CN103832975B - The method of chlorine and oxygen is reclaimed from the gas mixture of chloride and oxygen - Google Patents

The method of chlorine and oxygen is reclaimed from the gas mixture of chloride and oxygen Download PDF

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CN103832975B
CN103832975B CN201410034142.XA CN201410034142A CN103832975B CN 103832975 B CN103832975 B CN 103832975B CN 201410034142 A CN201410034142 A CN 201410034142A CN 103832975 B CN103832975 B CN 103832975B
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adsorption
oxygen
gas
chlorine
drying
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CN103832975A (en
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王农跃
冯孝庭
邵建明
闻国强
赵全忠
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Fangyuan New Material Technology Co ltd
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SHANGHAI FANGLUN NEW MATERIAL TECHNOLOGY Co Ltd
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Abstract

The invention discloses a kind of method reclaiming chlorine and oxygen from the gas mixture of chloride and oxygen, using the mixed tail gas of the product of hydrogen chloride oxidation reaction after the unreacted hydrogenchloride of water absorbing and removing as unstripped gas, be separated through two steps: a, unstripped gas remove moisture content remaining in tail gas by fractionation by adsorption drying; B, gas after dehydration are by alternating temperature pressure-variable adsorption, and complete being separated of chlorine and oxygen, the chlorine of Separation and Recovery and oxygen quality all reach the specification of quality that directly can be used as process feed gas.The present invention except to substitute with adsorption separation technology and to revolutionize vitriol oil drying and dehydrating traditional technology, the problems such as the difficult treatment, the dewatering efficiency that solve the burn into generation dilute sulphuric acid to equipment and materials be low, the pollution that causes environment; And invented alternating temperature pressure-variable adsorption (T & amp; PSA) be separated the technology of chlorine and oxygen, not only increase separation efficiency, and improve the adsorptive power of adsorption tower.

Description

The method of chlorine and oxygen is reclaimed from the gas mixture of chloride and oxygen
Technical field
The present invention relates to the separation and recovery technology of chlorine and oxygen in petrochemical industry muriate industry, be specifically related to the method adopting adsorption separating method high efficiency separation chlorine and oxygen from the gas mixture that the catalytic oxidation of hydrogen chloride reaction generates.
Background technology
China is chlorine production, consumption big country, and the family of producer more than 220 of domestic production chlorine, Some Enterprises chlorine is all used by oneself, the enterprise having commodity chlorine to sell about 150.Within 2003, add up to output 270.53 ten thousand tons, I Country chlorine aggregate consumption in 2012, more than 2,000 ten thousand tons, accounts for 1/3 of world's chlorine total quantity consumed; .Chlorinated products kind more than 200 that China produces, wherein organic chlorides kind more than 100, inorganic chlorine product kind more than 50, Pesticidal products is kind more than 30.
The chlorine of China is produced primarily of chlorine industry, and in chlor-alkali enterprises, the balance of chlorine and alkali is contradiction all the time---and be the supply of satisfied increase chlorine, caustic soda is just superfluous.But, in the organic chlorides production process that domestic petroleum chemical industry is numerous, chlorine atomic theory utilization ratio only 50%, the hydrogenchloride that by-product is a large amount of.Current national by-product hydrogen chloride reaches more than 5,000,000 tons/year, and looking for outlet for hydrogenchloride becomes the common problem restricting chlor-alkali and relate to chlorine industry development.
Chlor-alkali production belongs to high energy-consuming industry, about every output 1 ton of chlorine needs power consumption 2200 kilowatt-hour, if prepare chlorine with by-product hydrogen chloride, not only can realize the recycle of chlorine resource, also greatly can promote the energy-saving and emission-reduction level of industry, reduce costs and eliminate the pollution to environment.For this reason, China's independent development Deacon technology is used successfully to industrial production, in the tail gas of supporting solution less energy-consumption, corrosion-free, eco-friendly hydrogenchloride Oxygen Catalytic Oxidation resultant of reaction, chlorine and oxygen high efficiente callback utilize technology, are the dreams that chlor-alkali and chlorination industry are pursued----have less energy-consumption, corrosion-free, low cost, chlorine recycle, eco-friendly clearer production technology.
From hydrogenchloride Oxygen Catalytic Oxidation resultant of reaction containing in Separation and Recovery chlorine technology the tail gas of chlorine and oxygen, what should solve the drying of Off water and chlorine-containing gas is separated two technical barriers.So far, the dry all Bian vitriol oil dewaterings of China Off water, not only bring and the burn into of equipment and materials are increased to energy consumption, produce the difficult treatment of dilute sulphuric acid, and be directed at the pollution of environment.
After the drying of Off water, there is the isolation technique of different chlorine-containing gas, mainly contain:
1. liquefaction or cryogenic rectification method
Because the critical temperature of chlorine is high (chlorine tc=144 DEG C, Pc=7710kPa far beyond other component; Oxygen tc=-118.6 DEG C, Pc=5043kPa; Hydrogenchloride tc=51.4 DEG C, Pc=8258kPa), therefore chlorine is easy to liquefaction very much.When pure chlorine gas pressure rises to more than 1MPa, the common cooling water temperature of Bian, the liquefaction that just can realize chlorine is separated; But high efficiency separation oxygen is more difficult further, and energy consumption is higher.What such as EP-B0329385 patent described is exactly that low Warm condensation liquefaction--cryogenic rectification method produces chlorine.
2. solvent absorbing--distillation desorption method
Utilize organic solvent under the chlorine absorption in gas mixture under lesser temps and elevated pressures, then desorb at higher temperature and lower pressure, can obtain the very high chlorine of purity like this, make chlorine be able to purifying, wherein organic solvent is with CCl 4for good.This method already for suitability for industrialized production (as US33995387 (A), Chinese patent CN96122822.9), but according to Montreal Protocol on Substances that Deplete the Ozone Layer (1987), uses CCl 4the restriction being subject to Montreal Protocol.Therefore this technique needs to find alternative CCl 4active solvent.Such as: chlorination phenylfluoroform, toluene dichloride, sulfur monochloride, dichloride iodine aqueous solution and chlorsulfonic acid etc.In this Technology, organic solvent is in the working cycle of absorption and desorption, needs the loss that pressurization, alternating temperature, energy consumption are higher, can produce solvent, if be brought into hydrogen chloride oxidation reaction as the solvent of absorption agent, will affect catalytic reaction activity; And it is also more difficult to reclaim oxygen.
3, membrane separation process (MS)
Membrane separation process utilizes film to the selective penetrated property difference of gas with various to be separated various gas.By chlorine selected area update strategy through film, other foreign gases are blocked in outside film, thus reach the object of separation and concentration chlorine.The core of this type of separation means is the preparation of mould material, and the gas purity that membrane sepn goes out is difficult to reach more than 95%, if adopt Using Multistage Membranes to be separated, its gas reclaiming rate can decline to a great extent.The preparation of mould material will consider selectivity, perviousness, weather resistance, economy to chlorine.Also do not have at present a kind ofly can to meet separation requirement by the practical film of industry.
4, pressure-variable adsorption partition method (PSA)
PSA Gas Separation Technology selects effective solid adsorbent, and carried out the absorption and regeneration of realize target gas by the change of pressure, thus reproduction speed is fast, energy consumption is low, belongs to energy-saving gas separation.At present, pressure-variable adsorption (PSA) isolation technique has been widely used in the purification of hydrogen in hydrogen-containing gas, the field such as apyrexia drying of the producing of carbon monoxide, carbonic acid gas, oxygen, nitrogen, argon gas, ethene, purification of natural gas, coal mine mash gas concentrate and hydro carbons, various gas in mixed gas.Use pressure-variable adsorption from chlorine-containing gas, be separated chlorine and be still in the research and development stage.
For Deacon reaction product, need the sorbent material that the adsorption separation efficiency of exploitation to oxygen and chlorine is high.Current all kinds of sorbent material selectivity are poor, the chlorine gas concentration obtained after causing separation not high (being usually less than 85%), just play chlorine inrichment, for the dechlorination process of chloride tail gas, the requirement (during reuse needs >=99.5%) of reuse as reaction cannot be reached.Such as: patent EP-A0518553 have employed cryogenic condensation liquefaction and is separated the method combined with Vacuum Pressure Swing Adsorption isolation technique, the sorbent material of fractionation by adsorption Bian is natural zeolite or ZSM molecular sieve, carbonaceous molecular sieve etc., although this method can obtain high purity, resourcebility utilize chlorine, technical sophistication, invest high, energy consumption is high, the rate of recovery of chlorine is low.The Chinese patent " concentration method of chlorine " (patent publication No. is CN1053597A) of Mitsui East Asia KCC application, Bian zeolite or carbonaceous molecular sieve are sorbent material, the chlorine only simmer down to 72 ~ 83% obtained is separated through pressure-variable adsorption, the purity of chlorine also needs concentratedly further just can to utilize, and this patent does not relate to unstripped gas and dehydrates technology.Gan Su Silver reaches the Chinese patent "-kind of Bian pressure swing adsorption reclaims the method for chlorine and oxygen in chloration hydro-oxidation gas mixture " (patent publication No. is CN102502498A) that Chemical Co., Ltd. etc. declares, being separated chlorine-containing gas at employing pressure swing adsorption has had the sorbent material of important advance------employing to be silica gel and gac multiple-hearth (gac is 0 ~ 50%), can obtain chlorine (purity is more than 99.2%) and oxygen (purity is more than 99.5%), yield all reach more than 98.5% simultaneously; But, this patent Raw gas Off water dry technology is still Bian sulphate method, still cannot avoid being directed at equipment corrosion, system corrosion and environmental pollution, and dehydration precision not Enough, unstripped gas is still higher containing residuary water, will reduce the separation efficiency of rear operation pressure-variable adsorption separation; The purity that this method obtains chlorine ensures more than 99.2% (v.%), but the requirement of chlorination industry much production Bian industrial chlorine be >=99.5% (v.%), oxygen level answers≤0.05% (v.%), water-content≤20ppm, from current highest level, the purity of the chlorine of pressure-variable adsorption Separation and Recovery can guarantee that more than 99.2% (v.%) brings up to >=99.5% (v.%), oxygen level should≤0.05% (v.%), water-content≤20ppm, be unsolved technical barrier so far.
