CN101262926A - Method and apparatus for purifying a gas - Google Patents
Method and apparatus for purifying a gas Download PDFInfo
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- CN101262926A CN101262926A CN 200680033062 CN200680033062A CN101262926A CN 101262926 A CN101262926 A CN 101262926A CN 200680033062 CN200680033062 CN 200680033062 CN 200680033062 A CN200680033062 A CN 200680033062A CN 101262926 A CN101262926 A CN 101262926A
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Abstract
The present invention provides for a method and apparatus for purifying carbon dioxide. Sulfur species and other impurities are removed from the carbon dioxide by a series of steps which include heater means, impurity adsorption means and catalysis means. Economical on-site analytical capabilities are also provided for by concentrating the impurities prior to their analysis.
Description
Invention field
The invention provides a kind of method and apparatus that is used for purifying and analytical gas.Particularly, the invention provides a kind of method and apparatus that carbon dioxide as additive in the manufacture process that requires high-pureness carbon dioxide and composition is carried out purifying and analysis.
Background of invention
Carbon dioxide is used for many industry and domestic applications, does not contain various impurity in many these application requirements carbon dioxide.Unfortunately, the carbon dioxide that obtains by natural source such as gas well, chemical method, fermentation process, the carbon dioxide that perhaps produces in industrial production particularly by the carbon dioxide of hydrocarbon products burning generation, contains sulphur compound such as the carbonyl sulfide (COS) and the hydrogen sulfide (H of impurity level usually
2S), oxidation product (oxygenates) is as acetaldehyde and alcohol, and aromatic compounds such as benzene.When carbon dioxide is estimated to be used for the application (for example manufacturing of food and soda, medical product and electronic device and cleaning) of requirement high-pureness carbon dioxide, must before using, sulphur compound and other hydrocarbon impurity that contains in the air-flow be reduced to low-down content.The Impurity removal level that requires changes according to the application of carbon dioxide.For example, for the beverage articles for use, carbon dioxide (CO
2) in total sulfur content should be lower than 0.1ppm, the content of aromatic hydrocarbon must be lower than 0.02ppm.For the electronic product clean applications, the content of heavy hydrocarbon need be reduced to and be lower than 0.1ppm.
The whole bag of tricks of removing sulphur compound and hydrocarbon impurity from the gas of carbon dioxide and so on is known.For example, the United States Patent (USP) of authorizing Lieder etc. has disclosed for the 4th, 332, No. 781 by following steps and has removed COS and H in the air-flow
2The method of S: at first, contact the H that removes in the hydrocarbon stream with the aqueous solution of reproducible oxidation reactant by making air-flow
2S, described reproducible oxidation reactant can be a polyvalent metal ion, for example iron, vanadium, copper etc., thus produce air-flow that contains COS and the aqueous mixture that contains the reactant of sulphur and reduction.Be hydrolyzed to CO by making air-flow and water contact the COS that makes in the air-flow then with suitable hydrolyst
2And H
2S, described hydrolyst for example are nickel, platinum, palladium etc., after this, and with H
2S discharge and when needing with CO
2Discharge.This step can be by the H that describes before
2S removes step or finishes by absorbing.Said method relates to and uses heavy and expensive equipment and based on the system of liquid, this system needs close concern, and disadvantageous compound such as water vapour may be introduced in the carbon dioxide product.
United States Patent (USP) the 5th, 858,068 and 6,099, disclose the faujasite that uses the silver exchange and MFI type molecular sieve for No. 619 and removed sulphur, oxygen and other impurity in the carbon dioxide, this carbon dioxide will be used in the relevant application of food.United States Patent (USP) the 5th, 674 has disclosed for No. 463 and to have utilized hydrolysis and to remove carbonyl sulfide and hydrogen sulfide impurities in the carbon dioxide with the reaction of metal oxide such as iron oxide.
Know, contact with metal oxide such as cupric oxide, zinc oxide or their mixture, can directly remove sulphur compound in the air-flow (H for example by making air-flow
2S).Also know by following steps and can remove sulphur impurity: at first on hydrolyst, make COS be hydrolyzed to H
2S is then by removing H with reactive metal oxide
2S.As COS and H
2When the content of the impurity of S and so on surpasses trace, by removing H with reactive metal oxide
2It is higher that the expense of S can become, because this catalyst is non-renewable, and costs an arm and a leg.Need use cheaply material to remove COS and H
2S and other sulphur impurity (for example mercaptan and dimethyl sulfide) are to reduce purifying CO
2Cost.Also need to remove at low cost acetaldehyde, alcohol, aromatic compounds (for example benzene) and wait other impurity.According to using (need remove metal for electronic product and food applications, remove agricultural chemicals) for the food application need, may also need to remove other impurity as metal and agricultural chemicals and so on, thereby the method that also needs to remove these impurity.In addition, also needing can be with the various impurity of low cost analysis such as sulphur compound, aldehyde, pure and mild aromatic compounds.
