reaction.When just driving, advance tower bittern preheating temperature than just often improving (about 3-5 ℃) so that temperature rises rapidly in the tower, make reaction enter standard state as early as possible, temperature is the principal element that influences distillation procedure, and distillation temperature is mainly determined by two aspects, the one, the bittern preheating temperature, the one, feed the open steam amount.
Preheating temperature is for the influence of distillation procedure.Bittern preheating and do not reach its boiling point outside tower, enter in the tower and will contact with the steam in the tower, in the steam bromine vapour and steam are arranged in the tower, when running into high-temperature steam, low temperature halogen will carry out heat exchange, make bittern continue elevated temperature, make water vapor condensation, because the boiling point of bromine is lower than the boiling point of water, so the bromine vapor agglomerative is few, water recovery many, the dividing potential drop of bromine vapor in the mixed gas on tower top is increased, and the bromine vapor of using in the bromine mouth place mixed gas has increased, and it is just many that this mixed gas goes out the liquid bromine that condensation obtains behind the tower.
The size of bittern flow is to determine according to factors such as the output of production program bromine, equipment.
The 3rd, the temperature of waste liquid relief outlet and waste liquid amount.
The temperature of carrying bromine waste liquid relief outlet is generally 115 ℃～117 ℃, and the volume of carrying the bromine waste liquid generally increases by 8～10% than the raw brine volume that enters because of the condensation that feeds water vapor increases, and concentration reduces about 2 ° of Be '.
(3) condensation
The purpose of condensation is to make the Mixed Gas Condensation of discharging in the bromine tower.The height of condensing temperature has certain relation with the quality of the rate of recovery of bromine and bromine, the extraction yield and the chlorinity of bromine reduce along with the rising of condensing temperature, the content of bromine reduces with the rising of condensing temperature, and in general condensing temperature is controlled at about 20-30 ℃ and gets final product, and is unsuitable too high or too low.
(4) separate
After the bromine vapor mixture is condensed in condenser (preferred coil condenser), phlegma flows into separating bottle, the saturated bromine water proportion that contains small amount of bromine is about 1.02, and is lighter, above floating over, liquid bromine proportion is 3.1, at the bottom of heavily sinking to bottle than bromine water, from bromine water outlet and liquid bromine outlet outflow, bromine water generally enters in the bromine tower from the middle part of tower respectively for the two, continue distillation, the liquid bromine is that thick bromine inflow rectifying tower is made with extra care.
Because bromine water and AUTOMATIC ZONING different with the proportion of bromine liquid, its line of delimitation is separation level layer in separating bottle.If separating level layer to the height of bromine water laminar surface is H, be h by separating level layer to the height of liquid bromine center line of discharge, then preferred:
H/h=liquid bromine proportion/bromine water proportion=3.1/1.02=3, i.e. H=3h
Pressure in the bromine separator can separate automatically with the liquid bromine in this case, referring to Fig. 2.
Under the ordinary production situation, the bromine water amount and the liquid bromine amount that produce in the unit time are certain, and the position of then separating the level layer is also with regard to basic fixed, but when fluctuation of service, on the low side such as going out tower mouth temperature owing to the bromine vapor mixture, make the interior bromine water amount that produces of unit time reduce, corresponding liquid bromine amount increases, then separate the level layer and up move, cause H＜3h, bromine and bromine water flow into reaction tower simultaneously, on the contrary, when the bromine water amount was too big, H＞3h may cause bromine water to be pressed into rectifying tower.In order to prevent this situation, can adorn a pressure equalizing pipe in a side of separating bottle, the pressure of two place's liquid levels is equated, when occurring the situation of H＞3h again, just can not make bromine water enter rectifying tower.
