CN109161401A - A kind of production system of chlorinated paraffin by-product hydrochloric acid - Google Patents
A kind of production system of chlorinated paraffin by-product hydrochloric acid Download PDFInfo
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- CN109161401A CN109161401A CN201811112479.2A CN201811112479A CN109161401A CN 109161401 A CN109161401 A CN 109161401A CN 201811112479 A CN201811112479 A CN 201811112479A CN 109161401 A CN109161401 A CN 109161401A
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- hydrochloric acid
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- chlorination
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/38—Chemical modification of petroleum
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Abstract
The present invention relates to chlorinated-paraffin producing process, disclose a kind of production system of chlorinated paraffin by-product hydrochloric acid, solve the problems, such as that free chlorine contents are higher and reduce the product quality of by-product hydrochloric acid in existing by-product hydrochloric acid comprising chlorination of paraffin unit and hydrogen chloride absorption unit and hydrochloric acid separative unit；Chlorination of paraffin unit includes chlorinating container, chlorine supply main and engine manifold, it include the chlorination tube being connected to chlorine supply main in chlorinating container, the lower end nozzle of liquid level lower section and chlorination tube is provided with cataclasitlc structure in chlorination tube lower end insertion chlorinating container, cataclasitlc structure is the multiple stoppers being circumferentially arranged along chlorination tube or the blocking net for being covered on chlorination tube lower end, lead to hydrogen chloride absorption unit along engine manifold after exhaust collection after being obtained in chlorination of paraffin unit by paraffin and chlorine reaction rich in hydrogen chloride, reduce the chlorine content carried secretly in the tail gas of chlorinating container, improve the product quality and raw material availability of by-product hydrochloric acid, energy-saving and emission-reduction.
Description
Technical field
The present invention relates to chlorinated-paraffin producing process, in particular to a kind of production system of chlorinated paraffin by-product hydrochloric acid.
Background technique
It is generally obtained using paraffin and the direct haptoreaction of chlorine in existing chlorinated paraffin production method.Existing chlorination
Paraffin device includes chlorinating container, the paraffin of liquid phase is contained in chlorinating container, then be passed through chlorine in the paraffin of liquid phase
Mixing, paraffin and chlorine reaction obtain chlorinated paraffin, while tail gas after its reaction is absorbed, sprays final enrichment and obtain by-product
Hydrochloric acid.
The reason of the phenomenon that existing chlorinated paraffin by-product hydrochloric acid generally existing peculiar smell, peculiar smell is due to by-product hydrochloric acid
In free chlorine it is higher, caused by free chlorine therein comes out.And the free chlorine in by-product hydrochloric acid is due to gas-liquid phase reaction
Mass transfer rate is limited, and chlorine is passed through not react completely with paraffin in paraffin solution and just escape from paraffin solution, chlorinating container
Outlet tail gas in chlorine content it is higher, cause tail gas it is subsequent absorb, spray during part chlorine leach in by-product salt
In acid, and then cause the free chlorine contents of by-product hydrochloric acid higher, reduces the product quality of by-product hydrochloric acid.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of production of chlorinated paraffin by-product hydrochloric acid
System reduces chlorine content in the tail gas of chlorinating container, improves the product quality of by-product hydrochloric acid.
Above-mentioned technical purpose of the invention has the technical scheme that
A kind of production system of chlorinated paraffin by-product hydrochloric acid, including chlorination of paraffin unit and hydrogen chloride absorption unit and hydrochloric acid separation
Unit；The chlorination of paraffin unit includes chlorinating container, chlorine supply main and engine manifold, in the chlorinating container
Including the chlorination tube being connected to chlorine supply main, liquid level lower section and chlorination tube in the chlorination tube lower end insertion chlorinating container
Lower end nozzle be provided with cataclasitlc structure, the cataclasitlc structure is the multiple stoppers being circumferentially arranged along chlorination tube or is covered on logical
The blocking net of chlorine pipe lower end is rich in the exhaust collection of hydrogen chloride after being obtained in the chlorination of paraffin unit by paraffin and chlorine reaction
Lead to hydrogen chloride absorption unit along engine manifold afterwards.
By using above-mentioned technical proposal, chlorine is passed through liquid phase in chlorinating container along chlorination tube from chlorine supply main
Paraffin in, chlorine from chlorination tube lower end escape when, by cataclasitlc structure by stopper or stop net blocking, due to liquid
The paraffin viscosity of phase is larger, forms minute bubbles when chlorine is from after the evolution of chlorination tube lower end, and be blended in the state of minute bubbles
In the paraffin of liquid phase, avoids the bubbling of major diameter from generating chlorine and escaped from paraffin solution too quickly, make the stone of chlorine and liquid phase
Wax mixes more evenly, while the chlorine of minute bubbles state is easier to spread with the paraffin of liquid phase into the paraffin of liquid phase, and then extends
Motion path of the chlorine bubbles in liquid phase paraffin, thus chlorine reacts more abundant with paraffin, reduces the tail gas of chlorinating container
The chlorine content of middle entrainment improves the product quality and raw material availability of by-product hydrochloric acid, energy-saving and emission-reduction.