Because the terminal user of many carbon dioxide requires their employed carbon dioxide not sulfur-containing compound, hydrocarbon and other impurity substantially, and because the carbon dioxide that the carbon dioxide of natural origin and industry are made often contains sulphur and hydrocarbon compound, therefore people are still seeking sulphur and the hydrocarbon compound that can remove fully basically in the carbon dioxide gas stream, and other impurity can not introduced economy and effective method in the carbon dioxide simultaneously.People are also in the low-cost analytical method of seeking for various impurity.Hope can have easy and effective method is realized these purposes.
Summary of the invention
The invention provides a kind of method of purified gases, this method may further comprise the steps: heated air, gas is imported desulfurizing device; Further heating is from the carbon dioxide of desulfurizing device, with gas input reactor bed, to remove impurity by oxidation; The air-flow cooling of reactor will be left; Use film and/or absorption and reaction unit to remove moisture and other impurity; The gas input of purifying is needed in the technical process of purified gases.
In one embodiment, the gas that carries out purifying comprises carbon dioxide.In one embodiment, before gas is imported desulfurizing device, in carbon dioxide, add oxygen.According to the content of impurity in the incoming flow, not all step all is essential in this method.
In another embodiment, the invention provides a kind of equipment that is used for purified gas stream, this equipment comprises: first heater or first heat-exchange device; Desulfurizing device; Second heater or heat-exchange device; The reactor beds device; Cooling/heat-exchange device, film and/or absorption and reaction unit; Gas utilization unit.
In another embodiment, the invention provides and a kind of comprising carbon dioxide is analyzed method with the in-situ processing of purifying, this method may further comprise the steps: a) with impure carbon dioxide (impure carbondioxide) air-flow input reaction of Salmon-Saxl device bed, removing the sulfur-containing compound that exists in the carbon dioxide gas stream, form substantially the not carbon dioxide gas stream of sulfur-bearing; B) will be substantially not the carbon dioxide gas stream of sulfur-bearing be input in the reactor beds, thereby remove the hydrocarbon compound that exists in the carbon dioxide gas stream, form the carbon dioxide gas stream that does not contain hydrocarbon compound substantially; C) the carbon dioxide stream that will not contain hydrocarbon compound is substantially imported drier and/or adsorbent bed, forms the carbon dioxide stream of substantially dry; D) impurity in the concentrated carbon dioxide stream is with the carbon dioxide gas stream input analysis platform (analytical skid) of substantially dry, with any impurity that exists in the carbon dioxide of measuring substantially dry; E) in the running with high-pureness carbon dioxide (purified carbon dioxide) stream input producer, perhaps import in the carbon dioxide storage tank, perhaps be used for this two kinds of purposes simultaneously.
Brief Description Of Drawings
Though specification and claims have pointed out that clearly the applicant thinks its subject matter of an invention, by the present invention may be better understood in conjunction with the following drawings:
Fig. 1 be to be used to make, clean, the carbon dioxide of encapsulation, can or production process carries out the schematic diagram of the overall process of purifying and analysis;
Fig. 2 is the schematic diagram that carries out carbon dioxide purification in the carbon dioxide production facility.
Detailed Description Of The Invention
Usually the carbon dioxide that is used for industrial process of producing contains many impurity. These impurity usually are many The problem that Carbon Dioxide Application is concerned about, but estimating that being used for the people consumes (for example soda) and electronics system In the production of the product of making, the purity of carbon dioxide is very important, can affect taste, the matter of final products Amount and legitimacy.
Can usually contain following impurity by the impure carbon dioxide that any carbon dioxide source obtains: sulfuration is closed Thing, for example carbonyl sulfide, hydrogen sulfide, dimethyl sulfide, sulfur dioxide and mercaptan; Hydrocarbon impurity, for example aldehyde, alcohol, Aromatic compounds, propane, ethene; And other impurity, for example water, carbon monoxide, metal and agricultural chemicals. The invention describes the new method of removing various impurity and the new method of analyzing some impurity. Can be according to titanium dioxide Carbon be in process of production purifying or in the time will using purifying, can use in a different manner these to go Remove the method with analysing impurity. The various fields of employment of carbon dioxide comprise beverage filling equipment, food product refrigeration Equipment, electronic product manufacturing equipment and fountain type (fountain) carbon dioxide distribution place.