(5) rectifying
Generally speaking, brominated amount accounts for 98～96% in the thick bromine that makes by method of the present invention, and chlorinity accounts for 3～6%, also contains a small amount of high boiling organism etc., in order to obtain brominated amount height, impure few smart bromine, must make with extra care.Because the boiling point of pure bromine is 58.5 ℃, the boiling point of pure chlorine is-34.1 ℃, so chlorine is easily to bring into play component in thick bromine, bromine is difficult performance component, according to the boiling point of measuring thick bromine is about 58 ℃, when thick bromine is heated to boiling point, the vapor composition that is generated is different with thick bromine, wherein easily performance component chlorine content in steam reaches 32.4%, and difficult evaporable bromine content in steam is 67.6%, if the Mixed Gas Condensation of resulting this chlorine and bromine, boiling point height because of bromine, condensation many, chlorine is just more in the resulting live steam, can reach 57%, bromine just still less, be reduced to 43%, the condensation again of this live steam, the content of the more and bromine of the content of chlorine still less in the steam.The thick whole vaporizations of bromine can not make bromine separate with chlorine, have only the method with the part vaporization, could isolate volatile component chlorine from thick bromine.So thick bromine sequential portion ground is heated to boiling point, lower boiling chlorine is volatilized, again this chlorine, bromine mixed gas are controlled higher slightly condensing temperature, the chlorine major part is thrown out and bromine vapour major part is returned in condensation.
Rectifying is generally carried out in rectifying tower, and thick bromine enters from cat head, is heated in the rectifying still of bottom and boils.Reflux condensation mode part bromine in rectifying tower and in the condenser, chlorine has just volatilized.In order to obtain the high smart bromine of quality, the general control of the reflux condensation mode temperature of rectifying is higher slightly, is advisable with 30～35 ℃.
(6) reclaim
The gas that is recovered is two portions: thick bromine condensation tail gas and thick bromine tail gas.What the present invention will reclaim is chlorine and bromine, and absorption agent is a raw brine of making bromine, and chlorine solubleness in water was very little originally, but because the bromide anion (Br in chlorine and the absorption agent bittern
-) to carry out chemical reaction, so bittern is not simple absorption to chlorine, but with the generation of chemical reaction.Chemical reaction reduces with the rising of temperature, so absorb better with low temperature bittern.The solubleness of bromine in bittern mainly contains two factor affecting, and the one, temperature, temperature are higher, and solubleness is littler, and the 2nd, chlorion (Cl in the bittern
-) concentration, chlorion (Cl in the bittern
-) concentration is big more, can form complexing ion (BrCl with bromine
-), thereby the solubleness of bromine is increased, so to the absorption of bromine also be low temperature bittern preferably.So preferably adopt the bittern of normal temperature that tail gas is reclaimed on producing.
Three, the relevant system bromine equipment that the present invention relates to.
1, bromine tower
The bromine tower is the major equipment of system bromine, and bromine tower of the present invention can be selected packing tower and sieve-tray tower for use, excellent preferred filler tower, and disclosed any packing tower and sieve-tray tower all can be selected for use by requirement of the present invention in the prior art.
Below be to preferably being applicable to the related description of a kind of packing tower of the present invention.The cylindric tower joint that this tower can be made by granite or assembled by inner steel lining acid-proof cement (or diabase) forms, every joint height is about 0.6～0.7 meter, tower diameter is selected according to industrial scale, in fill ceramic cup or saddle packing, porcelain cup is irregular alignment, be generally about 15 joints, the about 8-10 rice of height overall, packing tower divides three parts: the tower lid, body of the tower and tower seat, raw brine adds from cat head, steam second joint under the tower enters, and chlorine generally enters from the 3rd joint, and steam and chlorine are wanted to go up along the short transverse of tower and moved, steam, chlorine and bittern counter current contact, the distillation of bromine and bromide anion are carried out in same equipment by oxychlorination, and two processes take place simultaneously, and this just requires the structure of bromine tower must adapt to this characteristics.
The reaction of chlorine and bromide anion, the reaction of chlorine and bittern, a size that important factor is a contact surface of influence reaction, contact area is big more, and speed of response is accelerated.