Preferably, the stopper is the zigzag being evenly distributed on the nozzle of chlorination tube lower end around chlorination tube.
By using above-mentioned technical proposal, when chlorine is escaped to chlorination tube lower end nozzle, one first is formed in chlorination tube lower end
A bubble, bubble, which abuts after constantly expanding with jagged stopper, keeps expansion limited, and bubble continues to expand and be blocked block
Tip scratches to form minute bubbles, and the broken minute bubbles formed are obstructed block shape limitation, is broken on form vertical direction from upper
And lower minute bubbles quantity increases, and increases from top to bottom towards horizontal direction impact force, thus expands after minute bubbles evolution chlorination tube
It dissipates area to increase, further increases the paraffin mixability of chlorine and liquid phase, reduce the chlorine carried secretly in the tail gas of chlorinating container
Gas content improves the product quality of by-product hydrochloric acid；Do not change under chlorination tube during this since stopper is set on nozzle simultaneously
End pipe mouth flow area, and then stopper is avoided to cause to hinder from chlorination tube evolution to chlorine.
Preferably, the chlorination of paraffin unit includes multiple chlorinating containers, the chlorinating container liquid phase is successively
It connects, it is paraffin, the chlorine supply main and all chlorinating containers that liquid phase is passed through in the chlorinating container of the first order
It is connected to, and the chlorine supply main successively decreases to the amount of each chlorinating container conveying chlorine by series, the chlorination reaction
The tail gas of entrainment hydrogen chloride and chlorine that kettle reaction generates enters from the chlorinating container of previous stage into next stage chlorinating container,
The tail gas that chlorinating container described in afterbody obtains enters engine manifold.
By using above-mentioned technical proposal, multiple chlorinating containers are set and its liquid phase is connected, the chlorination of the first order is anti-
The mixture for answering the chlorinated paraffin and paraffin that obtain after the paraffin and chlorine reaction of liquid phase in kettle, according to series along chlorinating container
Flowing, and with chlorine in batches in the case where the identical chlorine supply of multiple chlorinating container fractional order reactions, paraffin and chlorine
React more abundant, reduce chlorine residual quantity, at the same in chlorinating container the complete chlorine of unreacted with tail gas from the chlorine of previous stage
Change reaction kettle to enter into next stage chlorinating container, be supplied as chlorine feed, reduces tail gas of the entrainment containing chlorine and enter tail gas
General pipeline then reduces in engine manifold as chlorine content in tail gas, improves the product quality of by-product hydrochloric acid.
Preferably, the hydrogen chloride absorption unit includes hydrochloric acid absorption tower and secondary spraying tower, it is described to be rich in chlorination
The tail gas of hydrogen passes sequentially through hydrochloric acid absorption tower and secondary spraying tower, and the hydrochloric acid absorption tower tower bottom extraction liquid phase is secondary spraying tower
Absorbing liquid.
By using above-mentioned technical proposal, the tail gas rich in hydrogen chloride by hydrochloric acid absorption tower and secondary spraying tower in two times into
Row absorbs, and absorbs sufficiently, improves hydrogen cloride concentration in secondary spraying tower tower bottom extraction liquid phase, while hydrochloric acid first diluter by concentration
Or water absorbs the tail gas for being rich in hydrogen chloride, since chlorine ion concentration is lower in concentration diluter hydrochloric acid or water, promotes to inhale in hydrochloric acid
Chlorine when receiving tower in tail gas is reacted with water generates hydrochloric acid and hypochlorous acid, and then reduces free chlorine in secondary spraying tower absorbing liquid and contain
Amount, reduces free chlorine contents in final by-product hydrochloric acid, improves the product quality of by-product hydrochloric acid.
Preferably, the hydrogen chloride absorption unit further includes tail gas absorber, the secondary spraying column overhead extraction
Gas phase enters in tail gas absorber, and absorbing liquid is water in the tail gas absorber, and the tail gas absorber tower bottom produces liquid phase
For the absorbing liquid of hydrochloric acid absorption tower.
The hydrogen chloride in tail gas that secondary spraying column overhead is produced by using above-mentioned technical proposal, tail gas absorber into
Row recycles, while reducing the pollution in exhaust emissions.
Preferably, the hydrogen chloride absorption unit further includes lye absorption tower, the tail gas absorber overhead extraction
Gas phase enters lye absorption tower, and lye absorption tower absorbing liquid is lye.
By using above-mentioned technical proposal, lye absorption tower in tail gas sour gas and chlorine carry out reactive absorption take
Out, sour gas and chlorine direct emission is avoided to enter atmosphere.
Preferably, the hydrogen chloride absorption unit includes charge air cooler and knockout drum, the chlorination of paraffin unit
The tail gas for being rich in hydrogen chloride out passes sequentially through leads to hydrochloric acid absorption tower after charge air cooler and knockout drum again.