For the purposes of the present invention, at least some sulphur impurities (for example hydrogen sulfide and carbonyl sulfide) can be at 50-150 ℃ the rising temperature under remove. In production equipment, can be after final compression stage but at aftercooler Reach this temperature in the compression process of feed carbon dioxide before. When will using, this temperature can Obtain by the combination of using heater and heat-exchange device. The low-purity two of suitable temperature will be warmed up to Carbon oxide gas stream is incorporated into reaction of Salmon-Saxl device bed. This normally contains the appearance of some catalyst and sorbing material Device, these catalyst and sorbing material or with sulphur compound reaction or adsorption of sulfur compounds.
Preferably, catalyst material is to make H2S and COS are converted into elementary sulfur and are retained in purification media On catalyst material, or form the catalyst material of metal oxide with sulphur impurity reaction. Mercaptan it The sulphur impurity of class can be adsorbed on the purification media simply. Some materials may need oxygen make hydrogen sulfide it The sulphur compound of class is converted into sulphur, needs oxygen and water to make carbonyl sulfide be converted into hydrogen sulfide, and then is converted into sulphur. Material according to sulfur purification of the present invention comprises carbonate and hydroxide, for example the sodium on activated carbon and potassium Hydroxide or carbonate; Metal oxide, for example use separately or load on copper in the micro-porous adsorption agent, The oxide of zinc, chromium or iron, described micro-porous adsorption agent for example is activated alumina, activated carbon or silica gel. Its It also can remove carbonyl sulfide and sulfur dioxide impurities by reaction effectively such as the material of CuY zeolite and so on. With comparing near the processing under the ambient temperature, use higher temperature sulphur removal obviously to improve except devulcanization The ability of hydrogen and carbonyl sulfide.
For the purposes of the present invention, by with catalytic oxidation and absorption in conjunction with or only remove hydrocarbon impurity by absorption.Adsorbent bed can be removed from unconverted any impurity of catalyst bed and water, perhaps removes most of impurity when not using catalyst bed.In production equipment, catalytic reactor can be after sulfur removal bed, after the charging compression step, perhaps after water wash step.In the field of employment, catalyst bed can be after sulfur removal bed.Stream temperature need be elevated to 150-450 ℃, so that various hydrocarbon impurity oxidation.The temperature of reactor depends on the impurity that will remove and the catalyst of use.
The carbon dioxide gas stream that is substantially free of oxidation of sulfur compound impurities is imported above-mentioned catalytic reactor after improving its temperature by heater and/or heat exchanger device.Catalytic reactor can contain the catalyst of one piece catalyst or particle form.Employed material noble metal normally in catalytic reactor, as platinum or palladium, they load on particulate vector or the one piece carrier.This reactor beds is adding an amount of oxygen by the oxidation reaction purification of carbon dioxide before the catalyst bed or before the sulfur removal bed.In catalyst bed, the impurity conversion of propane, aldehyde, alcohol, acetic acid esters and aromatic compounds and so on is carbon dioxide and water.Any sulphur impurity residual after sulfur removal step can be converted into sulfur dioxide in catalyst bed.The temperature of catalyst bed depends on the impurity in the charging.For the impurity of alcohol, aldehyde and aromatic compounds and so on, need temperature 150 ℃ to 300 ℃ scope.But, for other impurity of methane, ethane and propane and so on, require temperature to be higher than 300 ℃, need temperature to be higher than 450 ℃ sometimes.Catalytic reactor can be by being oxidized to it impurity that carbon dioxide is removed carbon monoxide and so on.For suitably removing impurity, need to surpass the oxygen of the required stoichiometry of oxidation reaction, and the addition of essential suitably control oxygen.
The logistics of leaving reactor beds or sulfur removal bed or compressor reducer is cooled to send into adsorbent bed then near environment temperature in heat-exchange device, removes and anhydrate and other residual impurity.Used adsorbent depends on the impurity in the charging.Usually, the adsorbent of activated alumina (AA), zeolite (for example 4A or 13X) or silica gel and so on is used to remove moisture.In addition, for the purposes of the present invention, adsorbent bed contains zeolite such as NaY or its ion exchange form, to remove the sulphur compound (for example dimethyl sulfide compound) of impurity aldehyde, alcohol (for example methyl alcohol and ethanol), acetic acid esters (for example methyl acetate and ethyl acetate) and some traces.For these impurity, the ability of y-type zeolite is apparently higher than other zeolite and non-zeolitic materials.For the aromatic compounds of benzene and toluene and so on, can use other adsorbent of activated carbon or dealuminium Y type beta stone (DAY) and so on.