To sum up, the above-mentioned various isolation technique containing chlorine and oxygen is all unsatisfactory, suddenly treats that acquisition of technology breaks through.
Summary of the invention
The problems referred to above that the isolation technique that the object of the invention is to overcome existing chlorine-containing gas exists, a kind of method reclaiming chlorine and oxygen from the gas mixture of chloride and oxygen is provided, the present invention except to substitute with adsorption separation technology and revolutionize vitriol oil drying and dehydrating traditional technology cover disease, solve and the problems such as the difficult treatment of dilute sulphuric acid, dewatering efficiency are low, the pollution that causes environment produced to the burn into of equipment and materials; And invented the technology that alternating temperature pressure-variable adsorption (T & PSA) is separated chlorine and oxygen, not only increase separation efficiency, and improve the adsorptive power of adsorption tower.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of method reclaiming chlorine and oxygen from the gas mixture of chloride and oxygen, it is characterized in that: using the mixed tail gas of the product of hydrogen chloride oxidation reaction (Deacon reaction) after the unreacted hydrogenchloride of water absorbing and removing as unstripped gas, be separated through two steps:
A, unstripped gas remove moisture content remaining in tail gas by fractionation by adsorption drying;
B, dry unstripped gas after dehydration are separated by alternating temperature pressure-variable adsorption, complete being separated of chlorine and oxygen.
In described step a, Bian Temp .-changing adsorption drying installation, the composite adsorption oxidant layer that in Temp .-changing adsorption drying process, Bian inhales attached dose of Group close with two kinds, a kind of sorbent material is the aluminum oxide Off aqua being placed on adsorption tower top, another kind is placed on the sorbent material that adsorption tower bottom dehydrates, and the volume proportion of the sorbent material that upper oxide aluminium Off aqua and bottom dehydrate is 20 ~ 80%:80% ~ 20%.
In described step a, also pressure swing adsorption drying installation can be adopted, the composite adsorption oxidant layer that in Adsorbing drying by pressure variation process, Bian inhales attached dose of Group close with two kinds, a kind of sorbent material is the aluminum oxide Off aqua being placed on adsorption tower top, another kind is placed on the sorbent material that adsorption tower bottom dehydrates, and the volume proportion of the sorbent material that upper oxide aluminium Off aqua and bottom dehydrate is 20 ~ 80%:80% ~ 20%.Just apparatus design and operation scheme routinely Adsorbing drying by pressure variation technical requirements carry out.
Described Temp .-changing adsorption drying process is: unstripped gas is from below to up through composite adsorption oxidant layer, and unstripped gas goes out Temp .-changing adsorption drying installation and reaches dry target; In Temp .-changing adsorption drying process: adsorptive pressure is 0.30 ~ 0.80MPa, adsorption temp is 20 ~ 50 DEG C, desorption and regeneration pressure is 0.01 ~ 0.005MPa, desorption and regeneration temperature is 110 ~ 180 DEG C; Arrange all routinely in alternation procedure between absorption and regeneration: step-down, displacement, intensification and cooling step; Regeneration dehydration employing temperature is the carrier gas (unstripped gas or nitrogen) of 50 ~ 180 DEG C, when doing carrier gas regeneration with unstripped gas, unstripped gas is dry through predrying tower, enter steam heater heating again after enter the adsorption dry tower needing ramp regeneration Off water, the utilization of unstripped gas system recoveries is sent in moisture carrier gas back to after cooling, condensation, Separation of Water after going out the tower of absorption.
In described Adsorbing drying by pressure variation process: adsorptive pressure is 0.40 ~ 0.80MPa, desorption pressures is 0.02 ~-0.07MPa, adsorption temp is normal temperature; Arrange all routinely in alternation procedure between sorption and desorption all press, replace, the step such as vacuum take-off; Adsorbing drying by pressure variation device is set to four-column process flow usually routinely, rinses the dried unstripped gas of displacement, rinses and replace and send into the utilization of unstripped gas system recoveries after the equal cooled dehydrated of vacuum take-off tail gas in this process.
The described sorbent material dehydrated is 3A molecular sieve, 5A molecular sieve or silica gel.
Described aluminum oxide Off aqua is the SHFL-3 type aluminum oxide Off aqua of modification, and its preparation method is as follows:
By blended to macropore aluminium glue, macroporous silica gel, calcium oxide, the blue or green powder in zinc oxide and field evenly after, again successively through mediating, shaping, pelletizing, primary drying, bakes to burn the article, dipping, redrying, re-baking make finished product, aluminium glue: silica gel: calcium oxide: zinc oxide: the quality proportioning of the blue or green powder in field is 70-82:7-14:0.5-2.0:5-10:5-10.
The physical properties of described modified aluminas Off aqua is: be of a size of ф 3 ~ 5 × 6mm, and bulk density is 0.6-0.7 kg/L, intensity>=5.0 N/mm, specific surface>=200 m 2/ g, pore volume>=0.65ml/g, abrasion≤5.0%.
The chemical constitution of described modified aluminas Off aqua is: the Al of 75.0-82.0% 2o 3, the SiO of 8.0-11.5% 2, the Na of 0.8-1.2% 2o, the CaO of 1.6-3.0%, the ZnO of 4.0-9.0%, impurity≤0.5%.
In described kneading process, add deionized water in the mixture, the deionized water quality added is 40 ~ 65% of blend composition.
In described pelletizing process, the base substrate of extrusion forming is cut into the pellet that specification is Φ 3-5 × 5-6mm.
In described primary drying process, drying temperature is 110-130 DEG C, and time of drying is 2-3h.
In described bakes to burn the article process, maturing temperature is 380-450 DEG C, and roasting time is 2-3h.
In described steeping process, the solution of dipping is sodium carbonate solution, and the concentration of sodium carbonate solution is 10 ~ 25%, and dipping temperature is 50-80 DEG C, and dipping time is 0.5-1h.
In described redrying process, drying temperature is 110-130 DEG C, and time of drying is 1-1.5h.
In described re-baking process, maturing temperature is 550-580 DEG C, and roasting time is 2-3h.
In the alternating temperature pressure-variable adsorption of described step b: adsorptive pressure is 0.20 ~ 0.7MPa, the temperature of absorption phase drops to 20 ~ 35 DEG C gradually by 40 ~ 70 DEG C; Vacuum desorption pressure is-0.07MPa, desorption temperature is 40 ~ 70 DEG C; Pass into the unstripped gas being less than 40 DEG C during absorption, start to adsorb and lower the temperature; Pass into before desorption and regeneration be greater than 50 DEG C hot chlorine exchange system in gas, and heat up promote desorb, stop when reaching 40 ~ 70 DEG C send hot chlorine and start vacuum desorption; The displacement Bian oxygen before adsorbing is started after completing desorption and regeneration; The tail gas of hot chlorine displacement tail gas and replacement of oxygen all sends unstripped gas system back to.
In the alternating temperature pressure-variable adsorption of described step b, the sorbent material of employing is special-purpose activated charcoal, and its preparation method is: raw material gac makes finished product successively after dipping, drying and Roasting Decomposition.
The physical properties of described special-purpose activated charcoal is: bulk density 0.40 ~ 0.45 kg/L, intensity>=5.5 N/mm, specific surface>=900 m 2/ g, pore volume 0.9 ~ 1.0 ml/g, abrasion≤5%.
The chemical constitution of described special-purpose activated charcoal is: the La of weight percentage 0.5 ~ 2.0% 2o 3, the SiO of 1.2 ~ 1.5% 2, CaO+MgO≤2.0%, surplus is C.
Described special-purpose activated charcoal use pressure is negative pressure, normal pressure-2.5MPa; Use temperature is normal temperature-180 DEG C.
Described steeping process is: on raw material gac, flood La (NO 3) 3the aqueous solution, concentration is 5-12% (% by weight); Dipping temperature is 50-80 DEG C, and dipping time is 0.5-1.0 hours.
The condition of described drying is: drying temperature is 110-120 DEG C, and time of drying is 1.0-1.5 hours.
The condition of described Roasting Decomposition is: containing indifferent gas (N 2+ Ar) thermal treatment under the>=nitrogen protection of 99.9%, Oxygen in Nitrogen content≤0.10%, maturing temperature is 400 ~ 500 DEG C, and roasting time is 2.0 ~ 3.0 hours.