It is exothermic reaction since chlorine generates reacting for chlorinated paraffin with paraffin, with chlorine by using above-mentioned technical proposal
Change reaction in reaction kettle to carry out, chlorinating container temperature rises, and the oil liquid saturated vapour pressure of interior liquid phase increases, tail gas gas phase group
Increase at the ingredient of middle oil liquid, this time first cooled down before entering hydrochloric acid absorption tower, so that oil liquid is precipitated, and enters knockout drum
Interior buffering, so that the liquid phase oil liquid and gas phase tail gas separation that are precipitated, and then the oil content in by-product hydrochloric acid is reduced, improve by-product salt
The product quality of acid.
Preferably, the charge air cooler is direct heat exchanger, and the cold logistics of the charge air cooler is liquid
Paraffin, or the liquefied mixture for chlorinated paraffin and paraffin.
Chlorine and cold logistics by using above-mentioned technical proposal, when tail gas and the direct combination cooling of cold logistics, in tail gas
In paraffin component mixing, chlorine is partially dissolved in cold logistics in tail gas, and then reduces chlorine content in tail gas, reduces by-product
The content of free chlorine in hydrochloric acid, and then improve the product quality of by-product hydrochloric acid.
Preferably, cyclone separator is also provided with and communicated between the knockout drum and hydrochloric acid absorption tower, the separation
Hydrochloric acid absorption tower is entered back into after the cyclone separator that upper end extraction tail gas passes through work.
By using above-mentioned technical proposal, the oil liquid of a small amount of liquid phase, warp are also entrained with from knockout drum top extraction gas
The oil liquid that cyclone separator separates the part is crossed, and then reduces and enters oil content in hydrochloric acid absorption tower inner exhaust gas, improves by-product
The product quality of hydrochloric acid.
Preferably, the cold logistics after the charge air cooler heat exchange and the Partial Liquid Phase raw material as chlorinating container
It uses.
By using above-mentioned technical proposal, the chlorine in tail gas is absorbed while cold logistics exchanges heat in charge air cooler,
It is used as the Partial Liquid Phase raw material of chlorinating container, improves system to the utilization rate of raw material.
In conclusion the invention has the following advantages:
1. chlorine is passed through below the paraffin of liquid phase in chlorinating container along chlorination tube, when chlorine is escaped from chlorination tube lower end, pass through
Cataclasitlc structure is stopped, and is blended in the paraffin of liquid phase with the state of minute bubbles, and the bubbling of major diameter is avoided to generate chlorine mistake
It is escaped from the paraffin of liquid phase fastly, mixes chlorine more evenly with the paraffin of liquid phase, while the chlorine of minute bubbles state is easier to
It is spread with the paraffin of liquid phase into the paraffin of liquid phase, and then extends motion path of the chlorine bubbles in liquid phase paraffin, thus chlorine
Gas reacts more abundant with paraffin, reduces the chlorine content carried secretly in the tail gas of chlorinating container, improves the product matter of by-product hydrochloric acid
Amount and raw material availability, energy-saving and emission-reduction；
2. chlorine to chlorination tube lower end nozzle escape, first chlorination tube lower end formed a bubble, bubble constantly expand and by
The tip of stopper scratches to form minute bubbles, and the broken minute bubbles formed are obstructed block shape limitation, is broken into form side vertically
Minute bubbles quantity increases from top to bottom upwards, and increases from top to bottom towards horizontal direction impact force, and minute bubbles is made to escape logical chlorine
Diffusion area increases after pipe, further increases the paraffin mixability of chlorine and liquid phase, reduces in the tail gas of chlorinating container and press from both sides
The chlorine content of band improves the product quality of by-product hydrochloric acid；Do not change on nozzle during this due to stopper simultaneously logical
Chlorine pipe lower end nozzle flow area, and then stopper is avoided to cause to hinder from chlorination tube evolution to chlorine；
3. multiple concatenated chlorinating containers of liquid phase are arranged, the logistics of liquid phase is according to series along chlorine in the chlorinating container of the first order
Change reaction kettle flowing, and reacted with chlorine in batches in multiple chlorinating container internal classifications, paraffin and chlorine reaction are more abundant, subtract
Few chlorine residual quantity, while the complete chlorine of unreacted enters from the chlorinating container of previous stage under with tail gas in chlorinating container
It in level-one chlorinating container, is supplied as chlorine feed, reduces tail gas of the entrainment containing chlorine and enter engine manifold, then reduce tail
It is chlorine content in tail gas in gas general pipeline, improves the product quality of by-product hydrochloric acid；
4. the tail gas rich in hydrogen chloride is first absorbed the tail gas for being rich in hydrogen chloride by the diluter hydrochloric acid of concentration or water, since concentration is diluter
Hydrochloric acid or water in chlorine ion concentration it is lower, promote in hydrochloric acid absorption tower the middle chlorine of tail gas react generation hydrochloric acid and secondary with water
Chloric acid, and then free chlorine contents in secondary spraying tower absorbing liquid are reduced, free chlorine contents in final by-product hydrochloric acid are reduced, are improved secondary
Produce the product quality of hydrochloric acid；
5. the hydrogen chloride in the tail gas that tail gas absorber produces secondary spraying column overhead is recycled, tail gas absorber tower
Top extraction gas phase enters lye absorption tower and is absorbed by lye, avoids sour gas and chlorine direct emission from entering atmosphere, reduces
The exhaust emission of system；
6. the tail gas rich in hydrogen chloride first passes sequentially through charge air cooler, knockout drum and cyclonic separation before entering hydrochloric acid absorption tower
The oil liquid in tail gas is precipitated wherein the tail gas rich in hydrogen chloride is cooling in charge air cooler in device, reduces oil-containing in tail gas
Amount, and chlorine and the direct mixed heat transfer of paraffin component in cold logistics and reacted in tail gas, reduce chlorine content in tail gas, reduction
The content of free chlorine in by-product hydrochloric acid, and then improve the product quality of by-product hydrochloric acid；
The chlorine in tail gas, the part liquid as chlorinating container are absorbed while 7. cold logistics exchanges heat in charge air cooler
Phase raw material uses, and improves system to the utilization rate of raw material.