Bromine in the bittern is distilled, an essential condition is to improve brine temperature, this just need make steam fully contact along the unobstructed rising of tower direction and with bittern, Here it is requires steam and bittern that bigger contact area is not only arranged, and make the resistance of gas little, prevent that steam from discharging with waste liquid, influence is conducted heat.
Practice of trial production proves: oxidizing reaction mainly occurs in the middle and upper part of tower, still-process occurs in the middle and lower part of tower, this be because: in the bottom of tower, chlorine is by the violent dilution of steam, therefore the dividing potential drop of chlorine becomes very little, dividing potential drop with the gradually condensation chlorine of water vapour in tower also increases gradually, reacts with bromide anion so begin violent being dissolved in the bittern at the middle and upper part of tower chlorine; Raw brine drenches following time by cat head, and wherein bromide ion concentration is higher, so oxidizing reaction occurs in the middle and upper part; Steam enters under tower, and the bittern after the oxidation runs into high-temperature steam when flowing to the middle and lower part of tower, and bromine is just distilled in the gas phase tempestuously, so still-process mainly occurs in the middle and lower part of tower.
For oxidizing reaction, mainly be that the requirement filler has bigger surface-area, gas-liquid is fully contacted.
For still-process, not only require filler to have the contact area of increasing, and resistance is less, because being the bottom from tower, steam enters, condensation gradually in uphill process, thus bigger at the middle and lower part of tower pressure, need bigger space to pass through, otherwise steam does not increase, and discharges with waste liquid.
Therefore should fill different fillers for the oxidation panel (middle and upper part) of packing tower with distilling period (middle and lower part).The effect of filler mainly is in order to increase the surface in contact between the gas-liquid, because the less filler filler bigger than specification of specification has bigger surface-area, but free volume becomes down, be that the space slight drag is big, so fill out medium-sized or middle-size and small-size mixed fillers in the middle and upper part of tower more, general per three joints support filler by a dividing plate, and dividing plate also plays a part to shrink bittern, prevent wall bias current of bittern salt tower and gas loose contact in the tower.One of material separating disc is arranged at the top of tower, mainly is for bittern being evenly distributed, being stamped the fluid-tight bubble-cap on the aperture of material separating disc, current to prevent gas.
2, preheater
The bittern preheating can be selected conventional steel tube still heater for use.
3, condenser
The condenser that condenser preferably selects for use borosilicate glass to make.
4, separating bottle
The material of separating bottle is preferably selected borosilicate glass for use, selects for use separating bottle of the prior art to get final product by purpose requirement of the present invention, also can be by requirement self-control of the present invention.
5, rectifying tower
Rectifying tower also has sieve-tray tower, the first-class various ways of packing tower, and preferred filler is tower, and the present invention can select disclosed any rectifying tower that is applicable to the object of the invention in the prior art for use.General rectifying tower outer wall is useful granitic, also useful pottery, in fill the porcelain ring filler, the bottom is with enamel heating kettle water vapour indirect heating, slightly bromine adds from cat head, smart bromine is discharged from rectifying still.
6, recovery tower
Recovery tower mostly is packing tower, and outer wall useful granitic liquid is useful pottery also, in fill the porcelain ring filler.Bittern enters at the bottom of tower from cat head and discharges, and mixed gas enters at the bottom of tower, does not coagulate gas from top emptying.Gas, liquid countercurrent mass transfer in recovery tower.
Compared with prior art, technology of the present invention is reasonable, and is easy and safe to operate, and prepared bromine purity height is fit to industrialized production.
Description of drawings
Fig. 1 is a kind of flowage structure synoptic diagram of the present invention.
Fig. 2 is a kind of structural representation of separating bottle.
Embodiment
Following with reference to accompanying drawing, further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not constitute restriction to its right.