Employing the invention has the advantages that:
One, the present invention adopts Temp .-changing adsorption to be separated drying and dehydrating with pressure-variable adsorption, instead of in prior art and adopt the vitriol oil to dewater, have that technical process is simple, corrosion-free, pollution-free, environmental friendliness, energy consumption are low, separation efficiency is high, level of automation is high, low cost and other advantages, the purity of chlorine gas feeding of Separation and Recovery reaches >=and 99.5% (V.%) and oxygen purity reach >=99.5% (V.%), all can reach the specification of quality being directly used as process feed gas.
Two, the present invention adopts fractionation by adsorption to dewater, not only eradicated and adopted the shortcoming of vitriol oil dehydration---the dilute sulphuric acid of-technical process complexity, equipment corrosion, generation and wastewater treatment difficult and bring environmental pollution, and dehydrate precision and significantly improve, mixed tail gas water-content after adsorption dry is≤10ppm (namely reaching the water content that dew point is-50 ~-70 DEG C of temperature); Only can stablize during the dehydration of the Bian vitriol oil and reach >=200ppm, the corrosion speed of this moisture chlorine to common steel is about 0.219mm/; The present invention makes dehydration precision improve, and is not only conducive to improving the separation efficiency of sorbent material, for the purity of further fractionation by adsorption chlorine and oxygen, raising chlorine and oxygen and the rate of recovery create better basis; Water-content is that the chlorine of≤10 ppm is only about 0.01mm/ to the corrosion speed of common steel, be only that Bian sulphate method dehydrates technology (taking off moisture in chlorine >=200ppm) and causes common steel corrosion speed ~ 4.6%, namely essentially eliminate the corrosion to common steel; And unstripped gas is after Temp .-changing adsorption or Adsorbing drying by pressure variation device, its water-content all can be removed to≤level of 10ppm.
Three, feature of the present invention is: unstripped gas is after Temp .-changing adsorption or pressure-swing absorption apparatus drying, deliver in alternating temperature pressure-variable adsorption (the T & PSA) separation system of second step, the technical requirements of scale and alternating temperature pressure-variable adsorption (T & PSA) device is separated by device desired gas, mainly on the basis of PSA Technology, the heat exchange thermoregulating system that the adsorption temp being increased in absorption phase reduces gradually and raises gradually in the adsorbent layer temperature of regeneration desorption phase.Adsorptive pressure is 0.20 ~ 0.7MPa, absorption phase drop to 20 ~ 35 DEG C gradually by 40 ~ 70 DEG C; Vacuum desorption pressure is-0.07MPa, desorption and regeneration temperature is 40 ~ 70 DEG C; Pass into the unstripped gas of < 40 DEG C during absorption, start to adsorb and lower the temperature and reach 20 ~ 35 DEG C, until complete absorption phase; Then after carrying out drop pressure, from entering " displacement " before the desorption and regeneration stage, pass into the hot chlorine " displacement " of > 50 DEG C, complete " displacement " after namely enter the desorption and regeneration stage and send product chlorine, heating up reaches 40 ~ 70 DEG C and stops sending hot chlorine and start vacuum desorption and regenerate and continue to give off product chlorine.
That is: before beginning absorption phase, product oxygen blow exchange system is used, then unstripped gas enters from adsorption tower bottom and upwards flows, regulate unstripped gas temperature < 40 DEG C to control adsorbent layer by watercooler and remain on 20 ~ 35 DEG C of temperature (reduce temperature and can increase adsorptive capacity) that are lower, that be more conducive to adsorbing chlorine in the temperature of absorption phase middle and later periods, be also conducive to being separated of oxygen and chlorine simultaneously, the product chlorine of temperature > 50 DEG C is regulated to come " displacement " with steam heater when starting " displacement " before the desorption and regeneration stage, the product chlorine of " displacement " process sends unstripped gas system back to, " displacement " complete after the product chlorine of continuation > 50 DEG C raise the temperature of adsorbent layer, remain on higher and be conducive to chlorine vacuum desorption regeneration 40 ~ 70 DEG C of temperature (raised temperature also can improve the effect of vacuum desorption), reach 40 ~ 70 DEG C stop sending hot product chlorine and start vacuum desorption regeneration, product chlorine system is all sent to the chlorine of vacuum desorption regenerative process outlet after completing from " displacement ".
Four, Bian alternating temperature pressure-variable adsorption of the present invention is separated, the result of gac to the absorption property of chlorine is pointed out: reduce adsorption temp can significantly improve adsorptive power----in 45 DEG C of chlorine adsorptive capacitys for 100%, when when 25 DEG C, chlorine adsorptive capacity is 118%, 5 DEG C, chlorine adsorptive capacity is 135%; Obviously, when Bian is with traditional PSA Technology, the adsorption temp being simultaneously increased in absorption phase reduces by 20 ~ 30 DEG C gradually, can improve the adsorptive power to chlorine; 20 ~ 40 DEG C are raised gradually in the vacuum desorption regeneration temperature of vacuum desorption regeneration stage, not only can promote that vacuum desorption regenerates more thorough, but also the fractionation by adsorption effect of chlorine and oxygen can be improved---be not only conducive to improving the output of chlorine and oxygen in each fractionation by adsorption cycle, and the purity of product chlorine and oxygen can be improved further; In addition, the fractionation by adsorption that alternating temperature pressure-variable adsorption is separated is run and is no longer subject to envrionment temperature on the impact of pressure-variable adsorption tripping device adsorption separation efficiency.
Five, design technology system of the present invention, equipment, separation system control and working procedure arrange and (comprise adsorption tower element number to determine to design with the working procedure of alternating temperature, pressure-variable adsorption sepn process, for improving purity, the rate of recovery of gas product and saving energy and reduce the cost, all according to PSA Gas Separation Technology practice verified effective working procedure, experience is set to design the operation working procedure of each adsorption tower, that is: adsorbs, equal schedule of operation steps such as pressure, step-down, purging (displacement), vacuum desorption regeneration, displacement); Press the custom requirements that pressure-variable adsorption is separated between multiple adsorption tower, unified staggering is in different working procedure stage, marshalling, steady running.
Six, the present invention can obtain high-purity oxygen in absorption tail gas, and the purity of product oxygen is >=99.5%, the rate of recovery of oxygen reaches >=98.8%; Desorb is started and vacuuming stage can obtain high purity chlorine after completing " displacement ", the purity of product chlorine is >=99.5%, the rate of recovery of chlorine reaches >=98.8%.
Seven, the performance of modified aluminas Off aqua of the present invention is the water-absorbing dry drying prescription that can allow to use in the chlorine-containing gas containing a small amount of moisture content, Strong degree better, pore volume is comparatively large, water regain is larger, water content can be reached with the Off crystal degree that it carries out adsorption dry and be only≤10ppm (namely reaching water content when dew point is-50 ~-70 DEG C of temperature), only can stablize when dewatering far below the Bian vitriol oil and reach water content >=200ppm.
Eight, modified aluminas Off aqua in the present invention can form multiple-hearth sorbent material with silica gel, SHFL-3 type aluminum oxide Off aqua is placed on the exit end of gas in composite adsorption bed, be responsible for the effect of checking on to the dehydration of gas depth drying, there is good effect, be applied in adsorption dry technology, Off crystal degree can reach water content and be only≤10ppm (namely reaching water content when dew point is-50 ~-70 DEG C of temperature), only can stablize when dewatering far below the Bian vitriol oil and reach water content >=200ppm, make it possible to Bian fractionation by adsorption dehydrate technical substitution and thoroughly change vitriol oil drying and dehydrating traditional technology cover disease, solve the corrosion to equipment and materials, produce the difficult treatment of dilute sulphuric acid, dewatering efficiency is low, energy consumption is high causes the problems such as the pollution of environment, but also can improve the adsorption separation efficiency that rear operation alternating temperature pressure-variable adsorption (T & PSA) is separated chlorine and oxygen, and alternating temperature pressure-variable adsorption (T & PSA) sepn process operation is more stable, operation life is longer.
Nine, the special active carbon in the present invention impregnated of La (NO at gac 3) 3with the Roasting Decomposition that heats up after drying, make the gac of modification, not only 5 ~ 6% are improve to the adsorptive capacity of chlorine, the more important thing is the separation efficiency that improve chlorine and oxygen, be conducive to the purity improving product chlorine and product oxygen.
Ten, in the special active carbon that the present invention adopts, rare earth atoms structure is special, internal layer 4f track unpaired electron is many, magnetic moment of atom is high, electronic level is extremely abundant, almost can react with all elements, form multivalent state, the compound of polygamy figure place (3 ~ 12), there is the absorption of many excellences, leaching is disputed after La2O3, gac internal surface not only basicity increases to some extent, and be enriched in sorbent material (carrier) surface, define the ordered structure that some new multilayers containing rare earth arrange, add effective adsorption activity center number, thus improve the absorption property of gac, improve adsorptive power and the catalytic activity of sorbent material) and light, electricity, magnetic, the characteristics such as core, be called as magical " novel material treasure-house ".
11, the special active carbon in the present invention, be applied to adsorption separating method from the gas mixture that the catalytic oxidation of hydrogen chloride reaction generates in high efficiency separation chlorine and oxygen, the loading capacity of sorbent material, selectivity, stability, compressive strength, the performance such as wear resistance and quality uniformity obtain more obviously improving, special-purpose activated charcoal not only improves 5 ~ 6% to the adsorptive capacity of chlorine, the more important thing is the separation efficiency that improve chlorine and oxygen, be conducive to the purity improving product chlorine and product oxygen.
