CA2058132A1 - Process and apparatus for effecting regenerative sulfur binding - Google Patents
Process and apparatus for effecting regenerative sulfur bindingInfo
- Publication number
- CA2058132A1 CA2058132A1 CA002058132A CA2058132A CA2058132A1 CA 2058132 A1 CA2058132 A1 CA 2058132A1 CA 002058132 A CA002058132 A CA 002058132A CA 2058132 A CA2058132 A CA 2058132A CA 2058132 A1 CA2058132 A1 CA 2058132A1
- Authority
- CA
- Canada
- Prior art keywords
- sorbent
- reactor
- chamber
- duct
- regeneration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000011593 sulfur Substances 0.000 title claims abstract description 65
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 47
- 230000008569 process Effects 0.000 title claims abstract description 42
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 9
- 238000009739 binding Methods 0.000 title description 23
- 230000027455 binding Effects 0.000 title description 22
- 239000002594 sorbent Substances 0.000 claims abstract description 95
- 239000007789 gas Substances 0.000 claims abstract description 87
- 230000008929 regeneration Effects 0.000 claims abstract description 73
- 238000011069 regeneration method Methods 0.000 claims abstract description 73
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 22
- 230000023556 desulfurization Effects 0.000 claims abstract description 22
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 238000012545 processing Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims description 7
- 239000002826 coolant Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 229910002065 alloy metal Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 239000011236 particulate material Substances 0.000 claims 2
- 229960005349 sulfur Drugs 0.000 description 40
- 235000001508 sulfur Nutrition 0.000 description 40
- 239000007787 solid Substances 0.000 description 14
- 230000032258 transport Effects 0.000 description 10
- 238000000926 separation method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000005587 bubbling Effects 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/06—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds
- B01D53/10—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds with dispersed adsorbents
- B01D53/12—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds with dispersed adsorbents according to the "fluidised technique"
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3433—Regenerating or reactivating of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/56—Use in the form of a bed
Abstract
Abstract The invention relates to a process and an apparatus for the regenerative desulfurization of process gases by means of a recycle mass. In the process and appar-atus, the sulfur-containing gases are contacted with a particulate sorbent material forming a fluidized bed and conveyed together with the sorbent material through a reaction zone to bind the sulfur to the sorbent, and the sulfur-bearing sorbent is separated from the process gas which is conveyed into further processing, whereafter the sulfur-bearing sorbent is conveyed into regeneration to separate the sulfur from the sorbent, the sulfur separated from the sor-bent is conveyed into further processing, and the sorbent freed of sulfur is returned into contact with the process gas. The invention is characterized in that the sulfur-bearing sorbent which has been separated from the process gas is cooled in a return duct prior to being conveyed into regeneration for regulating the temperature of both the recycle mass and the reactor.
(Figure 1)
(Figure 1)
Description
2~132 Process and apparatus for effecting regenerative sul-fur binding The present invention relates to a process for the regenerative desulfurization of process gases by means of a recycle mass, in which process the sulfur-containing gases are contacted with a particulate sorbent material forming a fluidized bed and conveyed together with the sorbent material through a reaction zone to bind the sulfur to the sorbent, and the sul-fur-bearing sorbent is separated from the process gas which is conveyed into further processing, whereafter the sulfur-bearing sorbent is conveyed into regener-ation to separate the sulfur from the sorbent, the sulfur separated from the sorbent is conveyed into further processing, and the sorbent freed of sulfur is returned into contact with the process gas.
The invention further relates to an apparatus comprising a desulfurization reactor having a flui-dized bed chamber which contains a fluidized bedformed by particulate sorbent and into which the pro-cess gas is conveyed, a reactor chamber above the fluidized bed chamber, separator means in the top portion of the reactor chamber for separating the sulfur-bearing sorbent from the process gas, an exhaust duct for discharging the process gas, a regeneration reactor, at least one transport duct for conveying the sulfur-bearing sorbent to the regener-ation reactor, a duct for conveying regenerating gas and separated sulfur out from the regeneration reac-tor, and a return duct for returning the sorbent from the bottom portion of the regeneration reactor to the fluidized bed.
A central problem of desulfurization processes based on direct binding of sulfur, for instance on 3 ~
calcium, is the high amount of waste produced. When, moreover, the water-soluble compounds of the produced waste constitute a hazard to the groundwaters of waste dumping areas, it is evident that in the long term, processes must be developed wherein the amount of waste produced is minimized.
Nowadays a large number of processes for bind-ing sulfur oxides are known, wherein the final bind-ing takes place as solid phase elemental sulfur. In principle, as an intermediate step of all such pro-cesses, the sulfur oxide content must first be con-centrated to be sufficiently high, in order for the production process of elemental sulfur to be econ-omically feasible. In the concentration process, the sulfur oxides are first bound to a sorbent having suitable properties, which is regenerated, in which case sulfur is liberated and a sorbent capable of binding sulfur is produced. The binding of sulfur and the regeneration of the sulfur-bearing sorbent are then effected in separate reactors between which the sorbent is transported in such a way that the sulfur-bearing sorbent is transported to a regeneration reactor and correspondingly the regenerated sorbent is transported to a sulfur binding reactor simultane-ously as the purified gas is removed from the reactor and sulfur is removed separately from the regener-ator. The transport of the sorbent must be effected in a stable manner and so that mixing of gaseous com-pounds between the reactors is small.