Embodiment 1.With reference to Fig. 1-2.A kind of steam distillation method for preparing bromine by, its step is as follows:
(1) oxidation distillation: with pH is that 2.5 raw brine is squeezed into header tank 1, bittern flows into preheater 2 from header tank 1, cat head by bromine tower 3 after preheater 2 preheatings enters in the bromine tower 3, feed chlorine and steam from bromine tower 3 bottoms, after carrying out the oxidation distillation reaction in the bromine tower 3, carry the bromine waste liquid and discharge from bromine tower 3 bottoms, the mixed steam of bromine, chlorine G﹠W then is expelled to the condenser 5 from bromine tower 3 tops;
(2) condensation: mixed steam condensation in condenser 5 of bromine, chlorine G﹠W, get bromine and bromine water mixture after the condensation, coagulate gas and discharge by the road;
(3) separate: bromine and bromine water mixture that condensation is obtained flow in the separating bottle 6 by pipeline, because proportion difference, bromine and bromine water mixture natural layering in separating bottle 6, upper strata bromine water is back in the bromine tower 3 by pipeline, and the lower coarse bromine then flow in the rectifying tower still 7 by the road from separating bottle 6 bottoms;
(4) rectifying: rectifying is carried out in rectifying tower still 7, Heating temperature during rectifying is 58 ℃, mixed gas is discharged at top from rectifying tower still 7 during rectifying, mixed gas enters reflux exchanger 9 condensations by the road, phlegma is back in the rectifying tower still 7 by the road, coagulate gas and discharge by the road, the bromine liquid in the heating kettle of rectifying tower still 7 drains into water cooler 8, gets smart bromine.
Embodiment 2.With reference to Fig. 1-2.A kind of steam distillation method for preparing bromine by, its step is as follows:
(1) oxidation distillation: with pH is that 3.5 raw brine is squeezed into header tank 1, bittern flows into preheater 2 from header tank 1, cat head by bromine tower 3 after preheater 2 preheatings enters in the bromine tower 3, feed chlorine and steam from bromine tower 3 bottoms, after carrying out the oxidation distillation reaction in the bromine tower 3, carry the bromine waste liquid and discharge from bromine tower 3 bottoms, the mixed steam of bromine, chlorine G﹠W then is expelled to the condenser 5 from bromine tower 3 tops;
(2) condensation: mixed steam condensation in condenser 5 of bromine, chlorine G﹠W, get bromine and bromine water mixture after the condensation, coagulate gas and discharge by the road;
(3) separate: bromine and bromine water mixture that condensation is obtained flow in the separating bottle 6 by pipeline, because proportion difference, bromine and bromine water mixture natural layering in separating bottle 6, upper strata bromine water is back in the bromine tower 3 by pipeline, and the lower coarse bromine then flow in the rectifying tower still 7 by the road from separating bottle 6 bottoms;
(4) rectifying: rectifying is carried out in rectifying tower still 7, Heating temperature during rectifying is 58.5 ℃, mixed gas is discharged at top from rectifying tower still 7 during rectifying, mixed gas enters reflux exchanger 9 condensations by the road, phlegma is back in the rectifying tower still 7 by the road, coagulate gas and discharge by the road, the bromine liquid in the heating kettle of rectifying tower still 7 drains into water cooler 8, gets smart bromine.