Accompanying drawing explanation
Fig. 1 is drying nest TSA drying process figure;
Fig. 2 is drying nest PSA drying process figure;
Fig. 3 is T & PSA alternating temperature just pressure fractionation by adsorption chlorine and oxygen schema.
Embodiment
embodiment 1
The mixed tail gas (of the present invention unstripped gas) of product after the unreacted hydrogenchloride of water absorbing and removing (existing production technology) of hydrogen chloride oxidation reaction enters fractionation by adsorption (drying) device and removes moisture content remaining in tail gas: Temp .-changing adsorption drying installation (also can adopt Adsorbing drying by pressure variation device) can be adopted to carry out drying and dehydrating.
The in-built desiccant layer being filled with two kinds of Xi Fu Ji Group and closing of adsorption tower, a kind of sorbent material is the SHFL-3 type aluminum oxide Off aqua of modification, another kind is the 3A molecular sieve (or 5A molecular sieve, silica gel) dehydrated, SHFL-3 type aluminum oxide Off aqua is placed on the bottom that the top of adsorption tower, 3A molecular sieve or silica gel are placed on adsorption tower, and the volume proportion of SHFL-3 and 3A molecular sieve (or 5A molecular sieve, silica gel) is 20 ~ 80% and 80% ~ 20%.
In Temp .-changing adsorption drying process: adsorptive pressure is 0.30 ~ 0.80MPa, adsorption temp is 20 ~ 50 DEG C, desorption and regeneration pressure is 0.02 ~ 0.005MPa, desorption and regeneration temperature is 120 ~ 180 DEG C; In alternation procedure between absorption and regeneration, step-down, displacement, intensification and cooling step are set all routinely; Regeneration dehydration, with hot nitrogen (or unstripped gas of heat), sends unstripped gas system back to after cooling, condensation, Separation of Water.Process tolerance scale looked by Temp .-changing adsorption drying installation, selects to arrange 3 to 6 adsorption towers.
As shown in Figure 1:
The adsorption dry stage: unstripped gas enters system by intake pipeline import 1, moisture content remaining in tail gas is removed through absorption (drying) tower A (or absorption (drying) tower B and absorption (drying) tower C adsorbs) adsorption dry, dried unstripped gas exports dry unstripped gas by export pipeline outlet 2, and absorption (drying) tower A, B, C formation is staggered operation.
Inverse put buck stage: after adsorption dry stage Jie Bouquet, carry out inverse put step-down, isolates the regeneration tail gas after moisture content from absorption (drying) tower A Exhaust Gas through cooling separator F1 and returns unstripped gas system by export pipeline e outlet.
The displacement stage: partial raw gas (10 ~ 25%) is by after predrying tower D drying, after steam heater E heats, deliver to adsorption tower to be regenerated replace, displacement tail gas is isolated the regeneration tail gas after moisture content through cooling separator F1 and is returned unstripped gas system by export pipeline e outlet.
The vacuum regeneration stage: after Zhi Huan Jie Bouquet, continue to pass into partial raw gas (10 ~ 25%), run by the dried gas of predrying tower D, enter regeneration stage, while starting regeneration, adsorption tower temperature continues to raise, until when temperature liter reaches the temperature range of needs, part material tolerance is reduced to < 5% from 10 ~ 25% and is run, and stop the supple of gas or steam gradually, start vacuum regeneration, resurgent gases containing desorb moisture content all isolates the regeneration tail gas after moisture content by vacuum pump P through cooling separator F2, and tail gas exports f by export pipeline and returns unstripped gas system.
Cooling boost phase: after having regenerated, the unstripped gas partly entered from the mouth of pipe 1 waits the adsorption tower boosted of lowering the temperature after entering after predrying tower D drying and having regenerated, make that temperature in adsorption tower drops to normal temperature gradually, pressure is raised to and is adsorbed in pressure needed for the dry stage, preparation enters adsorption drying process next time, returns unstripped gas system from the unstripped gas of adsorption column outlet by export pipeline e outlet.
Predrying tower D regenerates and runs: the dry unstripped gas of the adsorption column outlet in adsorption dry stage separates 10% ~ 20% and heats laggard predrying tower D through steam heater E, the hydrolysis suction making to adsorb in predrying tower D, sorbent material dehydration regeneration, water-containing material gas separates the unstripped gas after moisture content through cooling separator F1 and returns unstripped gas system through outlet e.
In addition, in figure, E is steam heater, and P is vacuum pump, F1 and F2 is cooling separator, and a is heating steam import, and b is vapour outlet, and c is entrance of cooling water, and d is cooling water outlet, and g is condensed water discharge outlet.
This drying process also can Bian Adsorbing drying by pressure variation device: the desiccant layer that in adsorption tower, same filling two kinds of Xi Fu Ji Group close, a kind of sorbent material is SHFL-3 type aluminum oxide Off aqua, another kind is the 3A molecular sieve (or 5A molecular sieve, silica gel) dehydrated, SHFL-3 type aluminum oxide Off aqua is placed on the bottom that the top of adsorption tower, 3A molecular sieve or silica gel are placed on adsorption tower, and the volume proportion of SHFL-3 and 3A molecular sieve (or 5A molecular sieve, silica gel) is 20 ~ 80% and 80% ~ 20%; In Adsorbing drying by pressure variation process: adsorptive pressure is 0.40 ~ 0.70MPa, desorption pressures is 0.02 ~-0.07MPa, adsorption temp is normal temperature; For improving unstripped gas utilising efficiency, arrange all routinely in the alternation procedure between sorption and desorption all press, replace, rinse, vacuum pulling step; Adsorbing drying by pressure variation device is set to four-column process flow routinely.SHFL-3 type aluminum oxide Off aqua described herein and modified aluminas Off aqua, this is preferably, but is not limited thereto.
As shown in Figure 2:
The adsorption dry stage: unstripped gas is entered by intake pipeline 3, adsorbent drying in absorption (drying) tower A2 (or absorption (drying) tower B2, absorption (drying) tower C2 and absorption (drying) tower D2) removes the moisture content contained in unstripped gas, and dried unstripped gas is exported by export pipeline outlet 6.
The drop pressure stage: after the adsorption dry stage terminates, gas in absorption (drying) tower A2 is along air flow line, by gas and treat that absorption (drying) the tower B2 (or adsorbing (drying) tower C2 and absorption (drying) tower D2) all pressed all presses, the pressure of absorption (drying) tower B2 raises, and the gaseous tension in absorption (drying) tower A2 then reduces; After all having pressed, absorption (drying) tower A2 continues step-down, until replace and pressure needed for regeneration stage, this stage expellant gas (comprising a small amount of water vapor of desorb from sorbent material during step-down) is then discharged by pipeline outlet 5 and is delivered to unstripped gas system;
All the stage is pressed once all to press, also can repeatedly all press, when Bian secondary or more is all pressed, for marshalling all presses working procedure to need, be provided with equalizer tank E2, carry out inferior grade gaseous tension when all pressing, the gas of absorption (drying) tower and equalizer tank E2 all presses, gas is temporarily stored in equalizer tank E2; Gas is exported by all pressures of equalizer tank E2 and another adsorption tower.
In the displacement stage: entered by intake pipeline 4 with a small amount of dry unstripped gas, enter adsorption tower A2 its Inner gas displacement is clean, displacement tail gas then returns unstripped gas system by export pipeline 5.
The vacuum regeneration stage: after completing displacement, enter the vacuum desorption stage, adsorption tower A2 internal pressure is down to vacuum, the water vapor of desorb from sorbent material and a small amount of unstripped gas are sucked out, by returning unstripped gas system by vacuum pump P through export pipeline outlet 7 after cooling separator F2 refrigerated separation water.
The displacement stage: entered by intake pipeline 4 with a small amount of dry unstripped gas, top enters adsorption tower A2 and is replaced by the water vapor of its Inner clean, displacement tail gas out bottom adsorption tower, by returning unstripped gas system by vacuum pump P through export pipeline outlet 7 after cooling separator F2 refrigerated separation water.
The boost pressure stage: after the displacement stage completes, absorption (drying) tower A2 then requires with follow procedure that absorption (drying) tower terminating adsorption dry stage running carries out boost pressure, after completing boost pressure, switch and pass into the pressure condition that unstripped gas continues to boost to adsorption dry demands.Adsorption drying process next time can be entered.
In addition, in figure, E2 is equalizer tank, and a is entrance of cooling water, and b is cooling water outlet, and g is condensation-water drain.
Unstripped gas is after Temp .-changing adsorption or pressure-swing absorption apparatus drying, deliver in alternating temperature pressure-variable adsorption (the T & PSA) separation system of second step, the technical requirements of scale and alternating temperature pressure-variable adsorption (T & PSA) device is separated by device desired gas, mainly on the basis of PSA Technology, the heat exchange thermoregulating system that the adsorption temp being increased in absorption phase reduces gradually and raises gradually in the catalyst layer temperature of regeneration desorption phase.The sorbent material of Bian is SHFL-6 type gac, and adsorptive pressure is 0.20 ~ 0.7MPa, the adsorption temp of absorption phase drops to 20 ~ 35 DEG C gradually by 40 ~ 70 DEG C; Vacuum desorption pressure is-0.07MPa, desorption temperature is 40 ~ 70 DEG C; Pass into the unstripped gas of < 40 DEG C during absorption, start to adsorb cooling and reach 20 ~ 35 DEG C, until complete absorption phase; Then after carrying out drop pressure, from entering " displacement " before desorption phase, pass into the hot chlorine " displacement " of > 50 DEG C, complete " displacement " after namely enter desorption phase and send product chlorine, heating up reaches 40 ~ 70 DEG C and stops sending hot chlorine and starting vacuum desorption.SHFL-6 type gac described herein and special active carbon, this is preferably, but is not limited thereto.
