CA2195631A1 - Desulfurization of incondensible gases from the vacuum distillation of crude oil - Google Patents
Desulfurization of incondensible gases from the vacuum distillation of crude oilInfo
- Publication number
- CA2195631A1 CA2195631A1 CA002195631A CA2195631A CA2195631A1 CA 2195631 A1 CA2195631 A1 CA 2195631A1 CA 002195631 A CA002195631 A CA 002195631A CA 2195631 A CA2195631 A CA 2195631A CA 2195631 A1 CA2195631 A1 CA 2195631A1
- Authority
- CA
- Canada
- Prior art keywords
- column
- section
- gas stream
- liquid
- reservoir
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
-
- 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
- B01D53/14—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 absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/16—Fractionating columns in which vapour bubbles through liquid
- B01D3/22—Fractionating columns in which vapour bubbles through liquid with horizontal sieve plates or grids; Construction of sieve plates or grids
-
- 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
- B01D53/14—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 absorption
- B01D53/1456—Removing acid components
- B01D53/1468—Removing hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0408—Pretreatment of the hydrogen sulfide containing gases
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Gas Separation By Absorption (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Treating Waste Gases (AREA)
Abstract
Process and apparatus for desulfurizing the gaseous product of the vacuum distillation of the heavy fraction of crude oil. The initial gaseous mixture (8) to be desulfurized is an incondensible gas that contains hydrogen sulfide. A gas-liquid contact column (2) contains first and second sections (3, 4) that contain beds of packing material, which may be structured or random packing. The beds are supported below irrigation devices (18) that promote the wetting of the beds but cause minimal pressure loss in the gases passing through the column. The initial gaseous mixture is dried and introduced (14) into the first section (3) of the column. Also introduced into the first section of the column is a fresh ammonia solution (9) containing the stoichiometric quantity for reacting with the amount of hydrogen sulfide present in the initial gaseous mixture. Finally, the first section of the column receives a second ammonia solution that is passed from the second section of the column into the first section.
Description
~ WO96103198 P~,/~
~1 9563~
- D~SU~FURIZATION OF ~Nr~~()N1~N.~1s1.~. GASES
FROM THE VACU~M DISTILLATION OF CRUDE OIL
Backqround of the Tnvention This invention concerns apparatus and a process for the elimination of hydrogen sulfide from ;nrrln~pnr~ible gases derived f:rom the distillatio~ under vacuum of heavy fractions of~crude oil.
In the ma~ority of cases, these gases are burned directly in the furnaces o~ the same distillation column.
However, this mode of operation results in problems of atmospheric pollution, owing to sulfur dioxide which is formed during the com'oustion and which exits the furnace ! chimney. Moreover, the presence of humidity and of hydrug~ll sulfide in the gases is often the cause of l~ notaole p~Pn~ ~ of corrosion in the equipment concerned.
Increasingly stricter ;ntPrn~t;rn~l regnlati~nr concerning the control of gaseous wastes and the processing of crude oils, which are ever more rich in sulfur, make it imperative that the gase8 be treated, with the goal of eliminating the hydru~ll sulfide which, - in certain cases, can reach even up to fifty percent by weight.
On the other hand, different factors make it 2~ ;r111t to devise an efficient and convenient system for desulfurization. In fact, the use o~ amine washing WO96103198 .~ 5 ~
21 q~631 systems, normally used by refineries for that purpose, is in this case particularly hampered and maae 1~n~c~n~ ;c by the fact that oxygen (always present, often in appreciable quantity in the gaseous stream to be desulfurized) causes the degradation of the amines, with consequent formation and entrainment of foams.
Another dif_iculty is caused by the fact that the gases coming from the vacuum system are available at pressures only slightly above atmospheric, such that a desulfurlzation system must have extremely low pressure drop in order to allow the gas to be sent for combuetion, without the need to resort to the use of compression systems.