Embodiment 3.With reference to Fig. 1-2.A kind of steam distillation method for preparing bromine by, its step is as follows:
(1) oxidation distillation: with pH is that 3 raw brine is squeezed into header tank 1, bittern flows into preheater 2 from header tank 1, cat head by bromine tower 3 after preheater 2 preheatings enters in the bromine tower 3, feed chlorine and steam from bromine tower 3 bottoms, after carrying out the oxidation distillation reaction in the bromine tower 3, carry the bromine waste liquid and discharge from bromine tower 3 bottoms, the mixed steam of bromine, chlorine G﹠W then is expelled to the condenser 5 from bromine tower 3 tops;
(2) condensation: mixed steam condensation in condenser 5 of bromine, chlorine G﹠W, get bromine and bromine water mixture after the condensation, coagulate gas and discharge by the road;
(3) separate: bromine and bromine water mixture that condensation is obtained flow in the separating bottle 6 by pipeline, because proportion difference, bromine and bromine water mixture natural layering in separating bottle 6, upper strata bromine water is back in the bromine tower 3 by pipeline, and the lower coarse bromine then flow in the rectifying tower still 7 by the road from separating bottle 6 bottoms;
(4) rectifying: rectifying is carried out in rectifying tower still 7, Heating temperature during rectifying is 58.2 ℃, mixed gas is discharged at top from rectifying tower still 7 during rectifying, mixed gas enters reflux exchanger 9 condensations by the road, phlegma is back in the rectifying tower still 7 by the road, coagulate gas and discharge by the road, the bromine liquid in the heating kettle of rectifying tower still 7 drains into water cooler 8, gets smart bromine.
Embodiment 4.With reference to Fig. 1-2.A kind of steam distillation method for preparing bromine by, its step is as follows:
(1) oxidation distillation: with pH is that 3.1 raw brine is squeezed into header tank 1, bittern flows into preheater 2 from header tank 1, cat head by bromine tower 3 after preheater 2 preheatings enters in the bromine tower 3, feed chlorine and steam from bromine tower 3 bottoms, after carrying out the oxidation distillation reaction in the bromine tower 3, carry the bromine waste liquid and discharge from bromine tower 3 bottoms, the mixed steam of bromine, chlorine G﹠W then is expelled to the condenser 5 from bromine tower 3 tops;
(2) condensation: mixed steam condensation in condenser 5 of bromine, chlorine G﹠W, get bromine and bromine water mixture after the condensation, coagulate gas and discharge by the road;
(3) separate: bromine and bromine water mixture that condensation is obtained flow in the separating bottle 6 by pipeline, because proportion difference, bromine and bromine water mixture natural layering in separating bottle 6, upper strata bromine water is back in the bromine tower 3 by pipeline, and the lower coarse bromine then flow in the rectifying tower still 7 by the road from separating bottle 6 bottoms;
(4) rectifying: rectifying is carried out in rectifying tower still 7, Heating temperature during rectifying is 58.1 ℃, mixed gas is discharged at top from rectifying tower still 7 during rectifying, mixed gas enters reflux exchanger 9 condensations by the road, phlegma is back in the rectifying tower still 7 by the road, coagulate gas and discharge by the road, the bromine liquid in the heating kettle of rectifying tower still 7 drains into water cooler 8, gets smart bromine.
Embodiment 5.Among the embodiment 1-4 in any one described steam distillation method for preparing bromine by, it also is provided with recovery tower 4, feed normal temperature bittern in the recovery tower 4, the described gas that do not coagulate of step (2) and step (4) is expelled in the recovery tower 4 by the road, after bittern reclaims, enter bromine tower 3, and all the other are not reclaimed gaseous emission.
Embodiment 6.Among the embodiment 1-5 in any one described steam distillation method for preparing bromine by, in step (1), the chlorine rates of joining in the bromine tower 3 are 110, describedly join the per-cent that the chlorine rate is actual chlorine charge and theoretical chlorine charge.
Embodiment 7.Among the embodiment 1-5 in any one described steam distillation method for preparing bromine by, in step (1), the chlorine rates of joining in the bromine tower 3 are 120%, describedly join the per-cent that the chlorine rate is actual chlorine charge and theoretical chlorine charge.
Embodiment 8.Among the embodiment 1-5 in any one described steam distillation method for preparing bromine by, in step (1), the chlorine rates of joining in the bromine tower 3 are 115%, describedly join the per-cent that the chlorine rate is actual chlorine charge and theoretical chlorine charge.
Embodiment 9.In any one described steam distillation method for preparing bromine by, in step (1), the flow in bittern enters bromine tower 3 is 2～3 meters among the embodiment 1-8
3In/time, the preheating temperature of bittern in preheater 2 is 60 ℃.