As shown in Figure 3:
The cooling fractionation by adsorption stage: dried unstripped gas is inputted by intake pipeline 13, the fractionation by adsorption of carrying out oxygen and chlorine after water cooler G1 cools by adsorbing (drying) tower A1 (or absorption (drying) tower B1, absorption (drying) tower C1 and absorption (drying) tower D1), the temperature of simultaneously adsorbing (drying) tower A1 drop to predetermined adsorption temp gradually, chlorine is by adsorbent, oxygen is discharged as product oxygen from adsorption tower top, product oxygen is exported by export pipeline outlet 10.
The drop pressure stage: after the fractionation by adsorption stage terminates, gas in absorption (drying) tower A1 is along air flow line, by gas and treat that absorption (drying) the tower B1 (or adsorbing (drying) tower C1, absorption (drying) tower D1) all pressed all presses, the pressure of absorption (drying) tower B1 raises, and the gaseous tension in absorption (drying) tower A1 then reduces; After all having pressed, absorption (drying) tower A1 continues step-down, until pressure needed for the displacement stage, this stage expellant gas is all discharged by pipeline outlet 11 and delivered to unstripped gas system;
All the stage is pressed once all to press, also can repeatedly all press, when Bian secondary or more is all pressed, for marshalling all presses working procedure to need, be provided with equalizer tank E1, when inferior grade gaseous tension is all pressed, the gas of absorption (drying) tower and all press at equalizer tank E1, gas is temporarily stored in equalizer tank E1; Gas is exported by all pressures of equalizer tank E1 and another adsorption tower.
In the displacement stage: entered by intake pipeline 12 with product chlorine, improve after temperature through steam heater F, enter adsorption tower A1 its Inner gas displacement is clean, adsorption tower A1 starts to heat up simultaneously, and displacement tail gas then returns unstripped gas system by export pipeline 11.
The intensification vacuum desorption stage: after Zhi Huan Jie Bouquet, continue to pass into the product chlorine improved after temperature through steam heater F and enter adsorption tower A1, enter intensification desorption phase, while starting desorb, the temperature of adsorption tower A1 continues to raise, until when temperature liter reaches the temperature range of needs, stop sending hot chlorine, starting vacuum desorption, in the intensification vacuum desorption stage bottom adsorption tower A1 chlorine out all after water cooler H1 cools, by vacuum pump P, export pipeline outlet 8, output products chlorine.
In the displacement stage: after intensification vacuum desorption stage Jie Bouquet, from the mouth of pipe 9 input product oxygen, pass into adsorption tower A1, the chlorine displacement in it discharged, the displacement tail gas of discharging from adsorption tower A1 tower top returns unstripped gas system through export pipeline 11.
The boost pressure stage: after the displacement stage completes, absorption (drying) tower A1 then requires with follow procedure that absorption (drying) tower having terminated fractionation by adsorption stage running carries out boost pressure, after completing boost pressure, switch and pass into the pressure condition that unstripped gas continues to boost to adsorption dry demands.Preparation enters adsorption separation process next time.
In addition, in figure, E1 is equalizer tank, and F is steam heater, and G1 is watercooler, and H1 is watercooler, and P is vacuum pump, and a is heating steam import, and b is vapour outlet, and c is entrance of cooling water, and d is cooling water outlet.
embodiment 2
A kind of method reclaiming chlorine and oxygen from the gas mixture of chloride and oxygen, comprise: using the mixed tail gas of the product of hydrogen chloride oxidation reaction (Deacon reaction) after the unreacted hydrogenchloride of water absorbing and removing as unstripped gas, be separated through two steps:
A, unstripped gas remove moisture content remaining in tail gas by fractionation by adsorption drying;
B, dry unstripped gas after dehydration are separated by alternating temperature pressure-variable adsorption, complete being separated of chlorine and oxygen.The purity of chlorine gas feeding of Separation and Recovery reaches >=and 99.5% (V.%) and oxygen purity reach >=99.5% (V.%), all can reach the specification of quality being directly used as process feed gas.
In described step a, Bian Temp .-changing adsorption drying installation, the composite adsorption oxidant layer that in Temp .-changing adsorption drying process, Bian inhales attached dose of Group close with two kinds, a kind of sorbent material is the aluminum oxide Off aqua being placed on adsorption tower top, another kind is placed on the sorbent material that adsorption tower bottom dehydrates, and the volume proportion of the sorbent material that upper oxide aluminium Off aqua and bottom dehydrate is 20 ~ 80%:80% ~ 20%.
In described step a, also pressure swing adsorption drying installation can be adopted, the composite adsorption oxidant layer that in Adsorbing drying by pressure variation process, Bian inhales attached dose of Group close with two kinds, a kind of sorbent material is the aluminum oxide Off aqua being placed on adsorption tower top, another kind is placed on the sorbent material that adsorption tower bottom dehydrates, and the volume proportion of the sorbent material that upper oxide aluminium Off aqua and bottom dehydrate is 20 ~ 80%:80% ~ 20%.Just apparatus design and operation scheme routinely Adsorbing drying by pressure variation technical requirements carry out.
Described Temp .-changing adsorption drying process is: unstripped gas is from below to up through composite adsorption oxidant layer, and unstripped gas goes out Temp .-changing adsorption drying installation and reaches dry target; In Temp .-changing adsorption drying process: adsorptive pressure is 0.30 ~ 0.80MPa, adsorption temp is 20 ~ 50 DEG C, desorption and regeneration pressure is 0.01 ~ 0.005MPa, desorption and regeneration temperature is 110 ~ 180 DEG C; Arrange all routinely in alternation procedure between absorption and regeneration: step-down, displacement, intensification and cooling step; Regeneration dehydration employing temperature is the carrier gas (unstripped gas or nitrogen) of 50 ~ 180 DEG C, when doing carrier gas regeneration with unstripped gas, unstripped gas is dry through predrying tower, enter steam heater heating again after enter the adsorption dry tower needing ramp regeneration Off water, the utilization of unstripped gas system recoveries is sent in moisture carrier gas back to after cooling, condensation, Separation of Water after going out the tower of absorption.
In described Adsorbing drying by pressure variation process: adsorptive pressure is 0.40 ~ 0.80MPa, desorption pressures is 0.02 ~-0.07MPa, adsorption temp is normal temperature; Arrange all routinely in alternation procedure between sorption and desorption all press, replace, the step such as vacuum take-off; Adsorbing drying by pressure variation device is set to four-column process flow usually routinely, rinses the dried unstripped gas of displacement, rinses and replace and send into the utilization of unstripped gas system recoveries after the equal cooled dehydrated of vacuum take-off tail gas in this process.
The described sorbent material dehydrated is 3A molecular sieve, 5A molecular sieve or silica gel.
Described aluminum oxide Off aqua is the SHFL-3 type aluminum oxide Off aqua of modification, and its preparation method is as follows:
By blended to macropore aluminium glue, macroporous silica gel, calcium oxide, the blue or green powder in zinc oxide and field evenly after, again successively through mediating, shaping, pelletizing, primary drying, bakes to burn the article, dipping, redrying, re-baking make finished product, aluminium glue: silica gel: calcium oxide: zinc oxide: the quality proportioning of the blue or green powder in field is 70-82:7-14:0.5-2.0:5-10:5-10.
The physical properties of described modified aluminas Off aqua is: be of a size of ф 3 ~ 5 × 6mm, and bulk density is 0.6-0.7 kg/L, intensity>=5.0 N/mm, specific surface>=200 m 2/ g, pore volume>=0.65ml/g, abrasion≤5.0%.
The chemical constitution of described modified aluminas Off aqua is: the Al of 75.0-82.0% 2o 3, the SiO of 8.0-11.5% 2, the Na of 0.8-1.2% 2o, the CaO of 1.6-3.0%, the ZnO of 4.0-9.0%, impurity≤0.5%.
In described kneading process, add deionized water in the mixture, the deionized water quality added is 40 ~ 65% of blend composition.
In described pelletizing process, the base substrate of extrusion forming is cut into the pellet that specification is Φ 3-5 × 5-6mm.
In described primary drying process, drying temperature is 110-130 DEG C, and time of drying is 2-3h.
In described bakes to burn the article process, maturing temperature is 380-450 DEG C, and roasting time is 2-3h.
In described steeping process, the solution of dipping is sodium carbonate solution, and the concentration of sodium carbonate solution is 10 ~ 25%, and dipping temperature is 50-80 DEG C, and dipping time is 0.5-1h.
In described redrying process, drying temperature is 110-130 DEG C, and time of drying is 1-1.5h.
In described re-baking process, maturing temperature is 550-580 DEG C, and roasting time is 2-3h.