Nowadays apparatus based on the solid bed and fluidized bed technique for implementing regenerative sulfur bi.nding processes are under development. Since the temperature control is very important in regener-ative desulfurization, the prospects of the solid bed technique do not seem promising, since its temperat-~8~32 ure adjustment and reaction control are difficult to regulate. From the point of view of effective mass transport, it would also be important that a finely divided sorbent could be used, which will be diffi-S cult in a solid bed reactor. Correspondingly, obtain-ing a sufficient quantity of recycle mass and a suf-ficient separation capacity requires sufficient room, wherefore the diameters of reactors based on the fluidized bed technique are large. Since, however, the gas quantity of the regeneration reactor is typi-cally only l - 3% of the gas stream of the sulfur binding reactor, the problem of the large diameter is primarily related with the sulfur binding reactor.
The object of the present invention is to pro-vide a process and an apparatus wherewith the above-stated drawbacks can be eliminated. The process of the invention is characterized in that the sulfur-bearing sorbent which has been separated from the process gas is cooled prior to being conveyed into regeneration for regulating the temperature of both the recycle mass and the reactor.
The apparatus of the invention is characterized in that the reactor chamber has a smaller cross-sec-tion in the flow direction of the gas than the fluid-ized bed chamber has, and that the transport duct conveying the sulfur-bearing sorbent to the regen-eration reactor has a heat exchanger for regulating the temperatures of the sorbent and thereby the entire reactor.
Thus, in the process of the invention, the sul-fur binding ta~es place in a recycle mass reactor, in which situation a finely divided sorbent, such as metal oxides or preferably an alloy metal oxide, such as zinc ferrite oxide (~ 0.05 - 0.3 mm), and a fair gas velocity (3 6 m/s) can be used, in which case 2~8~3~
the diameter of the sulfur bind~ng reactor is not inordinately large. If bubbling fluidized bed techni-que were used, the gas velocity should be restricted below 0.5 m/s with said sorbent size. The gas stream of the regeneration reactor is typically only 1 - 3%
of the gas stream of the sulfur binding reactor, wherefore the diameter of the regeneration reactor will not be large, even though the gas velocity therein is restricted to the velocity range of a bubbling fluidized bed, that is, to a velocity of about 1 m/s.
The stabilizing of the temperature of the sul-fur binding reactor is effected in accordance with the essential concept of the invention in such a man-ner that the cooling surfaces are mainly arranged inthe return or recycle duct for recycle mass, in which event the flow of solids passing through the cooler, and thereby the efficiency of the cooler, will be automatically adjusted in accordance with the gas stream to be processed. Further, the -temperature may be regulated, if necessary, by using a separate re-cycle gas stream for regulating the efficiency of the cooler.
The way of controlling the streams of solids between the reactors is also essential to the inven-tion. This is accomplished by means of pulse feeders, the principle of operation of which is the following:
a plug-like layer, i.e. solids layer zone, is arran-ged at the outset of the pulse feeder, from the lower portion of which solids are transported by means of pulse-like gas feeds in the pneumatically most suit-able way. Controlled recycling of the solids between the sulfur binding reactor and the regeneration reac-tor is achieved by connecting the desulfurization reactor by means of a pulse feeder to the regener-ation reactor, and vice versa.
In the following, the invention will be explai-ned in more detail with reference to the accompanying drawings, wherein Figures 1 and la represent schematically a re-cycle mass reactor of the invention, and Figure 2 shows another embodiment of the re-cycle mass reactor of the invention partially cut open.
The recycle mass reactor shown in the figure comprises a sulfur binding reactor having a jetting base 1 through which the gas to be processed and the possible recycle gas are conveyed to a fluidized bed chamber 2 located in the lower portion of the recycle mass reactor. The lower portion of the reactor, i.e.
the fluidized bed chamber 2, is preferably larger in cross-section in the flow direction of the gas than the actual reactor chamber 3 located above it. Then a high particle density can be maintained in the lower portion without the particle density in the entire reactor space being unduly increased. In the annular reactor chamber 3 shown in the figure, the gases and the sorbent are conveyed upwards in the reactor as a suspension and arrive at a cyclone vane grate A dis-posed in the upper portion of the recycle mass reac-tor, the vanes of which serve as separator means and flow guides. Herein the suspension is conveyed tan-gentially to a cyclone chamber 5 wherein the sorbent particles are separated from the gas. The gas puri-fied of particles is conveyed into further proces-sing through a discharge duct, i.e. tube 6, in the centre of the cyclone, and the particulate mass separated onto the walls of the cyclone falls into a distribution chamber 7 disposed below the baffle plate. The purpose of the distribution chamber 7 is 3 ~
to distribute the recycled particulate mass evenly on the cross-sectional surface of the cooling member, i.e. heat exchanger 9, which is disposed symmetri-cally in the axial direction. This is achieved with a suitably shaped jet plate 8. Figure la presents sche-matically the cross-section of the reactor at point A
- A, showing how the reactor is constructed. The heat exchanger in the centre of the reactor is of a recu-perative mode of operation. The heat exchanger 9 has several return ducts or heat sxchanger ducts 9a through which the recycle mass is returned through the cooler 9 to the lower portion thereof. There is a space therebetween wherefrom a cooling medium such as gas, air, water, other liquid or steam/vapour f lows from the lower end of the cooler through duct 11 to the upper end thereof countercurrently to the direc-tion of travel of the recycle mass, cooling the outer surface of the ducts 9a and thereby the recycle mass flowing within them.
To guide the gas stream of the recycle mass reactor, a bottom cone 10 has been disposed at the lower end of the cooler 9, the free end of the cone being not more than 10% of the cross-section of the annular space 3. The inlet and outlet ducts for the cooling stream of gas or other medium to the cooler have been indicated with numerals 11 and 12.