Detailed description of the invention
Fig. 1 is the flow diagram of the production system of by-product hydrochloric acid；
Fig. 2 is the flow chart of chlorination of paraffin unit in embodiment one；
Fig. 3 is the structural schematic diagram of chlorination tube lower end nozzle in embodiment one；
Fig. 4 is the flow chart of hydrogen chloride absorption unit in embodiment one；
Fig. 5 is the flow chart of hydrochloric acid separative unit in embodiment one；
Fig. 6 is the flow chart of chlorination of paraffin unit in embodiment two；
Fig. 7 is the flow chart of hydrogen chloride absorption unit in embodiment three；
Fig. 8 is the flow chart of hydrogen chloride absorption unit in embodiment five.
Appended drawing reference: 1, chlorination of paraffin unit；11, wax feeds pipe；12, chlorine supply main；121, for chlorine branch pipe；
13, chlorinating container；13a, the first chlorinating container；13b, the second chlorinating container；13c, third chlorinating container；13d,
Four chlorinating containers；131, chlorination tube；1311, cataclasitlc structure；1311-1, stopper；14, engine manifold；15, chlorinated paraffin
Pipe；2, hydrogen chloride absorption unit；21, hydrochloric acid absorption tower；22, secondary spraying tower；23, tail gas absorber；231, pure water pipe；24,
Lye absorption tower；241, alkali liquor pipe；242, waste pipe；25, crude salt acid tube；26, charge air cooler；261, cold flow inlet pipe；262,
Cold flow outlet pipe；27, knockout drum；28, cyclone separator；3, hydrochloric acid separative unit；31, oleic acid knockout tower；32, hydrochloric acid tank；
311, oil liquid discharge pipe；312, product salt acid tube.
Specific embodiment
Below in conjunction with attached drawing, invention is further described in detail.
As shown in Fig. 1, a kind of production system of chlorinated paraffin by-product hydrochloric acid, including chlorination of paraffin unit 1 and hydrogen chloride
Absorptive unit 2 and hydrochloric acid separative unit 3, paraffin react to obtain chlorinated paraffin and by-product chlorine in chlorination of paraffin unit 1 with chlorine
Change hydrogen, byproduct hydrogen chloride enters hydrogen chloride absorption unit 2 and absorbed to obtain crude salt acid by absorbing liquid, and crude salt acid enters back into salt
Sour separative unit 3 separates the oil liquid carried secretly in crude salt acid, and then obtains by-product hydrochloric acid.By-product hydrochloric acid concentration refers in this production system
It is designated as 30.0-32.0wt%, preferably 31.0-32.0wt%.
Embodiment one,
As shown in Fig. 2, a kind of production system of chlorinated paraffin by-product hydrochloric acid, wherein chlorination of paraffin unit 1 includes a chlorination
Reaction kettle 13, chlorine supply main 12, engine manifold 14, wax feeds pipe 11.Jacket heat-exchanger is had outside chlorinating container 13,
Chlorinating container 13 is internally provided with ultraviolet lamp simultaneously, and jacket heat-exchanger and ultraviolet lamp are that the prior art is not done in detail herein
It illustrates.13 side of chlorinating container is connected with wax feeds pipe 11, also leads to inserted with chlorination tube 131 in chlorinating container 13
In the lower end insertion chlorinating container 13 of chlorine pipe 131 below liquid level.
As shown in Fig. 3, the lower end nozzle of chlorination tube 131 is provided with cataclasitlc structure 1311.Cataclasitlc structure 1311 is along logical
Multiple stopper 1311-1 that chlorine pipe 131 is circumferentially arranged or the blocking net for being covered on 131 lower end of chlorination tube.Cataclasitlc structure 1311 is excellent
Multiple jagged stopper 1311-1 are selected as, axial direction of the stopper 1311-1 around 131 lower end of chlorination tube is evenly distributed on logical
On the nozzle of chlorine end lower end.