In the alternating temperature pressure-variable adsorption of described step b: adsorptive pressure is 0.20 ~ 0.7MPa, the temperature of absorption phase drops to 20 ~ 35 DEG C gradually by 40 ~ 70 DEG C; Vacuum desorption pressure is-0.07MPa, desorption temperature is 40 ~ 70 DEG C; Pass into the unstripped gas being less than 40 DEG C during absorption, start to adsorb and lower the temperature; Pass into before desorption and regeneration be greater than 50 DEG C hot chlorine exchange system in gas, and heat up promote desorb, stop when reaching 40 ~ 70 DEG C send hot chlorine and start vacuum desorption; The displacement Bian oxygen before adsorbing is started after completing desorption and regeneration; The tail gas of hot chlorine displacement tail gas and replacement of oxygen all sends unstripped gas system back to.
In the alternating temperature pressure-variable adsorption of described step b, the sorbent material of employing is special-purpose activated charcoal, and its preparation method is: raw material gac makes finished product successively after dipping, drying and Roasting Decomposition.
The physical properties of described special-purpose activated charcoal is: bulk density 0.40 ~ 0.45 kg/L, intensity>=5.5 N/mm, specific surface>=900 m 2/ g, pore volume 0.9 ~ 1.0 ml/g, abrasion≤5%.
The chemical constitution of described special-purpose activated charcoal is: the La of weight percentage 0.5 ~ 2.0% 2o 3, the SiO of 1.2 ~ 1.5% 2, CaO+MgO≤2.0%, surplus is C.
Described special-purpose activated charcoal use pressure is negative pressure, normal pressure-2.5MPa; Use temperature is normal temperature-180 DEG C.
Described steeping process is: on raw material gac, flood La (NO 3) 3the aqueous solution, concentration is 5-12% (% by weight); Dipping temperature is 50-80 DEG C, and dipping time is 0.5-1.0 hours.
The condition of described drying is: drying temperature is 110-120 DEG C, and time of drying is 1.0-1.5 hours.
The condition of described Roasting Decomposition is: containing indifferent gas (N 2+ Ar) thermal treatment under the>=nitrogen protection of 99.9%, Oxygen in Nitrogen content≤0.10%, maturing temperature is 400 ~ 500 DEG C, and roasting time is 2.0 ~ 3.0 hours.
embodiment 3
A kind of method reclaiming chlorine and oxygen from the gas mixture of chloride and oxygen, comprise: using the mixed tail gas of the product of hydrogen chloride oxidation reaction (Deacon reaction) after the unreacted hydrogenchloride of water absorbing and removing as unstripped gas, be separated through two steps:
A, unstripped gas remove moisture content remaining in tail gas by fractionation by adsorption drying;
B, dry unstripped gas after dehydration are separated by alternating temperature pressure-variable adsorption, complete being separated of chlorine and oxygen.
In described step a, Bian Temp .-changing adsorption drying installation, the composite adsorption oxidant layer that in Temp .-changing adsorption drying process, Bian inhales attached dose of Group close with two kinds, a kind of sorbent material is the aluminum oxide Off aqua being placed on adsorption tower top, another kind is placed on the sorbent material that adsorption tower bottom dehydrates, and the volume proportion of the sorbent material that upper oxide aluminium Off aqua and bottom dehydrate is 20%:80%.
In described step a, also pressure swing adsorption drying installation can be adopted, the composite adsorption oxidant layer that in Adsorbing drying by pressure variation process, Bian inhales attached dose of Group close with two kinds, a kind of sorbent material is the aluminum oxide Off aqua being placed on adsorption tower top, another kind is placed on the sorbent material that adsorption tower bottom dehydrates, and the volume proportion of the sorbent material that upper oxide aluminium Off aqua and bottom dehydrate is 20%:80%.Just apparatus design and operation scheme routinely Adsorbing drying by pressure variation technical requirements carry out.
Described Temp .-changing adsorption drying process is: unstripped gas is from below to up through composite adsorption oxidant layer, and unstripped gas goes out Temp .-changing adsorption drying installation and reaches dry target; In Temp .-changing adsorption drying process: adsorptive pressure is 0.30MPa, adsorption temp is 20 DEG C, desorption and regeneration pressure is 0.01MPa, desorption and regeneration temperature is 110 DEG C; Arrange all routinely in alternation procedure between absorption and regeneration: step-down, displacement, intensification and cooling step; Regeneration dehydration employing temperature is the carrier gas (unstripped gas or nitrogen) of 50 ~ 180 DEG C, when doing carrier gas regeneration with unstripped gas, unstripped gas is dry through predrying tower, enter steam heater heating again after enter the adsorption dry tower needing ramp regeneration Off water, the utilization of unstripped gas system recoveries is sent in moisture carrier gas back to after cooling, condensation, Separation of Water after going out the tower of absorption.
In described Adsorbing drying by pressure variation process: adsorptive pressure is 0.40MPa, desorption pressures is 0.02MPa, adsorption temp is normal temperature; Arrange all routinely in alternation procedure between sorption and desorption all press, replace, the step such as vacuum take-off; Adsorbing drying by pressure variation device is set to four-column process flow usually routinely, rinses the dried unstripped gas of displacement, rinses and replace and send into the utilization of unstripped gas system recoveries after the equal cooled dehydrated of vacuum take-off tail gas in this process.
In the alternating temperature pressure-variable adsorption of described step b: adsorptive pressure is 0.20MPa, the temperature of absorption phase drops to 20 DEG C gradually by 40 DEG C; Vacuum desorption pressure is-0.07MPa, desorption temperature is 40 DEG C; Pass into the unstripped gas being less than 40 DEG C during absorption, start to adsorb and lower the temperature; Pass into before desorption and regeneration be greater than 50 DEG C hot chlorine exchange system in gas, and heat up promote desorb, stop when reaching 40 DEG C send hot chlorine and start vacuum desorption; The displacement Bian oxygen before adsorbing is started after completing desorption and regeneration; The tail gas of hot chlorine displacement tail gas and replacement of oxygen all sends unstripped gas system back to.
embodiment 4
A kind of method reclaiming chlorine and oxygen from the gas mixture of chloride and oxygen, comprise: using the mixed tail gas of the product of hydrogen chloride oxidation reaction (Deacon reaction) after the unreacted hydrogenchloride of water absorbing and removing as unstripped gas, be separated through two steps:
A, unstripped gas remove moisture content remaining in tail gas by fractionation by adsorption drying;
B, dry unstripped gas after dehydration are separated by alternating temperature pressure-variable adsorption, complete being separated of chlorine and oxygen.
In described step a, Bian Temp .-changing adsorption drying installation, the composite adsorption oxidant layer that in Temp .-changing adsorption drying process, Bian inhales attached dose of Group close with two kinds, a kind of sorbent material is the aluminum oxide Off aqua being placed on adsorption tower top, another kind is placed on the sorbent material that adsorption tower bottom dehydrates, and the volume proportion of the sorbent material that upper oxide aluminium Off aqua and bottom dehydrate is 80%:20%.
In described step a, also pressure swing adsorption drying installation can be adopted, the composite adsorption oxidant layer that in Adsorbing drying by pressure variation process, Bian inhales attached dose of Group close with two kinds, a kind of sorbent material is the aluminum oxide Off aqua being placed on adsorption tower top, another kind is placed on the sorbent material that adsorption tower bottom dehydrates, and the volume proportion of the sorbent material that upper oxide aluminium Off aqua and bottom dehydrate is 80%:20%.Just apparatus design and operation scheme routinely Adsorbing drying by pressure variation technical requirements carry out.
Described Temp .-changing adsorption drying process is: unstripped gas is from below to up through composite adsorption oxidant layer, and unstripped gas goes out Temp .-changing adsorption drying installation and reaches dry target; In Temp .-changing adsorption drying process: adsorptive pressure is 0.80MPa, adsorption temp is 50 DEG C, desorption and regeneration pressure is 0.005MPa, desorption and regeneration temperature is 180 DEG C; Arrange all routinely in alternation procedure between absorption and regeneration: step-down, displacement, intensification and cooling step; Regeneration dehydration employing temperature is the carrier gas (unstripped gas or nitrogen) of 180 DEG C, when doing carrier gas regeneration with unstripped gas, unstripped gas is dry through predrying tower, enter steam heater heating again after enter the adsorption dry tower needing ramp regeneration Off water, the utilization of unstripped gas system recoveries is sent in moisture carrier gas back to after cooling, condensation, Separation of Water after going out the tower of absorption.
In described Adsorbing drying by pressure variation process: adsorptive pressure is 0.80MPa, desorption pressures is-0.07MPa, adsorption temp is normal temperature; Arrange all routinely in alternation procedure between sorption and desorption all press, replace, the step such as vacuum take-off; Adsorbing drying by pressure variation device is set to four-column process flow usually routinely, rinses the dried unstripped gas of displacement, rinses and replace and send into the utilization of unstripped gas system recoveries after the equal cooled dehydrated of vacuum take-off tail gas in this process.