In Figure 1, the regeneration reactor 13 has been disposed annularly about the sulfur binding reactor 3. The inlet tubes for regeneration gas, such as steam or other suitable gas, have been denoted with reference numeral 14, reference numeral 13 indi-cates the annular regeneration chamber, and reference numeral 20 indicates the tube for the sulfur-contain-ing gas exiting from the regeneration. From the lower portion of the heat exchanger, a transport duct, i.e.
~ ~ ~ 8 3L G~ 2 a tube 16, leads to the upper portion of the regener-ation reactor 13, the cooler 9 end of said tube in-cluding a vertical forward part 15 wherein the sul-fur-bearing sorbent forms a plug-like layer. Through the adjoining horizontal tube part 16 and a gas duct 19 at the corner of said horizontal tube 16 forming an extension thereof, the transport gas - which is fed preferably in a pulse-like manner - conveys the sulfur-bearing sorbent through tube 16 to the regeneration reactor 13. Reference numeral 17 indi-cates a return duct for regenerated sorbent, connec-ted to the lower portion of the regeneration reac-tor, the regenerated sorbent forming another plug-like layer in the vertical part at the forward end of said return duct, wherefrom the gas - again preferably supplied in a pulse-like manner through a tube 18 - transports the sorbent to the sulfur binding reactor. The plug-like solids layer serving as sealing is produced by flowing solids into the substantially vertical tube 15 or 17 of the conveyor passage, in which tube the level of solids is main-tained sufficiently high above the horizontal part of the con~eyor tube. If no gas is supplied to the con-veyor tube through tube 19 or 18, the flow of solids stops, since the solids cannot travel by themselves in the substantially horizontal conveyor tube. If gas is supplied to the conveyor tube, the sorbent layer in the vertical tube starts flowing downward in a plug-like manner while the lowest part thereof is removed together with the gas, in which situation its gas tightness will remain intact. A solicls conveyor tube is connected to the lower end of the vertical tube part, wherein the solids are conveyed pneumati-cally with a suitable carrier gas by means of ei-ther continuous gas flow or gas pulses.
2 ~ 2 In the sulfur binding reactor, the typical gas velocity calculated for the entire cross-section 3 varies within the range 3 - 6 m/s. In the sulfur binding reactor, the suspension density in the lower portion is most suitably in the range 50 - 300 kg/m3, and in the upper portion 5 - 30 kg/m3. The temperature range is determined in accordance with the chemical kinetics of the binding reaction and typically varies within the range 450 - 1050~C. It is essential that with the use of recycle mass technology, the temper-ature can be set at the desired value in the entire volume of the binding reactor.
In the regeneration reactor wherein the gas stream is very small in comparison with the gas stream of the sulfur binding reactor, one can natur-ally employ a very low gas velocity, without its essentially adding to the outer dimensions of the apparatus. An advantageous solution in the apparatus-technical sense is to dispose the regeneration reac-tor in accordance with Figure 1 rotation-symmetri-cally about the sulfur binding reactor. A suitable gas velocity in the regeneration reactor is 0.2 - 1.0 m/s with a finely divided sorbent. The mean density of the suspension zone of a fluidized bed reactor operating in a bubbling state is preferably 100 - 500 kg/m3. The temperature is determined in accordance with the kinetics of the regeneration reaction and varies within the range 700 - 1300C. The temperature range of the regeneration reactor is rather narrow with most sorbents, wherefore it must also be pos-sible to regulate the temperature of the regeneration reactor accurately. Since the released heat energy is rather low, the fine adjustment of the temperature may be performed by a direct method based on steam-ing. In most cases, water is the most advantageous 2Q~i8~ 32 coolant.
Figure 2 shows schematically another embodiment of the reactor according to the invention partly cut open. In Figure 2, the actual desulfurization reac-tor, wherein the sulfurous gases are supplied to thereactor via duct 1, is shown on the right. Therefrom they are further conveyed to the fluidized bed cham-ber 2 wherein they flow through the fluidized bed material and flow further through the annular duct 3 to the upper portion of the reactor, wherefrom it is turned, guided by the flow guide 4, i.e. vane grate, to the separation chamber 5 wherein the recycle material, i.e. the sulfur-bearing sorbent material is separated from the gases. The gases are exhausted in the manner shown in Figure 1 through duct 6 from the centre of the separation chamber 5, and the sorbent material falls from the separation chamber downward and through recycle duct 5a falls again into the chamber 2. Part of the sorbent material falls into the vertical discharge duct 15 and further therefrom into the horizontal part 16 of the discharge duct, wherefrom it is transported into the regeneration reactor by means of the conveyor gas supplied through duct 19. The regeneration reactor ln principle oper-ates similarly as the desulfurization reactor, regen-eration gas and/or steam being fed into the lower portion of the regeneration reactor through duct 14, in which situation the regeneration gas and/or steam enters the chamber 13' which is preferably a fluid-ized bed chamber, and flows further through itsannular part, i.e. the regeneration chamber 13a, to the upper portion of the reactor and again arrives in the separation chamber 5' guided by the vane grate 4'. In the separation chamber, the regenerated sor-bent is separated from the regeneration gas and 2~1~i8~32 steam, which entrains the sulfur via duct 20 locatedin the centre of the chamber upon discharging. In chamber 5', the separated sorbent material further falls downward through another recycle duct 5a' back into the chamber 13' and again comes into contact with the regeneration gas or steam. However, part of the regenerated material again falls into the return duct, i.e. tube 15', and further into the horizontal part 17 in the lower portion thereof, through which the regenerated sorbent is conveyed to the chamber of the desulfurization reactor by supplying transport gas which carries the sorbent material through duct 18. In the solution of Figure 2, heat exchangers have been disposed about the hori7ontal transport duct, i.e. tube 16, leading from the desulfurization reac-tor to the regeneration reactor, as well as about the return duct, i.e. tube 17, for the sorbent. Cooling medium is conveyed to the heat exchanger 21 disposed about the transport duct 16 through tube 22, and it is discharged through tube 23, that is, the heat ex-changer operates on the countercurrent principle.