As shown in Fig. 2, chlorine supply main 12 includes for chlorine branch pipe 121, for the upper of chlorine branch pipe 121 and chlorination tube 131
End connection.There are also the connections of engine manifold 14, engine manifold 14 to lead to hydrogen chloride absorption unit at the top of chlorinating container 13 simultaneously
2。
The process flow of chlorination of paraffin unit 1: liquid phase paraffin enters chlorinating container 13 from wax feeds pipe 11 with 10L/h
Interior, pure chlorine is with 10m3The flow of/h enters in chlorinating container 13 from chlorination tube 131, the paraffin in chlorinating container 13
Oil and chlorine carry out the chlorinated paraffin that chlorination obtains under photocatalysis.Generate in chlorinating container 13 rich in hydrogen chloride
Tail gas then leads to hydrogen chloride absorption unit 2 along engine manifold 14.97-105 DEG C known to 13 temperature of chlorinating container, pressure (gauge pressure)
Control is 0.02-0.03MPa.
As shown in Fig. 4, hydrogen chloride absorption unit 2 includes hydrochloric acid absorption tower 21, secondary spraying tower 22, tail gas absorber 23
With lye absorption tower 24.Engine manifold 14 and 21 tower bottom of hydrochloric acid absorption tower are connected, the gone out tail gas of 21 tower top of hydrochloric acid absorption tower and two
Secondary 22 tower bottom of spray column is connected, and the gone out tail gas of 22 tower top of secondary spraying tower and 23 tower bottom of tail gas absorber are connected, tail gas absorber
The gone out tail gas of 23 tower tops is connected with 24 tower bottom of lye absorption tower.
The process flow of chlorination of paraffin unit 1: the tail gas in engine manifold 14 rich in hydrogen chloride is with 15m3The flow of/h from
The tower bottom of hydrochloric acid absorption tower 21 enters, and comes into full contact with the first absorbing liquid to flow down in hydrochloric acid absorption tower 21, tower pressure (gauge pressure) is
0.01MPa, temperature is 69-55 DEG C in tower.The tail gas of 21 overhead extraction of hydrochloric acid absorption tower enters from the tower bottom of secondary spraying tower 22,
It is come into full contact with the second absorbing liquid to flow down in secondary spraying tower 22, tower pressure (gauge pressure) is 0.01MPa, and temperature is 55-42 in tower
℃.The tail gas of 22 overhead extraction of secondary spraying tower from the tower bottom of tail gas absorber 23 enter, in tail gas absorber 23 flow down
Third absorbing liquid comes into full contact with, and tower pressure (gauge pressure) is 0.01MPa, and temperature is 42-32 DEG C in tower.23 overhead extraction of tail gas absorber
Tail gas enter from 24 tower bottom of lye absorption tower, from lye after being come into full contact with the 4th absorbing liquid to flow down in lye absorption tower 24
The discharge of 24 overhead extraction of absorption tower, tower pressure (gauge pressure) are 0.01MPa, and temperature is 31-28 DEG C in tower.Wherein 24 tower of lye absorption tower
Apical grafting is connected with alkali liquor pipe 241, and the 4th absorbing liquid of 24 tower of lye absorption tower is lye, molten for the sodium hydroxide of 20wt% herein
Liquid, 24 tower bottom liquid phase of lye absorption tower are pumped to waste pipe 242, are sent to purification tank for liquid waste or wastewater treatment equipment.
23 tower top of tail gas absorber connection simultaneously has pure water pipe 231, and the third absorbing liquid of tail gas absorber 23 is pure water, tail
After the liquid phase extraction of 23 tower bottom of aspiration tower, the first absorbing liquid as hydrochloric acid absorption tower 21 is used.21 tower bottom of hydrochloric acid absorption tower
Liquid phase extraction after, the second absorbing liquid as secondary spraying tower 22 uses.And 22 tower bottom of secondary spraying tower extraction liquid phase is thick
Hydrochloric acid, crude salt acid in HCl concentration be 32wt%, be sent to hydrochloric acid separative unit 3 along crude salt acid tube 25.
As shown in Fig. 5, hydrochloric acid separative unit 3 includes oleic acid knockout tower 31 and hydrochloric acid tank 32, and crude salt acid tube 25 is from side
Line accesses oleic acid knockout tower 31, the product salt acid tube 312 of 31 tower top of oleic acid knockout tower setting connection hydrochloric acid tank 32, oleic acid separation
31 tower bottom of tower is equipped with oil liquid discharge pipe 311.
Crude salt acid is separated by way of layering with oil liquid in oleic acid knockout tower 31.Oil liquid main component is herein
The heavy constituent of chlorinated paraffin and other by-products, hydrochloric acid density are less than the density of oil liquid, and hydrochloric acid is discharged to obtain product by-product from tower top
Hydrochloric acid is pumped to hydrochloric acid tank 32.The aperture of adjusting tower bottom outlet valve simultaneously, oleic acid layering interfaces height in control tower, and
When oil extraction.
According to aforementioned production method, embodiment 1A-1C is obtained, and to chlorine content in the tail gas in engine manifold 14, logical
Oil content is detected in free chlorine contents and by-product hydrochloric acid in chlorine pipe pressure, by-product hydrochloric acid, as a result as follows.
The chlorination tube 131 for having cataclasitlc structure 1311 is substituted with the chlorination tube 131 of no cataclasitlc structure 1311 simultaneously, as a comparison
Example 1A is tested, and chlorine content is 34.2wt% in the tail gas in engine manifold 14, and pressure is 0.17MPa in chlorination tube 131,
Free chlorine contents are 586mg/L in by-product hydrochloric acid.