For plurality of impurities, need be in adsorbent bed stacked multiple adsorbent.For from underfeed situation, the setting of adsorbent bed is to remove water absorbent in the bottom usually, and the centre is a y-type zeolite, and the top is activated carbon/DAY adsorbent.Adsorbent can be nonrecoverable pattern, and sorbing material is changed after using up fully, perhaps can regenerate.Usually carry out heat regeneration with logistics free from foreign meter comparatively speaking.For continued operation, need two or more adsorbent beds, when one or more regeneration of adsorbent beds, another or a plurality of adsorbent bed can be in the purifying pattern like this.
For the purposes of the present invention, use the various impurity of sulphur analyzer and hydrocarbon analyzer analysis in the different phase of this processing procedure.These two kinds of analyzers can be in an independent device, gas-chromatography for example, and perhaps they can be different devices.Before analyzing, can the impurity of various sulphur and hydrocarbon be concentrated, to improve their content in sample.This step has been improved the detection lower limit of each analyzer.This is specially adapted to content to be reduced to the impurity of benzene below the 20ppb and so in beverage application.
The sulphur analyzer will be analyzed the total sulfur content in charging, different phase and the final products or the content of various sulphur class materials.For beverage grade carbon dioxide, the total sulfur content in the product except that sulfur dioxide must be lower than 0.1ppm, and sulfur dioxide must be lower than 1ppm.
The hydrocarbon analyzer will be analyzed total hydrocarbon (for example methane) amount in charging, different phase and the final products or the content of various hydrocarbon materials.For beverage grade carbon dioxide, require the total hydrocarbon amount in the product to be lower than 50ppm, then different to the restriction of each component, for example the content of benzene needs less than 20ppb, and the content of acetaldehyde needs less than 0.1ppm, and the content of methyl alcohol needs less than 10ppm.
Adopt the various combinations of described purification technique and analytical technology to solve various CO
2Purifying needs.For in the time will using carbon dioxide, carrying out purifying, purification of carbon dioxide before beverage filling or electronic product are made for example, the flow velocity that uses with the user is transported to purifier apparatus with impure carbon dioxide from storage tank usually.These speed are 100-10000sm
3/ hour (standard cubic meter/hour), the final application and the scale of production facility specifically depended on.The pressure of carbon dioxide is about the 1.5-21 crust usually, generally is about the 15-19.5 crust.In some applications, particularly those relate to the application of the carbon dioxide that is used for the electronics cleaning, and the scope of pressure is that 60 crust are to hundreds of crust.
Referring to accompanying drawing, Fig. 1 is the overview of carbon dioxide being carried out purge process in the time will using.According to the impurity in the charging, the some parts in this process can omit.With impure carbon dioxide from storage tank 10 along pipeline 1, by pressure regulator 3, introduce first heat exchanger 20 along pipeline 5 again.By pipeline 2 oxygen is added in this logistics, be used for sulfur removal bed and catalytic reactor.Optional flow controller (not shown) can be used for measuring and control the impure carbon dioxide flow from storage tank 10.First heat exchanger 20 is elevated to about 40-120 ℃ with the temperature of impure carbon dioxide from room temperature.Not pure carbon dioxide through heating leaves first heat exchanger, arrives heater 30 by pipeline 7, and the temperature of logistics is maintained at about 50-150 ℃ in heater.For some situation, can omit heat exchanger 20, only use the raise temperature of logistics of heater 30.Impure carbon dioxide is left this heater, enters sulfur removal bed 40 by pipeline 9.Sulfur removal bed contains various materials, as supported carbonates, hydroxide and oxide, is used to remove various sulphur impurities such as hydrogen sulfide, COS and mercaptan.Can extract sample by pipeline 12, be transported to analysis platform 65, so that the real time data of sulfur impurity concentration in the reaction of Salmon-Saxl device bed to be provided.
The not pure carbon dioxide that does not contain most of sulphur impurity is substantially introduced second heat exchanger 50 by pipeline 11, and the temperature of logistics is elevated to more than 150 ℃ in second heat exchanger.This impure carbon dioxide is discharged from second heat exchanger by pipeline 13, further is heated to 150-450 ℃ in the unshowned in the drawings heater.The carbon dioxide of this heating enters in the catalyst bed 60 that contains pellet type catalyst or monolith catalyst.Various impurity in the charging (for example benzene and aldehyde) react in catalytic reactor with oxygen, are converted into carbon dioxide and water.In this reactor, some residual in charging sulphur impurities can be converted into sulfur dioxide.