In the alternating temperature pressure-variable adsorption of described step b: adsorptive pressure is 0.7MPa, the temperature of absorption phase drops to 35 DEG C gradually by 70 DEG C; Vacuum desorption pressure is-0.07MPa, desorption temperature is 70 DEG C; Pass into the unstripped gas being less than 40 DEG C during absorption, start to adsorb and lower the temperature; Pass into before desorption and regeneration be greater than 50 DEG C hot chlorine exchange system in gas, and heat up promote desorb, stop when reaching 70 DEG C send hot chlorine and start vacuum desorption; The displacement Bian oxygen before adsorbing is started after completing desorption and regeneration; The tail gas of hot chlorine displacement tail gas and replacement of oxygen all sends unstripped gas system back to.
embodiment 5
A kind of method reclaiming chlorine and oxygen from the gas mixture of chloride and oxygen, comprise: using the mixed tail gas of the product of hydrogen chloride oxidation reaction (Deacon reaction) after the unreacted hydrogenchloride of water absorbing and removing as unstripped gas, be separated through two steps:
A, unstripped gas remove moisture content remaining in tail gas by fractionation by adsorption drying;
B, dry unstripped gas after dehydration are separated by alternating temperature pressure-variable adsorption, complete being separated of chlorine and oxygen.
In described step a, Bian Temp .-changing adsorption drying installation, the composite adsorption oxidant layer that in Temp .-changing adsorption drying process, Bian inhales attached dose of Group close with two kinds, a kind of sorbent material is the aluminum oxide Off aqua being placed on adsorption tower top, another kind is placed on the sorbent material that adsorption tower bottom dehydrates, and the volume proportion of the sorbent material that upper oxide aluminium Off aqua and bottom dehydrate is 60%:40%.
In described step a, also pressure swing adsorption drying installation can be adopted, the composite adsorption oxidant layer that in Adsorbing drying by pressure variation process, Bian inhales attached dose of Group close with two kinds, a kind of sorbent material is the aluminum oxide Off aqua being placed on adsorption tower top, another kind is placed on the sorbent material that adsorption tower bottom dehydrates, and the volume proportion of the sorbent material that upper oxide aluminium Off aqua and bottom dehydrate is 60%:40%.Just apparatus design and operation scheme routinely Adsorbing drying by pressure variation technical requirements carry out.
Described Temp .-changing adsorption drying process is: unstripped gas is from below to up through composite adsorption oxidant layer, and unstripped gas goes out Temp .-changing adsorption drying installation and reaches dry target; In Temp .-changing adsorption drying process: adsorptive pressure is 0.50MPa, adsorption temp is 40 DEG C, desorption and regeneration pressure is 0.008MPa, desorption and regeneration temperature is 160 DEG C; Arrange all routinely in alternation procedure between absorption and regeneration: step-down, displacement, intensification and cooling step; Regeneration dehydration employing temperature is the carrier gas (unstripped gas or nitrogen) of 100 DEG C, when doing carrier gas regeneration with unstripped gas, unstripped gas is dry through predrying tower, enter steam heater heating again after enter the adsorption dry tower needing ramp regeneration Off water, the utilization of unstripped gas system recoveries is sent in moisture carrier gas back to after cooling, condensation, Separation of Water after going out the tower of absorption.
In described Adsorbing drying by pressure variation process: adsorptive pressure is 0.50MPa, desorption pressures is 0.01MPa, adsorption temp is normal temperature; Arrange all routinely in alternation procedure between sorption and desorption all press, replace, the step such as vacuum take-off; Adsorbing drying by pressure variation device is set to four-column process flow usually routinely, rinses the dried unstripped gas of displacement, rinses and replace and send into the utilization of unstripped gas system recoveries after the equal cooled dehydrated of vacuum take-off tail gas in this process.
In the alternating temperature pressure-variable adsorption of described step b: adsorptive pressure is 0.5Pa, the temperature of absorption phase drops to 25 DEG C gradually by 50 DEG C; Vacuum desorption pressure is-0.07MPa, desorption temperature is 50 DEG C; Pass into the unstripped gas being less than 40 DEG C during absorption, start to adsorb and lower the temperature; Pass into before desorption and regeneration be greater than 50 DEG C hot chlorine exchange system in gas, and heat up promote desorb, stop when reaching 50 DEG C send hot chlorine and start vacuum desorption; The displacement Bian oxygen before adsorbing is started after completing desorption and regeneration; The tail gas of hot chlorine displacement tail gas and replacement of oxygen all sends unstripped gas system back to.
embodiment 6
The present embodiment is described the modified aluminas Off aqua adopted in the present invention:
One, general description
Preparation method is: aluminium glue, silica gel, calcium oxide, zinc oxide, the blue or green powder in field are carried out blended, Pinch closes, SHFL-3 type aluminum oxide Off aqua finished product is made in shaping, pelletizing, drying, roasting, dipping sodium carbonate, drying, roasting.
Two, the preparation of SHFL-3 type aluminum oxide Off aqua
1. material proportion:
The ratio of components of mass percent: aluminium glue (powder): silica gel (powder): CaO: ZnO: sesbania powder=70-82:7-14:0.5-2.0:5-10:5-10; Adopt aluminium glue powder, during silica-gel powder, Mu Shuo No has particular requirement, because want Jia Shui Pinch to close.
Adding amount of deionized water when , Pinch closes by above-mentioned batching and after mixing is: 40 ~ 65% (in ingredients by weight for 100%).
2. preparation process requires:
Infusion entails: Na 2cO 3concentration is 10 ~ 25% (% by weight);
Dipping temperature is 50 ~ 80 DEG C;
Dipping time is 0.5 ~ 1.0 hour;
Primary drying requires: drying temperature is 110 ~ 130 DEG C;
Time of drying is 2 ~ 3 hours;
Redrying requires: drying temperature is 110 ~ 130 DEG C;
Time of drying is 1.0 ~ 1.5 hours;
Bakes to burn the article (carrier calcination) requires: maturing temperature is 380-450 DEG C;
Roasting time is 2-3h;
Re-baking requires: maturing temperature is 550 ~ 580 DEG C;
Roasting time is 2.0 ~ 3.0 hours.
Three, the physicochemical property of SHFL-3 type modified aluminas Off aqua
1. physical properties (seeing the following form)
2. chemical constitution (seeing the following form) % by weight
Project Al 2O 3 SiO2 Na 2O CaO ZnO Other
SHFL-3 75.0~82.0 8.0~11.5 0.8~1.2 1.6~3.0 4.0~9.0 ≤0.5
Note: other are the impurity that raw material brings.
Four, use range, performance
1. use pressure normal pressure ~ 1.5MPa
2. use temperature normal temperature ~ 300 DEG C
3. can be used for moisture content in acid gas removal body
4. during water regain normal temperature and pressure, maximum water regain is >=0.35 kg/L
5. life-span ~ 2 years.
embodiment 7
The present embodiment is described the special-purpose activated charcoal adopted in the present invention:
Through experimental study, the sorbent material being used for fractionation by adsorption chlorine and oxygen is selected to be modified activated carbon.
By the textural difference of natural material, chemical constitution and the changeable restriction of impurity, when being raw material production gac with it, being difficult to control its structural performance and chemical property and obtaining the very uniform product of quality.
Rare earth atoms structure is special, internal layer 4f track unpaired electron is many, magnetic moment of atom is high, electronic level is extremely abundant, almost can react with all elements, forms the compound of multivalent state, polygamy figure place (3 ~ 12), there is the absorption of many excellences, dipping La 2o 3after (being decomposed obtained by La (NO3) 3), gac internal surface not only basicity increases to some extent but also is enriched in sorbent material (carrier) surface, define ordered structure that some new multilayers containing rare earth arrange, add effective adsorption activity center number, thus improve the absorption property of gac, improve the adsorptive power of sorbent material and catalytic activity and optical, electrical, the characteristic such as magnetic, core; Be called as magical " novel material treasure-house ".
One, impregnated additive prepares principle scheme
La (NO can be flooded in face on the activated carbon 3) 3, La in its finished product 2o 3content can be 0.5%-2.0%; The dynamic adsorption capacity of chlorine improves 5-6%, the more important thing is and improve the related application performance such as separation efficiency and stability, compressive strength, wear resistance quality uniformity of activated carbon to chlorine and oxygen, not only be conducive to the purity improving product chlorine and product oxygen, and be conducive to full scale plant safety, steady running.
Two, the preparation of SHFL-6 type modified activated carbon absorbent
1. raw material:
(1). raw material gac: qualitative performance requirements sees the following form.
(2). raw material La (NO 3) 3for the crystallization containing six water.
2. preparation process:
Infusion entails: La (NO 3) 3the aqueous solution, concentration is 5-12% (% by weight);
Dipping temperature is 50-80 DEG C;
Dipping time is 0.5-1.0 hours;
Dry requirement: drying temperature is 110 ~ 120 DEG C;
Time of drying is 1.0 ~ 1.5 hours;
Roasting Decomposition requires: containing indifferent gas (N 2+ Ar) thermal treatment (Oxygen in Nitrogen content≤0.10%) under>=nitrogen protection of 99.9%; Maturing temperature is 400-500 DEG C; Roasting time is 2.0-3.0 hours.
La is added in gac 2o 3after, 5.0-6.0% is improve to the dynamic adsorbance of chlorine.
Three, the physicochemical property of SHFL-6 type acticarbon
1. physical properties (seeing the following form)
2. chemical constitution (seeing the following form) (% by weight)
Four, use range, performance
1. use pressure negative pressure ~ normal pressure ~ 2.5MPa;
2. use temperature normal temperature ~ 180 DEG C;
3. be applicable to chlorine and oxygen in mixing dry gas body, being separated of nitrogen;
4. about ~ 2 years work-ing life.