The use of ammonia solutions for the elimination of H2S from gaseous mixtures is a well-known process, which is based on the following reactions:
NH3 + H2S = NH4HS
2NH3 + ~2S ~ (NH4)2S
(NH4 )2S + H2S ~ 2NH4HS
Furth~ e, the practical realization of an ~ff;~;~nt and convenient process has until now been hampered by various operating difficulties. The currently known apparatus and processes for the abatement of H2S Fo within acceptable limits require the use of quantitie~ of NH3 in significant excess with respect to the stoichiometric ratio, the use of very dilute solutions to take into account the volatility of NH3 at temperatures normally used, and in any event the need to resort to quite high operating pressures Additionally, ~ W096/03198 2~ 9563I r~ r~
other processes resort to a high recir~ n flow rate of the washing solution, with a consequent increase in the investment cost and energy consumption. Finally, none of the treatment methods so far used is able to 5 guarantee that:the pressure drop is compatible with the requirements cited above Desc~i~tion of the Invention The invention now proposed overcomes the previously-cited limitations and problems of the earlier technology, making available desulfurization apparatus and procedure for gas which contains ~S by the use of ammonia solutions. The current invention is able to furnish recovery yields which are considerably higher with respect to those achievable by traditional methods.
An additional object of the invention is that of ro~l;7;ng desulfurization apparatus and process which enable the efficient removal of ~2S, even without the use of quantities of ammonia in excess of the stoichiometric amount.
The invention also achieves the goal of realizing desulfuri2ation apparatus and process with the use of ammonia solutions in which the desulfurized gases are completely ~ree o~ ~X3.
Another goal of the invention is that of rP~l i 7i n~
25 apparatus and process particularly adapted to obtain efficient desulfuri2ation of gases with an ammonia solution at a pressure that is substantially atmospheric.
W09~03198 ~ 2 1 q 5 6 3 1 The invention has additionally the goal of providing for the~efficient desulfurization of gases using a solution of ammonia, making available a proces~ and apparatus which does not cause~significant pressure drop in the gas stream that is being subjected ~o the desulfurization treatment.
It is yet another goal of the invention to minimize the quantity of liquid used in the desulfurization treatment, such that the unit which carries out the successive separation of the gas from the liquid phase is not overloaded.
~ inally, an additional goal of the invention is that of realizing an apparatus provided with packing beds which are able to offer high mass transfer and also provided wlth a distribution device having an ; _ vv~d ability, with respect to traditional devices, to irrigate the packing beds in the column sections, while at the same time having simpler and more economical structure than the already known analogous devices.
These and other goals are achieved in the desulfurization of ;n~n~nc;hle gases coming from the vacuum distillation of heavy fractions of crude by providing a desulfurization column having first and second contact sections for the said gases. An ammonia solution is fed between the first and second sections.
Water is fed to the top of the column above the second section_ Suitable means are provided for promoting the wetting of the packed beds of the said first and second sections of the said column.
~ W096/03198 ~ 2 1 q5 63 i P~
According to another characteristic of the apparatus of the invention the said means for ~etting take the form of liquid distribution device6 in the said sectior,s of the desulfurizing column, each liquid distribution device being provided with a cylindrical body having a perforated base.
The apparatus oi the invention is further characte~ized by the fact that the said distribution device may include a ring that is ppsitioned above the said cylindrical body and that is suitable to collect and distribute the liquid stream fed to the said first section of the column.
Both of the two sections of the desulfurizing column preferably are filled by random or stacked packing material such as sold under the trademark CASCADE MINI-RINGS~ or by structured packing such as the type sold under the trademark GEMPAK~.
The current process provides:
a first stage in which gas c~nt~lnlng ~2S and which 2~ forms the initial gaseous mi~ture is brought into contact with fresh ammonia solution and with an aqueous solution coming from a second stage, and said second stage, in which a gaseous stream liberated from the first stage is brought into 2~ contact with water, the aqueous solution resulting from the gas liquid contact in:the said second stage being sent to the said ~irst stage.
21-95=631 The said aqueous solution resulting from the said second stage is an ammonia solution obtained by contact between the water fed to the.second stage and the ammonia entrained by the gas rising from the first stage. The ammonia solutior employed in the first stage contains the stoichiometric quantity of ammonia available for the reaction with the X2S ~nnt~ d in the said initial gas mixture~
The process of the invention is characterized further by the fact that the said initial gaseous mixture ~ contains up to 500,000 ppm by weight of H2S, and the desulfurized gas contains from less than 1 to I0 ppm by weight of residual H2S. The said process additionally is carried out at a pressure below 1500 mbar abs, and the pressure drop of the gaseous stream between the inlet and the outlet of the column is not above 15 mbar.