From the foregoing, it will be observed that chlorine is from the stone for being passed through liquid phase in chlorinating container 13 in chlorine supply main 12 along chlorination tube 131
In wax, when chlorine is escaped from 131 lower end of chlorination tube, stops by cataclasitlc structure 1311 and be crushed and form minute bubbles, and with stingy
The state of bubble is blended in the paraffin of liquid phase, is avoided the bubbling of major diameter from generating chlorine and is escaped from the paraffin of liquid phase too quickly,
Mix chlorine more evenly with the paraffin of liquid phase, while the chlorine of minute bubbles state is easier to be stirred with the paraffin of liquid phase to liquid phase
Diffusion in paraffin, and then extend motion path of the chlorine bubbles in liquid phase paraffin, thus chlorine reacts more abundant with paraffin, subtracts
The chlorine content carried secretly in the tail gas of few chlorinating container 13, improves the product quality of by-product hydrochloric acid.And stopper 1311-1
To be evenly distributed on the zigzag on 131 lower end nozzle of chlorination tube around chlorination tube 131,1311 effect of cataclasitlc structure is preferable.
Simultaneously in hydrogen chloride absorption unit 2, tail gas is individually absorbed with single secondary spraying tower 22 work, and is set respectively
Vertical comparative example 1B and comparative example 1C, design parameter are as follows.
From the foregoing, it will be observed that the tail gas rich in hydrogen chloride is absorbed in two times by hydrochloric acid absorption tower 21 and secondary spraying tower 22,
It absorbs sufficiently, improves hydrogen cloride concentration in 22 tower bottom of secondary spraying tower extraction liquid phase, while hydrochloric acid or water first diluter by concentration
The tail gas for being rich in hydrogen chloride is absorbed, since chlorine ion concentration is lower in concentration diluter hydrochloric acid or water, is promoted in hydrochloric acid absorption tower
The middle chlorine of tail gas is reacted with water when 21 generates hydrochloric acid and hypochlorous acid, and then reduces free chlorine in 22 absorbing liquid of secondary spraying tower and contain
Amount, reduces free chlorine contents in final by-product hydrochloric acid, improves the product quality of by-product hydrochloric acid.
Embodiment two,
As shown in Fig. 6, a kind of production system of chlorinated paraffin by-product hydrochloric acid, is based on embodiment one, and difference place is pair
Chlorination of paraffin unit 1 improves.
Chlorination of paraffin unit 1 includes multiple chlorinating containers 13, forms reaction kettle group, chlorinating container 13 in reaction kettle group
Quantity according to the actual situation depending on, this time 13 quantity of chlorinating container be four, actual quantity as the case may be depending on, can be
Three, five, six, seven etc..13 liquid phase of chlorinating container is sequentially connected in series in reaction kettle group, and liquid phase material transmission order is divided into from kettle
Monochlor(in)ate reaction kettle 13a, the first chlorinating container 13a, the second chlorinating container 13b, third chlorinating container 13c and tetrachloro
Change reaction kettle 13d.
The paraffin of 10L/h, chlorine supply main 12 and each chlorinating container 13 are passed through in first chlorinating container 13a
Chlorination tube 131 is connected to.It is removed outside afterbody chlorinating container 13 in reaction kettle group, 13 groups of reaction temperatures of each chlorinating container
Control is 97-105 DEG C, and pressure control is 0.02-0.025MPa.13 temperature of afterbody chlorinating container is controlled in 97-105
DEG C, pressure control is 0.02-0.03MPa.
Chlorinating container of the tail gas of entrainment hydrogen chloride and chlorine that the reaction of chlorinating container 13 simultaneously generates from previous stage
13 enter into next stage chlorinating container 13, and the tail gas that chlorinating container 13 obtains described in afterbody enters engine manifold 14,
Simultaneously and chlorine supply main 12 supplies chlorine total amount as 10m3/ h, but grade is pressed to the amount of each chlorinating container 13 conveying chlorine
Number successively decreases, to keep pressure in kettle to stablize.
According to aforementioned production method, embodiment 2A-2C is obtained, and to chlorine content in the tail gas in engine manifold 14, logical
Free chlorine contents are detected in 131 pressure of chlorine pipe and by-product hydrochloric acid, as a result as follows.
From the foregoing, it will be observed that multiple chlorinating containers 13 are set and its liquid phase is connected, liquid in the chlorinating container 13 of the first order
The mixture of the chlorinated paraffin and paraffin that obtain after the paraffin and chlorine reaction of phase is flowed according to series along chlorinating container 13,
And with chlorine in batches in the case where the identical chlorine supply of multiple 13 fractional order reactions of chlorinating container, paraffin and chlorine are anti-
More sufficiently should reduce chlorine residual quantity, at the same in chlorinating container 13 the complete chlorine of unreacted with tail gas from the chlorine of previous stage
Change reaction kettle 13 to enter into next stage chlorinating container 13, be supplied as chlorine feed, reduces tail gas of the entrainment containing chlorine and enter
Engine manifold 14 then reduces in engine manifold 14 as chlorine content in tail gas, improves the product quality of by-product hydrochloric acid.