At this moment, the carbon dioxide gas stream of purifying is left catalytic reactor substantially, turns back in second heat exchanger 50 by pipeline 15.Part in this high-pureness carbon dioxide (purified carbon dioxide) gas is drawn towards analysis platform 65 by pipeline 14, analyzes the purity of this carbon dioxide gas stream at analysis platform.
Purified carbon dioxide gas steam is left second heat exchanger, enters first heat exchanger 20 by pipeline 17, and the temperature of this logistics is brought down below 40 ℃ in first heat exchanger.The pure carbon dioxide air-flow of cooling leaves first heat exchanger, enters optional film drier 70 by pipeline 19, and the most of water in the film drier in the carbon dioxide gas stream is removed.This high-pureness carbon dioxide leaves optional film drier, enter adsorbent bed 80 by pipeline 21, this adsorbent bed helps to remove any impurity that may still exist in the carbon dioxide gas stream as the backup unit (bakeup) of catalytic reactor bed 60 and sulfur removal bed 40.If use the film drier to dewater, then adsorbent 80 contains two adsorption layers usually, promptly is used to the activated carbon layer of removing zeolite such as the y-type zeolite layer of aldehyde, alcohol, acetic acid esters and DMS and being used to remove the aromatic compounds impurity of benzene and toluene and so on.Described activated carbon layer can be used to remove residual sulphur, for example hydrogen sulfide and carbonyl sulfide by carbonate, hydroxide or metal oxide impregnated.If do not use the film drier, then must use the other adsorption layer that constitutes by activated alumina or silica gel or zeolite (for example 3A, 4A, 13X and NaY) to remove moisture.This adsorbent bed can carry out heat regeneration with logistics free from foreign meter substantially under 150-300 ℃ temperature.A part of carbon dioxide behind the purifying can be used as regeneration gas.
The sub-fraction sample of the purification of carbon dioxide that adsorbent bed 80 is discharged returns analysis platform 65 by pipeline 24, detects any impurity that may still exist in the carbon dioxide gas stream.Most of carbon dioxide leaves adsorbent bed, reaches valve 25A by pipeline 23.This valve is divided into two parts with carbon dioxide gas stream, about 90% air communication is crossed pipeline 25 and is directly guided in the manufacturing operation, about 10% air communication is crossed pipeline 27, becomes liquefied carbon dioxide by cooler 85 again, arrives the pure carbon dioxide jar 90 of deposit then by pipeline 29.
Analysis platform comprises sample concentrator and one or more detector that is used to analyze various impurity such as sulphur compound, hydrocarbon, aromatic compounds and oxidation product.Sample concentrator is sent into their desorption in the detector then normally based on impurity is adsorbed for a long time.FID (flame ionization detector) or PID (photoionization detector) can be used for detecting hydrocarbon, aromatic compounds and oxidation product.FPD (flame photometric detector) or SCD (sulfur chemistry luminescence detector) can be used for measuring sulphur impurity.
Equipment of the present invention and method are to design with solving carbon dioxide impurities, particularly are being used for the relevant problem of carbon dioxide that manufacture process will be supplied with in the time will using.By carrying out purifying and analysis simultaneously, the operator of production facility can obtain stable supply and the purification of carbon dioxide of quality assurance is arranged, and the present invention also provides the conservation tank that contains purification of carbon dioxide, the particular case that can be used for the real-time under-supply of any purification of carbon dioxide or can not satisfy the demands.This makes the operator can control purge process better, because if impurity content can not satisfy the requirement to each impurity content in the carbon dioxide, then the operator can stop or ending purge process.
Shown among Fig. 2 and used each side of the present invention purification of carbon dioxide in carbon dioxide production plant.To be transported to from the carbon dioxide in source 100 in the optional metals/pesticides removal device 105.As indicated above, this device can be made up of one or more purge processes that are selected from absorption, water wash column, electrostatic precipitator or filter.The carbon dioxide of being discharged by device 105 is transfused in the compressor reducer 110, its pressure is brought up to 14-20 crust (barg), adds oxygen from pipeline 115 to compressed air stream.The logistics of being discharged by final compression stage is in 70-95 ℃ temperature, be transported to then in the optional heater assembly 120, further the rising temperature is to 75-150 ℃, be transported to then in the optional desulfurizing device 125, in this desulfurizing device, react by zeolite, remove the sulphur impurity of hydrogen sulfide, carbonyl sulfide and mercaptan and so on metal oxide, hydroxide or carbonate or copper exchange.Some product such as sulphur can also be attracted on the carrier of activated carbon and activated alumina and so on.