Correspondingly, cooling medium is conveyed to the heat exchanger disposed about the return duct 17 through tube 22', and it is removed through tube 23', likewise on the countercurrent principle. Further, in Figure 2 there is a heat exchanger or cooler 24 and 24' about the desulfurization reactor and the regen-eration reactor, through which heat exchangers or coolers a heat exchanger medium is conveyed through tubes 11, 11' and 12, 12'.
In the foregoing description and drawings, the invention has been set forth only by way of example, and it is in no way bound to said description and drawings. Except for a reactor arrangement construc-ted as one unit and a fixed entity, separate arrange-2 ~ 3 ~
ments may be used in the manner shown in Figure 2, inwhich event the desulfurization reactor can be con-structed to be as efficient as possible in view of desulfurization, and the regeneration reactor can be constructed to be of another type and as efficient as possible specifically in view of regeneration.
The invention further relates to an apparatus comprising a desulfurization reactor having a flui-dized bed chamber which contains a fluidized bedformed by particulate sorbent and into which the pro-cess gas is conveyed, a reactor chamber above the fluidized bed chamber, separator means in the top portion of the reactor chamber for separating the sulfur-bearing sorbent from the process gas, an exhaust duct for discharging the process gas, a regeneration reactor, at least one transport duct for conveying the sulfur-bearing sorbent to the regener-ation reactor, a duct for conveying regenerating gas and separated sulfur out from the regeneration reac-tor, and a return duct for returning the sorbent from the bottom portion of the regeneration reactor to the fluidized bed.
A central problem of desulfurization processes based on direct binding of sulfur, for instance on 3 ~
calcium, is the high amount of waste produced. When, moreover, the water-soluble compounds of the produced waste constitute a hazard to the groundwaters of waste dumping areas, it is evident that in the long term, processes must be developed wherein the amount of waste produced is minimized.
Nowadays a large number of processes for bind-ing sulfur oxides are known, wherein the final bind-ing takes place as solid phase elemental sulfur. In principle, as an intermediate step of all such pro-cesses, the sulfur oxide content must first be con-centrated to be sufficiently high, in order for the production process of elemental sulfur to be econ-omically feasible. In the concentration process, the sulfur oxides are first bound to a sorbent having suitable properties, which is regenerated, in which case sulfur is liberated and a sorbent capable of binding sulfur is produced. The binding of sulfur and the regeneration of the sulfur-bearing sorbent are then effected in separate reactors between which the sorbent is transported in such a way that the sulfur-bearing sorbent is transported to a regeneration reactor and correspondingly the regenerated sorbent is transported to a sulfur binding reactor simultane-ously as the purified gas is removed from the reactor and sulfur is removed separately from the regener-ator. The transport of the sorbent must be effected in a stable manner and so that mixing of gaseous com-pounds between the reactors is small.
Nowadays apparatus based on the solid bed and fluidized bed technique for implementing regenerative sulfur bi.nding processes are under development. Since the temperature control is very important in regener-ative desulfurization, the prospects of the solid bed technique do not seem promising, since its temperat-~8~32 ure adjustment and reaction control are difficult to regulate. From the point of view of effective mass transport, it would also be important that a finely divided sorbent could be used, which will be diffi-S cult in a solid bed reactor. Correspondingly, obtain-ing a sufficient quantity of recycle mass and a suf-ficient separation capacity requires sufficient room, wherefore the diameters of reactors based on the fluidized bed technique are large. Since, however, the gas quantity of the regeneration reactor is typi-cally only l - 3% of the gas stream of the sulfur binding reactor, the problem of the large diameter is primarily related with the sulfur binding reactor.
The object of the present invention is to pro-vide a process and an apparatus wherewith the above-stated drawbacks can be eliminated. The process of the invention is characterized in that the sulfur-bearing sorbent which has been separated from the process gas is cooled prior to being conveyed into regeneration for regulating the temperature of both the recycle mass and the reactor.
The apparatus of the invention is characterized in that the reactor chamber has a smaller cross-sec-tion in the flow direction of the gas than the fluid-ized bed chamber has, and that the transport duct conveying the sulfur-bearing sorbent to the regen-eration reactor has a heat exchanger for regulating the temperatures of the sorbent and thereby the entire reactor.
Thus, in the process of the invention, the sul-fur binding ta~es place in a recycle mass reactor, in which situation a finely divided sorbent, such as metal oxides or preferably an alloy metal oxide, such as zinc ferrite oxide (~ 0.05 - 0.3 mm), and a fair gas velocity (3 6 m/s) can be used, in which case 2~8~3~
the diameter of the sulfur bind~ng reactor is not inordinately large. If bubbling fluidized bed techni-que were used, the gas velocity should be restricted below 0.5 m/s with said sorbent size. The gas stream of the regeneration reactor is typically only 1 - 3%
of the gas stream of the sulfur binding reactor, wherefore the diameter of the regeneration reactor will not be large, even though the gas velocity therein is restricted to the velocity range of a bubbling fluidized bed, that is, to a velocity of about 1 m/s.
The stabilizing of the temperature of the sul-fur binding reactor is effected in accordance with the essential concept of the invention in such a man-ner that the cooling surfaces are mainly arranged inthe return or recycle duct for recycle mass, in which event the flow of solids passing through the cooler, and thereby the efficiency of the cooler, will be automatically adjusted in accordance with the gas stream to be processed. Further, the -temperature may be regulated, if necessary, by using a separate re-cycle gas stream for regulating the efficiency of the cooler.