With respect to traditional processes for the removal of H2S from gaseous mixtures, that of the invention of~ers the advantage of allowing the almos~~
complete absorption of the said sulfur l ~_UIld by the use of a stoichiometric quantity of ammonia. _In this~
way, as well as avoiding the extra costs due to the traditional use of excess quantities of reactants, the process of the invention ~urnishes desulfurized gases which are completely free of ammonia. The absence of excess quantities o~ liquid irtroduced into the column allows for a liquid stream leaving the desulfurization unit to have a total volume which can be treated by ~he downstream units of the apparatusl without the need to install new equipment of larger capacity than those .
originally installed.
~ WO96/03198 P~~ ,~9b -- 21 q5631 In vlew of the current state of the art of available knowledge, the current invention provides the surprising and unexpected result of allowing the effective application of packed columns (of the type more fully described in the following) as desulfurization columns operating at a pressure slightly above atmospheric. In this way it has also been possible to obtain, downstream oi the desulfurization treatment, a gas that has not been subjected to substantial pressure drop and which can be used without the need for additional compression equipment. In such a way, the current invention is particularly adapted to perform the desulfurization of ;nnnn~n~ible gases coming from vacuum crude distillation units. These gases, after desulfurization, are reused in the furnaces of the same column.
The current invention, thanks to the presence o~ the previously-mentioned distribution device, offers the advantage of providing notable irrigation of the packing bed, with 300-400 irrigation points per square meter, while leaving an open area for the passage of the gases equal to twenty to twenty-five percent of the total cross-sectional area of the column. In traditional towers with riser-style distributors, in arder to r-int~in the same area available for the passage of the gases, it has not been possible to obtain more than 60-65 irrigation points per s~uare meter.
The distributor described herein offers in addition the advantage of havin~ a very simple structure, which allows it to be inserted as a single cartridge into the column without requiring the internal supports or WO96/03198 r~
~2 ~ q563 1 intermediate flanges normall~y necessary in traditional equipment.
DescriQtiQn of the Drawinqs The brie~ description above, as well as further objects, features and advantages of the present invention will be more fully appreciated by reference to~the following detailed description of.presently preferred but ~nn~th~less illustrative embodiments in accord with the present inventiQr when taken in conjunction with the 0 A~l _ ying drawings wherein: ~ :
Figure l illustrates a flow scheme of the invented apparatus.
Fiqure 2 illustrates in longitudinal cross-section the details of the desulfurization column of the apparatus in ~igure l. :: ~
Figure 3 illustrates the-detail of the distribution device used in the column in Figure 2.
~escriQtion of the Preferred Embodiments Figure 1 shows a knock out drum I for the~separation of the liquid phase which generally is entrained in the gas stream 8 coming from a vacuum crude dist;ll~t;nn column and from which it is desired to eliminaFe the H2S.
Above the knock out drum 1, mounted directly on top, is a desulfurization column 2. For the treatment of a refinery gas coming from apparatus processing 3,000,000 tons/year of crude oil, this column would typically have a diameter varying between 200 and 300 mm.
~ WO96/03198 2 1 ~ 5 ~ 3 ~ , 5 ~L~0 Inslde column 2 are two distinct sections, each having a single packed bed. A lower or first section 3 and an upper or second section 4 are positioned in cascade o~e above the other. Each of the sections is characterized by a portion ~ntA;n;ng a packing material.
The preferred packing material is the metal version of a type shown in patents GB 1 385 672 and GB 1 385 673. It is sold underRthe trademark CASCADE MINI-RINGS~. An alternative but also suitable type of packing material would be structured packing of the type sold under the trademark GEMPAK~
The first or lower section 3 of the column 2 ef~ects the first stage of desulfurization, in which gas stream 14 from the knock out drum 1 is brought into count~l~uLL~-lt contract with a fresh ammonia solution g Solution 9 c~nt~;nq a stoichiometric quantity of NH3 that reacts with the H2S ~ntA;n~d in the initial gas mixture.