Described logistics of discharging from optional desulfurizing device 125 further heating optional heat exchanger 130 and optional heater 135 enters optional catalytic reactor 140 then.This catalytic reactor comprises loaded noble metal catalyst, for example the palladium of graininess or monolith forms or platinum.According to the impurity in the incoming flow, catalytic reactor moves under 150-450 ℃ temperature.In this reactor, hydrocarbon impurity is oxidized to water and carbon dioxide.The logistics that this reactor 140 is discharged is cooled off in heat exchanger 130, further is cooled near room temperature in water-cooled aftercooler 145 then.
The logistics that aftercooler 145 is discharged is transported in the adsorption system 150, is used to remove moisture and other impurity.The size of adsorbent bed depends on the impurity in the incoming flow 100, and whether uses reactor 140.Adsorbent bed in the adsorption system 150 contains adsorbent, the adsorbent that is used for removing oxidation product (for example aldehyde, pure and mild acetic acid esters), adsorbent that is used for remaining sulphur impurity (for example DMS) and the adsorbent of using except that moisture that is used for remaining aromatic compounds (for example toluene and benzene).Typical bed structure comprises and is used for dewatered activated alumina, silica gel, zeolite 13X or 4A, is used to remove NaY zeolite or its ion exchange form of oxidation product and DMS, and the activated carbon or the DAY zeolite that are used to remove aromatic compounds and other impurity.For continued operation, use two or more beds usually, one of them bed carries out purifying to carbon dioxide stream, the logistics regeneration that another usefulness is free from foreign meter.From purification of carbon dioxide liquefaction device 160 that adsorption system 150 is discharged, randomly distill, be transported to products-supply place by pipeline 170 then.Use analytical system mentioned above to analyze charging and purified carbon dioxide streams.The purification of carbon dioxide that does not meet purity requirement can not be transported to the deposit place by pipeline 165 dischargings.Any uncooled material is discharged by pipeline 155 in the product.
Applicable industry of the present invention or consumption industry include but not limited to the manufacturing and the cleaning of food; The manufacturing of the manufacturing of electronic product, electronic unit and assembly; The cleaning of medical product; The carbonating of soft drink, beer and water; Contain the covering of the storage tank and the container of flammable liquid or powder; The covering of the material that in air, can degrade, for example vegetable oil, spices and essence.
Further specify the present invention by following examples.
Adopt and the similar purifying platform of Fig. 1 purification of carbon dioxide, test.The situation of feed carbon dioxide is as follows:
25 ℃ of temperature
Flow 109.7 standard cubic meters/hour
H
2S 5-9ppm
COS 5ppm
Benzene 2.5ppm
Methyl alcohol 160ppm
Acetaldehyde 11ppm
The oxygen ratio is removed H
2The required amount of S, COS, benzene, acetaldehyde and methyl alcohol is about 50ppm how.
Reaction of Salmon-Saxl device bed is 100 ℃ of operations, and contains 17.1 kilograms of activated carbon that flood 20 weight % potash.Catalytic reactor bed is moved down at 250 ℃, and comprises the catalyst of palladium coating.
Described device moved more than 1 week, used the gas-chromatography that comprises FID and FPD detector and sample concentrator that product is analyzed.In test process, the total sulfur content in the product that sulfur removal bed 40 is discharged keeps below 0.05ppm, and the content of benzene, methyl alcohol and acetaldehyde all is lower than the detection lower limit of instrument, respectively less than 10ppb.Sample concentrator based on absorption has increased more than 100 times the concentration of hydrocarbon impurity, has obviously improved the detection limit value of these impurity.
In order to detect among Fig. 1 the operation of device 80, make pressure be 14.6 crust, temperature be 25 ℃ the feed carbon dioxide that contains 145ppm methyl alcohol with the flow velocity of 19.8 standard liter/min by containing the bed of 0.295 kilogram of 6 * 8 order NaY zeolite.Do not observe methanol crossover (breakthrough) (in the product＜1ppm methyl alcohol) in 170 hours, obtain the methyl alcohol balancing capacity (equilibrium capacity) of 16.4 weight %.
Though described the present invention with reference to plurality of embodiments and embodiment, those skilled in the art can carry out various changes, interpolation and omission under the situation that does not deviate from spirit and scope of the invention.
Claims (37)
1. the equipment of a purified gas stream, it comprises:
Primary heater/heat-exchange device;
Desulfurizing device;
Secondary heater/heat-exchange device;
The reactor beds device;
Cooling/heat-exchange device;
The adsorption and purification device; With
Gas concentration unit.
2. equipment as claimed in claim 1 is characterized in that described air-flow comprises carbon dioxide.
3. equipment as claimed in claim 1 is characterized in that, described desulfurizing device comprises reaction of Salmon-Saxl device bed.