Embodiment 10.In any one described steam distillation method for preparing bromine by, in step (1), the flow in bittern enters bromine tower 3 is 4～5 meters among the embodiment 1-8
3In/time, the preheating temperature of bittern in preheater 2 is 65 ℃.
Embodiment 11.In any one described steam distillation method for preparing bromine by, in step (1), the flow in bittern enters bromine tower 3 is 6～9 meters among the embodiment 1-8
3In/time, the preheating temperature of bittern in preheater 2 is 75 ℃.
Embodiment 12.In any one described steam distillation method for preparing bromine by, in step (1), the feed rate of steam is regulated according to the tower mouth temperature that goes out of the mixed steam of bromine, chlorine G﹠W among the embodiment 1-11, and the mixed steam of bromine, chlorine G﹠W goes out tower mouth temperature and is controlled at 80 ℃.
Embodiment 13.In any one described steam distillation method for preparing bromine by, in step (1), the feed rate of steam is regulated according to the tower mouth temperature that goes out of the mixed steam of bromine, chlorine G﹠W among the embodiment 1-11, and the mixed steam of bromine, chlorine G﹠W goes out tower mouth temperature and is controlled at 90 ℃.
Embodiment 14.In any one described steam distillation method for preparing bromine by, in step (1), the feed rate of steam is regulated according to the tower mouth temperature that goes out of the mixed steam of bromine, chlorine G﹠W among the embodiment 1-11, and the mixed steam of bromine, chlorine G﹠W goes out tower mouth temperature and is controlled at 85 ℃.
Embodiment 15.In any one described steam distillation method for preparing bromine by, in step (2), the condensing temperature of condenser 5 is 20 ℃ among the embodiment 1-14.
Embodiment 16.In any one described steam distillation method for preparing bromine by, in step (2), the condensing temperature of condenser 5 is 30 ℃ among the embodiment 1-14.
Embodiment 17.In any one described steam distillation method for preparing bromine by, in step (2), the condensing temperature of condenser 5 is 25 ℃ among the embodiment 1-14.
Embodiment 18.Among the embodiment 1-17 in any one described steam distillation method for preparing bromine by, in step (3), bromine water and the line of delimitation of bromine liquid are for separating the level layer in the described separating bottle 6, if separation level layer to the height of bromine water laminar surface is H, separating level layer to the height that the liquid bromine exports 10 medullary rays is h, then: H=3h.
Embodiment 19.In any one described steam distillation method for preparing bromine by, adorn a pressure equalizing pipe 11 among the embodiment 1-18 in a side of separating bottle 6.
Embodiment 20.In any one described steam distillation method for preparing bromine by, in step (4), the condensing temperature of reflux exchanger 9 is 30 ℃ during rectifying among the embodiment 1-19.
Embodiment 21.In any one described steam distillation method for preparing bromine by, in step (4), the condensing temperature of reflux exchanger 9 is 35 ℃ during rectifying among the embodiment 1-19.
Embodiment 22.In any one described steam distillation method for preparing bromine by, in step (4), the condensing temperature of reflux exchanger 9 is 32 ℃ during rectifying among the embodiment 1-19.
Embodiment 23.Among the embodiment 1-22 in any one described steam distillation method for preparing bromine by, in step (4), during the rectifying heating with thick bromine sequential portion be heated to described Heating temperature.