The way of controlling the streams of solids between the reactors is also essential to the inven-tion. This is accomplished by means of pulse feeders, the principle of operation of which is the following:
a plug-like layer, i.e. solids layer zone, is arran-ged at the outset of the pulse feeder, from the lower portion of which solids are transported by means of pulse-like gas feeds in the pneumatically most suit-able way. Controlled recycling of the solids between the sulfur binding reactor and the regeneration reac-tor is achieved by connecting the desulfurization reactor by means of a pulse feeder to the regener-ation reactor, and vice versa.
In the following, the invention will be explai-ned in more detail with reference to the accompanying drawings, wherein Figures 1 and la represent schematically a re-cycle mass reactor of the invention, and Figure 2 shows another embodiment of the re-cycle mass reactor of the invention partially cut open.
The recycle mass reactor shown in the figure comprises a sulfur binding reactor having a jetting base 1 through which the gas to be processed and the possible recycle gas are conveyed to a fluidized bed chamber 2 located in the lower portion of the recycle mass reactor. The lower portion of the reactor, i.e.
the fluidized bed chamber 2, is preferably larger in cross-section in the flow direction of the gas than the actual reactor chamber 3 located above it. Then a high particle density can be maintained in the lower portion without the particle density in the entire reactor space being unduly increased. In the annular reactor chamber 3 shown in the figure, the gases and the sorbent are conveyed upwards in the reactor as a suspension and arrive at a cyclone vane grate A dis-posed in the upper portion of the recycle mass reac-tor, the vanes of which serve as separator means and flow guides. Herein the suspension is conveyed tan-gentially to a cyclone chamber 5 wherein the sorbent particles are separated from the gas. The gas puri-fied of particles is conveyed into further proces-sing through a discharge duct, i.e. tube 6, in the centre of the cyclone, and the particulate mass separated onto the walls of the cyclone falls into a distribution chamber 7 disposed below the baffle plate. The purpose of the distribution chamber 7 is 3 ~
to distribute the recycled particulate mass evenly on the cross-sectional surface of the cooling member, i.e. heat exchanger 9, which is disposed symmetri-cally in the axial direction. This is achieved with a suitably shaped jet plate 8. Figure la presents sche-matically the cross-section of the reactor at point A
- A, showing how the reactor is constructed. The heat exchanger in the centre of the reactor is of a recu-perative mode of operation. The heat exchanger 9 has several return ducts or heat sxchanger ducts 9a through which the recycle mass is returned through the cooler 9 to the lower portion thereof. There is a space therebetween wherefrom a cooling medium such as gas, air, water, other liquid or steam/vapour f lows from the lower end of the cooler through duct 11 to the upper end thereof countercurrently to the direc-tion of travel of the recycle mass, cooling the outer surface of the ducts 9a and thereby the recycle mass flowing within them.
To guide the gas stream of the recycle mass reactor, a bottom cone 10 has been disposed at the lower end of the cooler 9, the free end of the cone being not more than 10% of the cross-section of the annular space 3. The inlet and outlet ducts for the cooling stream of gas or other medium to the cooler have been indicated with numerals 11 and 12.
In Figure 1, the regeneration reactor 13 has been disposed annularly about the sulfur binding reactor 3. The inlet tubes for regeneration gas, such as steam or other suitable gas, have been denoted with reference numeral 14, reference numeral 13 indi-cates the annular regeneration chamber, and reference numeral 20 indicates the tube for the sulfur-contain-ing gas exiting from the regeneration. From the lower portion of the heat exchanger, a transport duct, i.e.
~ ~ ~ 8 3L G~ 2 a tube 16, leads to the upper portion of the regener-ation reactor 13, the cooler 9 end of said tube in-cluding a vertical forward part 15 wherein the sul-fur-bearing sorbent forms a plug-like layer. Through the adjoining horizontal tube part 16 and a gas duct 19 at the corner of said horizontal tube 16 forming an extension thereof, the transport gas - which is fed preferably in a pulse-like manner - conveys the sulfur-bearing sorbent through tube 16 to the regeneration reactor 13. Reference numeral 17 indi-cates a return duct for regenerated sorbent, connec-ted to the lower portion of the regeneration reac-tor, the regenerated sorbent forming another plug-like layer in the vertical part at the forward end of said return duct, wherefrom the gas - again preferably supplied in a pulse-like manner through a tube 18 - transports the sorbent to the sulfur binding reactor. The plug-like solids layer serving as sealing is produced by flowing solids into the substantially vertical tube 15 or 17 of the conveyor passage, in which tube the level of solids is main-tained sufficiently high above the horizontal part of the con~eyor tube. If no gas is supplied to the con-veyor tube through tube 19 or 18, the flow of solids stops, since the solids cannot travel by themselves in the substantially horizontal conveyor tube. If gas is supplied to the conveyor tube, the sorbent layer in the vertical tube starts flowing downward in a plug-like manner while the lowest part thereof is removed together with the gas, in which situation its gas tightness will remain intact. A solicls conveyor tube is connected to the lower end of the vertical tube part, wherein the solids are conveyed pneumati-cally with a suitable carrier gas by means of ei-ther continuous gas flow or gas pulses.
2 ~ 2 In the sulfur binding reactor, the typical gas velocity calculated for the entire cross-section 3 varies within the range 3 - 6 m/s. In the sulfur binding reactor, the suspension density in the lower portion is most suitably in the range 50 - 300 kg/m3, and in the upper portion 5 - 30 kg/m3. The temperature range is determined in accordance with the chemical kinetics of the binding reaction and typically varies within the range 450 - 1050~C. It is essential that with the use of recycle mass technology, the temper-ature can be set at the desired value in the entire volume of the binding reactor.