4. equipment as claimed in claim 3 is characterized in that, described sulphur bed contains and H
2S and COS catalyst for reaction.
5. equipment as claimed in claim 4, it is characterized in that described catalyst is selected from down group: carbonate and hydroxide, the carbonate on the activated carbon, on the activated alumina carbonate, metal oxide, load on metal oxide and CuY zeolite in the micro-porous adsorption agent.
6. equipment as claimed in claim 1 is characterized in that, described reactor beds is particle or one piece reactor beds.
7. equipment as claimed in claim 1 is characterized in that, described one piece reactor beds contains one or more catalyst materials.
8. equipment as claimed in claim 1 is characterized in that, described adsorption and purification device is one or more sorbing materials.
9. equipment as claimed in claim 8 is characterized in that described activated alumina and 13X are stacked together mutually.
10 equipment as claimed in claim 9 is characterized in that described equipment also comprises the NaY zeolite adsorbents.
11. equipment as claimed in claim 8 is characterized in that, being shaped as bead, particle, powder, netted, ring-type, monolithic or extruding shape of described sorbing material.
12. equipment as claimed in claim 1 is characterized in that, described adsorption and purification device comprises activated carbon.
13. equipment as claimed in claim 1 is characterized in that, described air scavenge device comprises valving, is used for guiding gas into manufacturing, cleaning, encapsulation, storage or filling process or device.
14. equipment as claimed in claim 1 is characterized in that, this equipment also comprises the gas analyzing apparatus that is used for sulphur and hydrocarbon impurity.
15. equipment as claimed in claim 1 is characterized in that, this equipment also comprise from described gas remove degerm, agricultural chemicals and heavy metal.
16. the method for a purified gases, this method may further comprise the steps:
A) gas is imported primary heater/heat exchanger, the temperature of rising gas;
B) will be from the gas of step a) input desulfurizing device, to form substantially the not gas of sulfur-bearing;
C) will be substantially the gas of sulfur-bearing input secondary heater/heat exchanger not, thereby the temperature of rising gas;
D) with described gas input reactor bed, to remove impurity;
E), reduce the temperature of gas with described gas input cooling/heat-exchange device;
F) with described gas input adsorption and purification device; With
G) with in described gas input manufacturing, cleaning, can, storage, mixing or packaging technology or the device.
17. method as claimed in claim 16 is characterized in that, described gas comprises carbon dioxide.
18. method as claimed in claim 16 is characterized in that, described desulfurizing device comprises reaction of Salmon-Saxl device bed.
19. method as claimed in claim 18 is characterized in that, described sulphur bed contains and H
2S and COS catalyst for reaction.
20. method as claimed in claim 19, it is characterized in that described catalyst is selected from down group: carbonate and hydroxide, the carbonate on the activated carbon, on the activated alumina carbonate, metal oxide, load on metal oxide and CuY zeolite in the micro-porous adsorption agent.
21. method as claimed in claim 16 is characterized in that, described reactor beds is particle or one piece reactor beds.
22. method as claimed in claim 16 is characterized in that, described single blocks formula reactor beds contains one or more catalyst materials.
23. method as claimed in claim 16 is characterized in that, described adsorption and purification device is activated alumina and 13X zeolite.
24. method as claimed in claim 23 is characterized in that, this method also comprises the NaY zeolite adsorbents.
25. method as claimed in claim 23 is characterized in that, described sorbing material be shaped as the bead shape.
26. method as claimed in claim 24 is characterized in that, described adsorption and purification device also comprises activated carbon.
27. method as claimed in claim 16 is characterized in that, described air scavenge device comprises valving, is used for guiding described gas into production process or deposit place, perhaps guides both simultaneously into.
28. method as claimed in claim 16 is characterized in that, this method also comprises gas analyzing apparatus.
29. method as claimed in claim 16 is characterized in that, this method also comprise from carbon dioxide remove degerm, agricultural chemicals and heavy metal.
30. a method of handling carbon dioxide, this method may further comprise the steps:
A) with impure carbon dioxide air-flow input reaction of Salmon-Saxl device bed, remove the sulfur-containing compound that exists in the carbon dioxide gas stream, form substantially the not carbon dioxide gas stream of sulfur-bearing;
B) with the described carbon dioxide gas stream input reactor bed of sulfur-bearing not substantially, thereby remove the hydrocarbon compound that exists in the carbon dioxide gas stream, form the carbon dioxide gas stream that does not contain hydrocarbon compound substantially;
C), form the carbon dioxide stream of substantially dry with described carbon dioxide stream input drier and/or the adsorbent bed that does not contain hydrocarbon compound substantially;
D) impurity in the carbon dioxide stream is concentrated,, measure any impurity that exists in the carbon dioxide gas stream of substantially dry the carbon dioxide gas stream input analysis platform of substantially dry;
E) purified carbon dioxide streams is imported in manufacture process or the carbon dioxide storage tank, perhaps imported both simultaneously.