Embodiment three,
As shown in Fig. 7, a kind of production system of chlorinated paraffin by-product hydrochloric acid, is based on embodiment one, and difference place is pair
Hydrogen chloride absorption unit 2 improves.
Hydrogen chloride absorption unit 2 includes charge air cooler 26 and knockout drum 27, and chlorination of paraffin unit 1 is rich in hydrogen chloride out
Tail gas pass sequentially through and lead to hydrochloric acid absorption tower 21 after charge air cooler 26 and knockout drum 27 again.Charge air cooler 26 includes cold flow
Inlet pipe 261 and cold flow outlet pipe 262, cold flow logistics is self cooling flow into pipe 261 into, cold flow outlet pipe 262 goes out, in charge air cooler 26 with
Tail gas heat exchange rich in hydrogen chloride, makes the tail gas rich in hydrogen chloride cool down.This time charge air cooler 26 is indirect heat exchanger, is rich in
The temperature when tail gas of hydrogen chloride leaves charge air cooler 26 is 65 DEG C, and 27 gauge pressure of knockout drum is 0.01MPa.
According to aforementioned production method, embodiment 3A-3C is obtained, and in free chlorine contents and by-product hydrochloric acid in by-product hydrochloric acid
Oil content detected, it is as a result as follows.
From the foregoing, it will be observed that being exothermic reaction since chlorine generates reacting for chlorinated paraffin with paraffin, in chlorinating container 13
Reaction carries out, and 13 temperature of chlorinating container rises, and the oil liquid saturated vapour pressure of interior liquid phase increases, oil liquid in tail gas gas phase composition
Ingredient increase, this time enter hydrochloric acid absorption tower 21 before first cooled down so that oil liquid be precipitated, and enter knockout drum 27 in delay
Punching, so that the liquid phase oil liquid and gas phase tail gas separation that are precipitated, and then the oil content in by-product hydrochloric acid is reduced, improve by-product hydrochloric acid
Product quality.
Example IV,
A kind of production system of chlorinated paraffin by-product hydrochloric acid is based on embodiment three, and difference place is, to hydrogen chloride absorption
Unit 2 improves.
Charge air cooler 26 is direct heat exchanger, and the cold logistics of charge air cooler 26 is the paraffin of liquid, or is chlorine
The liquefied mixture of fossil waxes and paraffin.
Hydrogen chloride absorption unit 2 further includes cold stream reservoir, and cold stream reservoir is collected cold after charge air cooler 26 exchanges heat
Logistics and Partial Liquid Phase raw material as chlorinating container 13 uses.
According to aforementioned production method, embodiment 4A-4C is obtained, and in free chlorine contents and by-product hydrochloric acid in by-product hydrochloric acid
Oil content detected, it is as a result as follows.
From the foregoing, it will be observed that when tail gas and the direct combination cooling of cold logistics, the chlorine in tail gas and the paraffin component in cold logistics
It mixes and reacts, and then reduce chlorine content in tail gas, reduce the content of free chlorine in by-product hydrochloric acid, and then improve by-product hydrochloric acid
Product quality.
Embodiment five,
As shown in Fig. 8, a kind of production system of chlorinated paraffin by-product hydrochloric acid is based on example IV, and difference place is, point
From cyclone separator 28 is also provided with and communicated between tank 27 and hydrochloric acid absorption tower 21,27 top of knockout drum extraction tail gas passes through work
Cyclone separator 28 after enter back into hydrochloric acid absorption tower 21.
According to aforementioned production method, embodiment 5A-5C is obtained, and in free chlorine contents and by-product hydrochloric acid in by-product hydrochloric acid
Oil content detected, it is as a result as follows.
From the foregoing, it will be observed that from the oil liquid for being also entrained with a small amount of liquid phase in gas is produced at the top of knockout drum 27, by cyclonic separation
Device 28 separates the oil liquid of the part, and then reduces and enter oil content in 21 inner exhaust gas of hydrochloric acid absorption tower, improves by-product hydrochloric acid
Product quality.
Above-mentioned specific embodiment is only explanation of the invention, is not limitation of the present invention, art technology
Personnel can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as
All by the protection of Patent Law in scope of the presently claimed invention.
Claims (10)
1. a kind of production system of chlorinated paraffin by-product hydrochloric acid, which is characterized in that inhaled including chlorination of paraffin unit (1) and hydrogen chloride
Receive unit (2) and hydrochloric acid separative unit (3)；The chlorination of paraffin unit (1) includes chlorinating container (13), chlorine supply main
It (12) and engine manifold (14) include, the chlorination tube being connected to chlorine supply main (12) in the chlorinating container (13)
(131), the lower end nozzle of the interior liquid level lower section of chlorination tube (131) lower end insertion chlorinating container (13) and chlorination tube (131)
It is provided with cataclasitlc structure (1311), the cataclasitlc structure (1311) is the multiple stoppers being circumferentially arranged along chlorination tube (131)
(1311-1) or the blocking net for being covered on chlorination tube (131) lower end, the chlorination of paraffin unit (1) are interior by paraffin and chlorine reaction
Lead to hydrogen chloride absorption unit (2) along engine manifold (14) after exhaust collection after obtaining rich in hydrogen chloride.