In the regeneration reactor wherein the gas stream is very small in comparison with the gas stream of the sulfur binding reactor, one can natur-ally employ a very low gas velocity, without its essentially adding to the outer dimensions of the apparatus. An advantageous solution in the apparatus-technical sense is to dispose the regeneration reac-tor in accordance with Figure 1 rotation-symmetri-cally about the sulfur binding reactor. A suitable gas velocity in the regeneration reactor is 0.2 - 1.0 m/s with a finely divided sorbent. The mean density of the suspension zone of a fluidized bed reactor operating in a bubbling state is preferably 100 - 500 kg/m3. The temperature is determined in accordance with the kinetics of the regeneration reaction and varies within the range 700 - 1300C. The temperature range of the regeneration reactor is rather narrow with most sorbents, wherefore it must also be pos-sible to regulate the temperature of the regeneration reactor accurately. Since the released heat energy is rather low, the fine adjustment of the temperature may be performed by a direct method based on steam-ing. In most cases, water is the most advantageous 2Q~i8~ 32 coolant.
Figure 2 shows schematically another embodiment of the reactor according to the invention partly cut open. In Figure 2, the actual desulfurization reac-tor, wherein the sulfurous gases are supplied to thereactor via duct 1, is shown on the right. Therefrom they are further conveyed to the fluidized bed cham-ber 2 wherein they flow through the fluidized bed material and flow further through the annular duct 3 to the upper portion of the reactor, wherefrom it is turned, guided by the flow guide 4, i.e. vane grate, to the separation chamber 5 wherein the recycle material, i.e. the sulfur-bearing sorbent material is separated from the gases. The gases are exhausted in the manner shown in Figure 1 through duct 6 from the centre of the separation chamber 5, and the sorbent material falls from the separation chamber downward and through recycle duct 5a falls again into the chamber 2. Part of the sorbent material falls into the vertical discharge duct 15 and further therefrom into the horizontal part 16 of the discharge duct, wherefrom it is transported into the regeneration reactor by means of the conveyor gas supplied through duct 19. The regeneration reactor ln principle oper-ates similarly as the desulfurization reactor, regen-eration gas and/or steam being fed into the lower portion of the regeneration reactor through duct 14, in which situation the regeneration gas and/or steam enters the chamber 13' which is preferably a fluid-ized bed chamber, and flows further through itsannular part, i.e. the regeneration chamber 13a, to the upper portion of the reactor and again arrives in the separation chamber 5' guided by the vane grate 4'. In the separation chamber, the regenerated sor-bent is separated from the regeneration gas and 2~1~i8~32 steam, which entrains the sulfur via duct 20 locatedin the centre of the chamber upon discharging. In chamber 5', the separated sorbent material further falls downward through another recycle duct 5a' back into the chamber 13' and again comes into contact with the regeneration gas or steam. However, part of the regenerated material again falls into the return duct, i.e. tube 15', and further into the horizontal part 17 in the lower portion thereof, through which the regenerated sorbent is conveyed to the chamber of the desulfurization reactor by supplying transport gas which carries the sorbent material through duct 18. In the solution of Figure 2, heat exchangers have been disposed about the hori7ontal transport duct, i.e. tube 16, leading from the desulfurization reac-tor to the regeneration reactor, as well as about the return duct, i.e. tube 17, for the sorbent. Cooling medium is conveyed to the heat exchanger 21 disposed about the transport duct 16 through tube 22, and it is discharged through tube 23, that is, the heat ex-changer operates on the countercurrent principle.
Correspondingly, cooling medium is conveyed to the heat exchanger disposed about the return duct 17 through tube 22', and it is removed through tube 23', likewise on the countercurrent principle. Further, in Figure 2 there is a heat exchanger or cooler 24 and 24' about the desulfurization reactor and the regen-eration reactor, through which heat exchangers or coolers a heat exchanger medium is conveyed through tubes 11, 11' and 12, 12'.
In the foregoing description and drawings, the invention has been set forth only by way of example, and it is in no way bound to said description and drawings. Except for a reactor arrangement construc-ted as one unit and a fixed entity, separate arrange-2 ~ 3 ~
ments may be used in the manner shown in Figure 2, inwhich event the desulfurization reactor can be con-structed to be as efficient as possible in view of desulfurization, and the regeneration reactor can be constructed to be of another type and as efficient as possible specifically in view of regeneration.
Claims (16)
1. A process for the regenerative desulfur-ization of process gases by means of a recycle mass, in which process the sulfur-containing gases are con-tacted with a particulate sorbent material forming a fluidized bed and conveyed together with the sorbent material through a reaction zone to bind the sulfur to the sorbent, and the sulfur-bearing sorbent is separated from the process gas which is conveyed into further processing, whereafter the sulfur-bearing sorbent is conveyed into regeneration to separate the sulfur from the sorbent, the sulfur separated from the sorbent is conveyed into further processing, and the sorbent freed of sulfur is returned into contact with the process gas, c h a r a c t e r i z e d in that the sulfur-bearing sorbent which has been separ-ated from the process gas is cooled prior to being conveyed into regeneration for regulating the temper-ature of both the recycle mass and the reactor.