31. method as claimed in claim 30 is characterized in that, described processing comprises carries out purifying to carbon dioxide.
32. method as claimed in claim 30 is characterized in that, described processing comprises the analysis carbon dioxide.
33. method as claimed in claim 30 is characterized in that, described processing is that carry out at the scene.
34. method as claimed in claim 30 is characterized in that, described desulfurizing device comprises reaction of Salmon-Saxl device bed.
35. method as claimed in claim 34 is characterized in that, described sulphur bed contains and H
2S and COS catalyst for reaction.
36. method as claimed in claim 35, it is characterized in that described catalyst is selected from down group: carbonate and hydroxide, the carbonate on the activated carbon, on the activated alumina carbonate, metal oxide, load on metal oxide and CuY zeolite in the micro-porous adsorption agent.
37. method as claimed in claim 30 is characterized in that, described carbon dioxide remover comprises valving, is used for guiding carbon dioxide into production process or deposit place, perhaps guides both simultaneously into.
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| CN102596368A (en) * | 2009-08-21 | 2012-07-18 | 布莱恩·杨大学 | Off gas purification |
| CN106537115A (en) * | 2014-02-14 | 2017-03-22 | 可口可乐公司 | System and method for continuous, real-time monitoring of chemical contaminants in carbon dioxide |
| JP2019063778A (en) * | 2017-10-05 | 2019-04-25 | 住友精化株式会社 | Catalytic oxidation system, and purification method of carbon dioxide |
| CN109813797A (en) * | 2019-04-13 | 2019-05-28 | 中国烟草总公司郑州烟草研究院 | The rapid detection method of sulphur compound in a kind of cigarette mainstream flue gas |
| CN110376087A (en) * | 2018-04-11 | 2019-10-25 | 堀场仪器（上海）有限公司 | It is a kind of for determining the method and system of the performance rate of activated carbon canister |
| CN111333037A (en) * | 2020-04-15 | 2020-06-26 | 大连科利德光电子材料有限公司 | System and method for preparing high-purity hydrogen sulfide gas |
| CN111650007A (en) * | 2020-06-12 | 2020-09-11 | 云南省能源研究院有限公司 | Carbon dioxide online sampling analysis method |
| CN114563520A (en) * | 2022-02-23 | 2022-05-31 | 中国计量大学 | Device for detecting carbon dioxide adsorption capacity in laboratory |
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- 2006-08-08 CN CN 200680033062 patent/CN101262926A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102596368A (en) * | 2009-08-21 | 2012-07-18 | 布莱恩·杨大学 | Off gas purification |
| CN106537115A (en) * | 2014-02-14 | 2017-03-22 | 可口可乐公司 | System and method for continuous, real-time monitoring of chemical contaminants in carbon dioxide |
| JP2019063778A (en) * | 2017-10-05 | 2019-04-25 | 住友精化株式会社 | Catalytic oxidation system, and purification method of carbon dioxide |
| JP7017897B2 (en) | 2017-10-05 | 2022-02-09 | 住友精化株式会社 | Catalyzed oxidation system and carbon dioxide purification method |
| CN110376087A (en) * | 2018-04-11 | 2019-10-25 | 堀场仪器（上海）有限公司 | It is a kind of for determining the method and system of the performance rate of activated carbon canister |
| CN109813797A (en) * | 2019-04-13 | 2019-05-28 | 中国烟草总公司郑州烟草研究院 | The rapid detection method of sulphur compound in a kind of cigarette mainstream flue gas |
| CN109813797B (en) * | 2019-04-13 | 2021-07-06 | 中国烟草总公司郑州烟草研究院 | Rapid detection method for sulfur compounds in cigarette mainstream smoke |
| CN111333037A (en) * | 2020-04-15 | 2020-06-26 | 大连科利德光电子材料有限公司 | System and method for preparing high-purity hydrogen sulfide gas |
| CN111333037B (en) * | 2020-04-15 | 2022-11-11 | 大连科利德光电子材料有限公司 | System and method for preparing high-purity hydrogen sulfide gas |
| CN111650007A (en) * | 2020-06-12 | 2020-09-11 | 云南省能源研究院有限公司 | Carbon dioxide online sampling analysis method |
| CN114563520A (en) * | 2022-02-23 | 2022-05-31 | 中国计量大学 | Device for detecting carbon dioxide adsorption capacity in laboratory |
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