2. a kind of production system of chlorinated paraffin by-product hydrochloric acid according to claim 1, which is characterized in that the stopper
(1311-1) is around the equally distributed zigzag of chlorination tube (131) lower end nozzle.
3. a kind of production system of chlorinated paraffin by-product hydrochloric acid according to claim 1, which is characterized in that the paraffin chlorine
Changing unit (1) includes multiple chlorinating containers (13), and chlorinating container (13) liquid phase is sequentially connected in series, the chlorine of the first order
To change and is passed through liquid phase in reaction kettle (13) as paraffin, the chlorine supply main (12) is connected to all chlorinating containers (13),
And the chlorine supply main (12) successively decreases to the amount of each chlorinating container (13) conveying chlorine by series, the chlorination reaction
The tail gas of entrainment hydrogen chloride and chlorine that kettle (13) reaction generates enters from the chlorinating container (13) of previous stage to next stage chlorination
In reaction kettle (13), the tail gas that chlorinating container described in afterbody (13) obtains enters engine manifold (14).
4. a kind of production system of chlorinated paraffin by-product hydrochloric acid according to claim 1, which is characterized in that the hydrogen chloride
Absorptive unit (2) includes hydrochloric acid absorption tower (21) and secondary spraying tower (22), and the tail gas rich in hydrogen chloride passes sequentially through salt
Acid absorption column (21) and secondary spraying tower (22), hydrochloric acid absorption tower (21) the tower bottom extraction liquid phase is secondary spraying tower (22)
Absorbing liquid.
5. a kind of production system of chlorinated paraffin by-product hydrochloric acid according to claim 4, which is characterized in that the hydrogen chloride
Absorptive unit (2) further includes tail gas absorber (23), and secondary spraying tower (22) the overhead extraction gas phase enters tail gas absorber
(23) in, the interior absorbing liquid of the tail gas absorber (23) is water, and the tail gas absorber (23) tower bottom extraction liquid phase is hydrochloric acid
The absorbing liquid on absorption tower (21).
6. a kind of production system of chlorinated paraffin by-product hydrochloric acid according to claim 5, which is characterized in that the hydrogen chloride
Absorptive unit (2) further includes lye absorption tower (24), and tail gas absorber (23) the overhead extraction gas phase enters lye absorption tower
(24), lye absorption tower (24) absorbing liquid is lye.
7. a kind of production system of chlorinated paraffin by-product hydrochloric acid according to claim 4, which is characterized in that the hydrogen chloride
Absorptive unit (2) includes charge air cooler (26) and knockout drum (27), and the chlorination of paraffin unit (1) is rich in hydrogen chloride out
Tail gas leads to hydrochloric acid absorption tower (21) again after passing sequentially through charge air cooler (26) and knockout drum (27).
8. a kind of production system of chlorinated paraffin by-product hydrochloric acid according to claim 7, which is characterized in that the air inlet is cold
But device (26) is direct heat exchanger, and the cold logistics of the charge air cooler (26) is the paraffin of liquid, or is chlorinated paraffin
With the liquefied mixture of paraffin.
9. a kind of production system of chlorinated paraffin by-product hydrochloric acid according to claim 8, which is characterized in that the knockout drum
(27) it is also provided with and communicated between hydrochloric acid absorption tower (21) cyclone separator (28), knockout drum (27) top produces tail gas
By entering back into hydrochloric acid absorption tower (21) after the cyclone separator (28) of work.
10. a kind of production system of chlorinated paraffin by-product hydrochloric acid according to claim 8, which is characterized in that the air inlet
Cold logistics after cooler (26) heat exchange and Partial Liquid Phase raw material as chlorinating container (13) uses.
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| CN110422825A (en) * | 2019-09-09 | 2019-11-08 | 丹阳市助剂化工厂有限公司 | A kind of HCl recovery Processes and apparatus in chlorinated paraffin production process |
| CN115232645A (en) * | 2022-08-17 | 2022-10-25 | 山东沾化阳光化学有限公司 | Refining process and equipment for recovering hydrochloric acid in chlorinated paraffin production process |
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| CN109161401B (en) | 2021-04-27 |
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Address after: 315000 Haitian Middle Road, Ningbo Petrochemical Economic and Technological Development Zone, Zhenhai District, Ningbo City, Zhejiang Province Patentee after: Zhejiang Zhenyang Development Co.,Ltd. Address before: 315000 chemical industry zone, Ningbo, Zhejiang (Xipu) Patentee before: NINGBO OCEANKING CHEMICAL DEVELOPMENT Co.,Ltd. |
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Inventor after: Zhou Qiang Inventor after: Wang Shiliang Inventor after: Hu Jianhao Inventor after: Hu Guiyong Inventor after: Lin Shaojie Inventor before: Zhou Qiang Inventor before: Xie Haizhou Inventor before: Hu Jianhao Inventor before: Hu Guiyong Inventor before: Lin Shaojie |