2. A process as claimed in claim 1, c h a r -a c t e r i z e d in that the cooling is realized by means of a heat exchanger (9, 21) disposed in the duct conveying recycle mass into regeneration, that a plug-like layer of recycle mass is formed in the transport duct (15, 16) to regulate the gas flow, that sorbent is conveyed from the layer formed by the plug to the regeneration reactor (13) by means of gas pulses supplied to the transport duct (16), and that another plug-like layer of regenerated sorbent is formed at the lower end of the regeneration reactor (13), said sorbent being transported from the second plug-like layer into the fluidized bed by means of gas pulses supplied to the return duct (17).
3. A process as claimed in claim 1 or 2, c h a r a c t e r i z e d in that the flow of recycle mass through the heat exchanger (9) is regu-lated by supplying a suitable recycle gas or equi-valent to the fluidized bed.
4. A process as claimed in claim 2 or 3, c h a r a c t e r i z e d in that the fluidized bed utilizes particulate material of at least two coarse-ness grades to achieve a suitable suspension density, in which case the coarser particulate material is of a diameter 0.5 - 2 mm, and the recycle mass flow is produced by means of a material of a substantially smaller diameter, preferably 0.05 - 0.3 mm.
5. A process as claimed in any one of the pre-ceding claims, c h a r a c t e r i z e d in that the sulfur-bearing sorbent is formed of at least one metal oxide or alloy metal oxide.
6. An apparatus for implementing the process of claim l, comprising a desulfurization reactor having a fluidized bed chamber (2) which contains a fluid-ized bed formed by particulate sorbent and into which the process gas is conveyed, a reactor chamber (3) above the fluidized bed chamber (2), separator means in the top portion of the reactor chamber (3) for separating the sulfur-bearing sorbent from the pro-cess gas, an exhaust duct (6) for discharging the process gas, a regeneration reactor (13), at least one transport duct (15, 16) for conveying the sulfur-bearing sorbent to the regeneration reactor (13), a duct (20) for conveying regenerating gas and separ-ated sulfur out from the regeneration reactor (13), and a return duct (17) for returning the sorbent from the bottom portion of the regeneration reactor (13) to the fluidized bed, c h a r a c t e r i z e d in that the reactor chamber (3) has a smaller cross-sec-tion in the flow direction of the gas than the fluid-ized bed chamber (2) has, and that the transport duct conveying the sulfur-bearing sorbent to the regener-ation reactor (13) has a heat exchanger (9, 21) for regulating the temperatures of the sorbent and there-by the entire reactor.
7. An apparatus as claimed in claim 6, c h a r a c t e r i z e d in that the fluidized bed chamber (2), reactor chamber (3) and the part of the transport duct (15, 16) conveying sorbent to the regeneration reactor are constructed to be substan-tially coaxially cylindrical, so that the part (15) of the transport duct conveying sorbent to the regen-eration reactor is above the fluidized bed chamber (2) substantially coaxially therewith, and that the reactor chamber (3) is constructed about the transport duct as an annular duct, that there is a cyclone chamber (5) in the upper portion of the reac-tor chamber (3), having flow guides (4) in the upper portion thereof so that the suspension formed by the process gas and the sorbent is directed tangentially toward the centre of the cyclone chamber (5), that the discharge duct (6) is in the centre of the cyc-lone chamber (5) coaxially therewith, in which case the process gas is exhausted through the discharge duct (6) and the sorbent falls into a distribution chamber (7) disposed below the cyclone chamber (5) and therefrom at least partly further into that part of the transport duct (15) which is below the distribution chamber (7).
8. An apparatus as claimed in claim 7, c h a r a c t e r i z e d in that the heat exchanger (9) is constructed in the transport duct disposed above the fluidized bed chamber (2) substantially coaxially with the fluidized bed chamber (2), that the transport duct comprises several heat transfer ducts going through the heat exchanger, through which the sulfur-bearing sorbent flows and the outer sur-face of which is cooled by a cooling medium flowing through the heat exchanger (9).
9. An apparatus as claimed in claim 8, c h a r a c t e r i z e d in that the regeneration reactor (13) has been annularly disposed about the reactor chamber (3).
10. An apparatus as claimed in claim 7, c h a r a c t e r i z e d in that the regeneration reactor (13) is a separate reactor whereinto the sor-bent that has reacted with sulfur is conveyed and wherefrom the regenerated sorbent is returned into the fluidized bed chamber (2) of the desulfurization reactor, and that there is a recycle duct (5a) in the desulfurization reactor about the transport duct (15) for the sorbent substantially coaxially therewith for returning part of the sorbent directly to the fluid-ized bed chamber (2).
11. An apparatus as claimed in claim 10, c h a r a c t e r i z e d in that the regeneration reactor (13) has another fluidized bed chamber (13') which has a fluidized bed of a particulate sorbent and to which the regeneration gas is conveyed, a regeneration chamber (13a) above said second fluid-ized bed chamber (13'), said regeneration chamber being of a smaller cross-section in the flow direc-tion of the regeneration gas than the second fluid-ized bed chamber (13'), separator means in the upper portion of the regeneration chamber (13a) for separ-ating the regenerated sorbent from the regeneration gas, and a discharge duct (20) for the regeneration gas and a return duct (15', 17) for returning the regenerated sorbent from the lower portion of the regeneration reactor (13) to the fluidized bed of the desulfurization reactor (13).
12. An apparatus according to claim 11, c h a r a c t e r i z e d in that the second fluid-ized bed chamber (13'), the regeneration chamber (13a) and a part of the return duct (15') conveying regenerated sorbent to the fluidized bed chamber (2) of the desulfurization reactor have been constructed to be substantially coaxially cylindrical in such a way that that part (15') of the return duct which conveys sorbent to the desulfurization reactor is above the second fluidized bed chamber (13') so that there is another cyclone chamber (5') in the upper portion of the regeneration chamber (13a), having flow guides (4') in the upper end thereof so that the suspension formed by the regeneration gas and the sorbent is directed tangentially to the centre of the other cyclone chamber (5'), that the discharge duct (20) is at the centre of the second cyclone chamber (5') coaxially therewith, in which case the regener-ation gas and the separated sulfur are removed through the discharge duct (20) and at least part of the regenerated sorbent falls into the return duct (15') disposed below the second cyclone chamber (5').