Claims (9)
1. a steam distillation method for preparing bromine by is characterized in that, its step is as follows:
(1) oxidation distillation: with pH is that 2.5～3.5 raw brine is squeezed into header tank (1), bittern flows into preheater (2) from header tank (1), cat head by bromine tower (3) after preheater (2) preheating enters in the bromine tower (3), feed chlorine and steam from bromine tower (3) bottom, after carrying out the oxidation distillation reaction in the bromine tower (3), carry the bromine waste liquid and discharge from bromine tower (3) bottom, the mixed steam of bromine, chlorine G﹠W then is expelled to the condenser (5) from bromine tower (3) top;
(2) condensation: the condensation in condenser (5) of the mixed steam of bromine, chlorine G﹠W, get bromine and bromine water mixture after the condensation, coagulate gas and discharge by the road;
(3) separate: bromine and bromine water mixture that condensation is obtained flow in the separating bottle (6) by pipeline, because proportion difference, bromine and bromine water mixture be natural layering in separating bottle (6), upper strata bromine water is back in the bromine tower (3) by pipeline, and the lower coarse bromine then flow in the rectifying tower still (7) by the road from separating bottle (6) bottom;
(4) rectifying: rectifying is carried out in rectifying tower still (7), Heating temperature during rectifying is 58～58.5 ℃, mixed gas is discharged at top from rectifying tower still (7) during rectifying, mixed gas enters reflux exchanger (9) condensation by the road, phlegma is back in the rectifying tower still (7) by the road, coagulate gas and discharge by the road, the bromine liquid in the heating kettle of rectifying tower still (7) drains into water cooler (8), gets smart bromine.
2. steam distillation method for preparing bromine by according to claim 1, it is characterized in that, it also is provided with recovery tower (4), feed normal temperature bittern in the recovery tower (4), the described gas that do not coagulate of step (2) and step (4) is expelled in the recovery tower (4) by the road, after bittern reclaims, enter bromine tower (3), and all the other are not reclaimed gaseous emission.
3. steam distillation method for preparing bromine by according to claim 1 and 2 is characterized in that, in step (1), the chlorine rate of joining in the bromine tower (3) is 110～120%, describedly joins the per-cent that the chlorine rate is actual chlorine charge and theoretical chlorine charge.
4. steam distillation method for preparing bromine by according to claim 1 and 2 is characterized in that, in step (1), the flow in bittern enters bromine tower (3) is 2～9 meters
3In/time, the preheating temperature of bittern in preheater (2) is 60～75 ℃.
5. steam distillation method for preparing bromine by according to claim 1 and 2, it is characterized in that, in step (1), the feed rate of steam is regulated according to the tower mouth temperature that goes out of the mixed steam of bromine, chlorine G﹠W, and the mixed steam of bromine, chlorine G﹠W goes out tower mouth temperature and is controlled at 80～90 ℃.
6. steam distillation method for preparing bromine by according to claim 1 and 2 is characterized in that, in step (2), the condensing temperature of condenser (5) is 20～30 ℃.
7. steam distillation method for preparing bromine by according to claim 1 and 2, it is characterized in that, in step (3), bromine water and the line of delimitation of bromine liquid are for separating the level layer in the described separating bottle (6), if separation level layer to the height of bromine water laminar surface is H, separating level layer to the height that the liquid bromine exports (10) medullary ray is h, then: H=3h.
8. steam distillation method for preparing bromine by according to claim 1 is characterized in that, adorns a pressure equalizing pipe (11) in a side of separating bottle (6).
9. steam distillation method for preparing bromine by according to claim 1 and 2 is characterized in that, in step (4), the condensing temperature of reflux exchanger during rectifying (9) is 30～35 ℃.
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| RU2789134C1 (en) * | 2021-10-18 | 2023-01-30 | Общество с ограниченной ответственностью "ИРКУТСКАЯ НЕФТЯНАЯ КОМПАНИЯ" | Method for producing ammonium bromide |
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2009
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|---|---|---|---|---|
| RU2789134C1 (en) * | 2021-10-18 | 2023-01-30 | Общество с ограниченной ответственностью "ИРКУТСКАЯ НЕФТЯНАЯ КОМПАНИЯ" | Method for producing ammonium bromide |
| WO2023068963A1 (en) * | 2021-10-18 | 2023-04-27 | Общество с ограниченной ответственностью "ИРКУТСКАЯ НЕФТЯНАЯ КОМПАНИЯ" | Process for producing ammonium bromide |
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