Be described specific embodiments of the invention above, what embodiment adopted is all four tower pressure swing adsorption processs.It is to be appreciated that the present invention is not limited to above-mentioned particular implementation, those skilled in the art can make various distortion or amendment within the scope of the claims, and this does not affect flesh and blood of the present invention.

Claims (8)

1. from the gas mixture of chloride and oxygen, reclaim a method for chlorine and oxygen, it is characterized in that: using the mixed tail gas of the product of hydrogen chloride oxidation reaction after the unreacted hydrogenchloride of water absorbing and removing as unstripped gas, be separated through two steps:
A, unstripped gas remove moisture content remaining in tail gas by fractionation by adsorption drying;
B, dry unstripped gas after dehydration are separated by alternating temperature pressure-variable adsorption, complete being separated of chlorine and oxygen;
In the alternating temperature pressure-variable adsorption of described step b: adsorptive pressure is 0.20 ~ 0.7MPa, the temperature of absorption phase drops to 20 ~ 35 DEG C gradually by 40 ~ 70 DEG C; Vacuum desorption pressure is-0.07MPa, desorption temperature is 40 ~ 70 DEG C; Pass into the unstripped gas being less than 40 DEG C during absorption, start to adsorb and lower the temperature; Pass into before desorption and regeneration be greater than 50 DEG C hot chlorine exchange system in gas, and heat up promote desorb, stop when reaching 40 ~ 70 DEG C send hot chlorine and start vacuum desorption; The displacement Bian oxygen before adsorbing is started after completing desorption and regeneration; The tail gas of hot chlorine displacement tail gas and replacement of oxygen all sends unstripped gas system back to;
In the alternating temperature pressure-variable adsorption of described step b, the sorbent material of employing is special-purpose activated charcoal, and its preparation method is: raw material gac makes finished product successively after dipping, drying and Roasting Decomposition; Described steeping process is: on raw material gac, flood La (NO 3) 3the aqueous solution, weight percent concentration is 5-12%; Dipping temperature is 50-80 DEG C, and dipping time is 0.5-1.0 hours; The condition of described drying is: drying temperature is 110-120 DEG C, and time of drying is 1.0-1.5 hours; The condition of described Roasting Decomposition is: containing indifferent gas N 2thermal treatment under the nitrogen protection of+Ar>=99.9%, Oxygen in Nitrogen content≤0.10%, maturing temperature is 400 ~ 500 DEG C, and roasting time is 2.0 ~ 3.0 hours.
2. the method reclaiming chlorine and oxygen from the gas mixture of chloride and oxygen according to claim 1, it is characterized in that: in described step a, Bian Temp .-changing adsorption drying installation, the composite adsorption oxidant layer that in Temp .-changing adsorption drying process, Bian inhales attached dose of Group close with two kinds, a kind of sorbent material is the aluminum oxide Off aqua being placed on adsorption tower top, another kind is placed on the sorbent material that adsorption tower bottom dehydrates, and the volume proportion of the sorbent material that upper oxide aluminium Off aqua and bottom dehydrate is 20 ~ 80%:80% ~ 20%.
3. the method reclaiming chlorine and oxygen from the gas mixture of chloride and oxygen according to claim 1, it is characterized in that: in described step a, adopt pressure swing adsorption drying installation, the composite adsorption oxidant layer that in Adsorbing drying by pressure variation process, Bian inhales attached dose of Group close with two kinds, a kind of sorbent material is the aluminum oxide Off aqua being placed on adsorption tower top, another kind is placed on the sorbent material that adsorption tower bottom dehydrates, and the volume proportion of the sorbent material that upper oxide aluminium Off aqua and bottom dehydrate is 20 ~ 80%:80% ~ 20%.
4. the method reclaiming chlorine and oxygen from the gas mixture of chloride and oxygen according to claim 2, it is characterized in that: described Temp .-changing adsorption drying process is: unstripped gas is from below to up through composite adsorption oxidant layer, and unstripped gas goes out Temp .-changing adsorption drying installation and reaches dry target; In Temp .-changing adsorption drying process: adsorptive pressure is 0.30 ~ 0.80MPa, adsorption temp is 20 ~ 50 DEG C, desorption and regeneration pressure is 0.01 ~ 0.005MPa, desorption and regeneration temperature is 110 ~ 180 DEG C; All arrange in alternation procedure between absorption and regeneration: step-down, displacement, intensification and cooling step; Regeneration dehydration employing temperature is the carrier gas of 50 ~ 180 DEG C, when doing carrier gas regeneration with unstripped gas, unstripped gas is dry through predrying tower, enter steam heater heating again after enter the adsorption dry tower needing ramp regeneration Off water, the utilization of unstripped gas system recoveries is sent in moisture carrier gas back to after cooling, condensation, Separation of Water after going out the tower of absorption.
5. the method reclaiming chlorine and oxygen from the gas mixture of chloride and oxygen according to claim 3, is characterized in that: in described Adsorbing drying by pressure variation process: adsorptive pressure is 0.40 ~ 0.80MPa, desorption pressures is 0.02 ~-0.07MPa, adsorption temp is normal temperature; All arrange in alternation procedure between sorption and desorption all press, replace, vacuum pulling step; Adsorbing drying by pressure variation device is set to four-column process flow usually routinely, rinses the dried unstripped gas of displacement, rinses and replace and send into the utilization of unstripped gas system recoveries after the equal cooled dehydrated of vacuum take-off tail gas in this process.
6. according to claim 2, 3, the method reclaiming chlorine and oxygen from the gas mixture of chloride and oxygen described in 4 or 5, it is characterized in that: described aluminum oxide Off aqua is modified aluminas Off aqua, its preparation method is as follows: by macropore aluminium glue, macroporous silica gel, calcium oxide, the blue or green powder in zinc oxide and field blended evenly after, again successively through mediating, shaping, pelletizing, primary drying, bakes to burn the article, dipping, redrying, re-baking makes finished product, aluminium glue: silica gel: calcium oxide: zinc oxide: the quality proportioning of the blue or green powder in field is 70-82:7-14:0.5-2.0:5-10:5-10.
7. the method reclaiming chlorine and oxygen from the gas mixture of chloride and oxygen according to claim 6, it is characterized in that: the physical properties of described modified aluminas Off aqua is: be of a size of ф 3 ~ 5 × 6mm, bulk density is 0.6-0.7 kg/L, intensity>=5.0 N/mm, specific surface>=200 m 2/ g, pore volume>=0.65ml/g, abrasion≤5.0%; The chemical constitution of described modified aluminas Off aqua is: the Al of 75.0-82.0% 2o 3, the SiO of 8.0-11.5% 2, the Na of 0.8-1.2% 2o, the CaO of 1.6-3.0%, the ZnO of 4.0-9.0%, impurity≤0.5%.
8. the method reclaiming chlorine and oxygen from the gas mixture of chloride and oxygen according to claim 1, is characterized in that: the physical properties of described special-purpose activated charcoal is: bulk density 0.40 ~ 0.45 kg/L, intensity>=5.5 N/mm, specific surface>=900 m 2/ g, pore volume 0.9 ~ 1.0 ml/g, abrasion≤5%; The chemical constitution of described special-purpose activated charcoal is: the La of weight percentage 0.5 ~ 2.0% 2o 3, the SiO of 1.2 ~ 1.5% 2, CaO+MgO≤2.0%, surplus is C; Described special-purpose activated charcoal use pressure is negative pressure, normal pressure-2.5MPa; Use temperature is normal temperature-180 DEG C.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1590279A (en) * 1995-10-04 2005-03-09 巴斯福股份公司 Method for separating and recovering chlorine from service gas containing chlorine
CN1865127A (en) * 2005-05-18 2006-11-22 浙江巍华化工有限公司 Separation and purification method of mixed waste gas containing chlorine and hydrogen chloride
CN101454240A (en) * 2006-05-23 2009-06-10 拜尔材料科学股份公司 Method for producing chlorine from hydrogen chloride and oxygen
CN102502498A (en) * 2011-10-19 2012-06-20 甘肃银达化工有限公司 Method for separating and recovering chlorine and oxygen of hydrogen chloride oxidation gas mixture by use of PSA (Pressure Swing Adsorption) technology
CN103380078A (en) * 2011-02-18 2013-10-30 巴斯夫欧洲公司 Distillation method for removing chlorine from gas flows that contain oxygen and chlorine

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1590279A (en) * 1995-10-04 2005-03-09 巴斯福股份公司 Method for separating and recovering chlorine from service gas containing chlorine
CN1865127A (en) * 2005-05-18 2006-11-22 浙江巍华化工有限公司 Separation and purification method of mixed waste gas containing chlorine and hydrogen chloride
CN101454240A (en) * 2006-05-23 2009-06-10 拜尔材料科学股份公司 Method for producing chlorine from hydrogen chloride and oxygen
CN103380078A (en) * 2011-02-18 2013-10-30 巴斯夫欧洲公司 Distillation method for removing chlorine from gas flows that contain oxygen and chlorine
CN102502498A (en) * 2011-10-19 2012-06-20 甘肃银达化工有限公司 Method for separating and recovering chlorine and oxygen of hydrogen chloride oxidation gas mixture by use of PSA (Pressure Swing Adsorption) technology

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