13. An apparatus as claimed in claim 12, c h a r a c t e r i z e d in that there is a second recycle duct (5a') about the return duct (15') for the sorbent substantially coaxially therewith for returning part of the sorbent back to the second fluidized bed chamber (13').
14. An apparatus as claimed in any one of claims 10 to 13, c h a r a c t e r i z e d in that at least one heat exchanger (21) has been installed in the tube (16) leading from the desulfurization reactor to the regeneration reactor and serving as a transport duct.
15. An apparatus as claimed in any one of claims 10 to 14, c h a r a c t e r i z e d in that at least one heat exchanger (21') has been installed in the tube (17) leading from the regeneration reac-tor to the desulfurization reactor and serving as a transport duct.
16. An apparatus as claimed in any one of claims 6 to 15, c h a r a c t e r i z e d in that an essentially horizontal part (16) of the conveyor duct leading to the regeneration reactor (13) is con-nected to the lower end of the vertical part (15) of the sorbent conveyor passage wherein the sulfur-bear-ing sorbent forms a plug-like layer, to which part (16) a gas duct (19) is connected for conveying the sorbent from the plug-like layer by means of gas pulses fed through the horizontal duct part (16) to the regeneration reactor (13), that a substantially horizontal duct part (17) leading to the fluidized bed chamber (2) is connected to the lower end of that part (15') of the vertical sorbent return duct dis-posed at the centre of the regeneration reactor (13), in which lower end (15') the sorbent which has bound sulfur forms another plug-like layer, a second gas supply duct (18) being connected to said duct part (17) for feeding the sorbent by means of gas pulses from the second plug-like layer to the fluidized bed chamber (2).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI910732 | 1991-02-14 | ||
| FI910732A FI910732A (en) | 1991-02-14 | 1991-02-14 | FOERFARANDE OCH ANORDNING FOER FOERVERKLING AV EN REGENERATIV SVAVELBINDNING. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2058132A1 true CA2058132A1 (en) | 1992-08-15 |
Family
ID=8531924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002058132A Abandoned CA2058132A1 (en) | 1991-02-14 | 1991-12-19 | Process and apparatus for effecting regenerative sulfur binding |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPH04310211A (en) |
| CN (1) | CN1064026A (en) |
| CA (1) | CA2058132A1 (en) |
| CS (1) | CS390191A3 (en) |
| DE (1) | DE4142813A1 (en) |
| FI (1) | FI910732A (en) |
| FR (1) | FR2672819A1 (en) |
| GB (1) | GB9127070D0 (en) |
| HU (1) | HU913965D0 (en) |
| IT (1) | ITMI913414A1 (en) |
| PL (1) | PL293009A1 (en) |
| SE (1) | SE9103769L (en) |
| ZA (1) | ZA9110051B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101422689B (en) * | 2007-11-02 | 2011-04-06 | 中国科学院过程工程研究所 | Flue gas denitration method and device by storing and reducing nitrogen oxides in circulating fluid bed |
| CN103801172B (en) * | 2014-02-19 | 2015-10-28 | 中国科学院山西煤炭化学研究所 | Ciculation fluidized moving bed is used to catch CO in power-plant flue gas 2technique and device |
-
1991
- 1991-02-14 FI FI910732A patent/FI910732A/en unknown
- 1991-12-16 HU HU913965A patent/HU913965D0/en unknown
- 1991-12-19 SE SE9103769A patent/SE9103769L/en not_active Application Discontinuation
- 1991-12-19 CS CS913901A patent/CS390191A3/en unknown
- 1991-12-19 IT IT91MI003414A patent/ITMI913414A1/en not_active Application Discontinuation
- 1991-12-19 CA CA002058132A patent/CA2058132A1/en not_active Abandoned
- 1991-12-20 ZA ZA9110051A patent/ZA9110051B/en unknown
- 1991-12-20 GB GB919127070A patent/GB9127070D0/en active Pending
- 1991-12-23 DE DE4142813A patent/DE4142813A1/en not_active Withdrawn
- 1991-12-30 CN CN91112609A patent/CN1064026A/en active Pending
- 1991-12-30 FR FR9116318A patent/FR2672819A1/en active Pending
- 1991-12-31 PL PL29300991A patent/PL293009A1/en unknown
-
1992
- 1992-01-20 JP JP4007812A patent/JPH04310211A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04310211A (en) | 1992-11-02 |
| DE4142813A1 (en) | 1992-08-20 |
| ZA9110051B (en) | 1992-09-30 |
| SE9103769L (en) | 1992-08-15 |
| ITMI913414A1 (en) | 1992-08-14 |
| CN1064026A (en) | 1992-09-02 |
| FR2672819A1 (en) | 1992-08-21 |
| HU913965D0 (en) | 1992-02-28 |
| FI910732A0 (en) | 1991-02-14 |
| PL293009A1 (en) | 1992-08-24 |
| CS390191A3 (en) | 1992-09-16 |
| FI910732A (en) | 1992-08-15 |
| GB9127070D0 (en) | 1992-02-19 |
| SE9103769D0 (en) | 1991-12-19 |
| ITMI913414A0 (en) | 1991-12-19 |
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| FZDE | Discontinued |