In this first stage an initial desulfurization of the gas to be treated is effected.
The gas stream 15 liberated by section 3 still contains a certain quantity of H2S. Stream 15 also entrains part of the ammonia with which it entered into contact in the packing material of the first section 3.
The gas stream so composed enters the upper section 4 of the column 2, where it enters into countel~uLL~llt contact with a stream of water lQ, again in a bed of packing material like that in section 3.
The ammonia entrained by the gas 15 which comes from section i of the column, by contact with the water stream in the packing of section 4, forms a weak ammonia W096/03198 .~ ,~0 solution which in practice contains the stoichiometric quantity of NH3 that was not reacted in the first section of the column 2. In this way in the second section 4 the H2S not removed=in the first stage is absorbed, with the use of a quantity of ammonia which corresponds stoichiometrically to the composition of H2S in the gas stream 15 liberated from section 3 of the desulfurization column. The sulfur-ammonia solution generated=by section 4 of the column, by contact between the water lQ and the gas stream 15 previously described/ makes liquid stream 1~ which in turn falls back into section 3 below, combining with that produced by the stream of ammonia solution 9 The total sulfur ammonia liqu~id stream 16 exiting from the bottom of the column 2 falls into the knock out drum 1.
In effect therefore, due~to a particular feature of the invention, the upper section 4 of the column realizes the final desulfurization of the initial gas mixture, eliminating the traces of H2S~not absorbed by the first stage 3. This absorption is additionally achievea by using a quantity of ammonia ~present ir, gas stream 15) which comes directly from the first stage and which for this reason is that which corresponds exactly, from the stoichiometric point of view, to the concentration of H2S
in the gas exiting from the lower section 3 of the desulfurization column.
In this way the desulfurized gas 11 which exits finally from the top of the column 2 has a con:tent of~ H2S
ranging from less than 1 ppm up to a maximum of 10 ppm by weight.
~ WO96/03198 2 1 9 5 6 3 1 E~llu~
. ~ . .
Added to this is the fact that the desulfurized gas exiting from the column 2 does nrt rnntA;n any trace of NH3 because it has reacted completely with~the H2S in the initial gas mixture. In traditional methods for desulfurization treatment the final gae always rrn~A;n~ a certain ~uantity of NH3, the elimination of which, as well as being necessary, ie made particularly difiicult due to:the simultaneous presence of significant rluantities of residual H2S in the treated gas mixture.
Thanks to the use of the packed tower previously described and also due to the contribution of the direct connection between the column 2 and the knock out drum 1, the desulfurized gases 11 still have snff;riPnt pressure to be sent to the vacuum crude tower furnaces. The method of construction indicated above has the advantage of reducing to the minimum the pressure drop (the reduction in pressure is in general less than 15 mbar) so as to make unnecessary the use of All~; 1; Ary compressors for the feeding of the desulfurized gas to the burners.
2D ~rom the bottom of the knock out drum 1 there exits therefore a liriuid phase 12 which contains the condensate separated from the gas stream 8 coming from the vacuum column, plus the sulfur-ammonia solution 16 composed of monosulfide and bisulfide of ammonia, exiting from the bottom of the desulfurization column 2. In particular, due to the invention, the quantity of the li~uid phase 16 which comes from the desulfurization column 2 does not exceed usually ten percent of the total rate of the li~uid lZ exiting the knock out drum. In this way, as already explained, the liriuid stream 12 exiting the knock out drum 1 and being sent to the stripper 5 has a volume .
WO96103198 P~
21 9~631 which does not exceed the design capacity of t~e latter, even in apparatus that exlsted prior to the installation of the column 2. The gas fractio~ 13 separated by the stripper 5 is finally sent to the Claus unit for the recovery of the sulfur.
As better seen in Figure~2, the desulfurization column 2 has inlets 6 and 7~for the input of ammonia solution 9 to section 3 and the water stream 10 to section 4 respectively. These liquid streams 9 and 10 are in turn received within the respective sections 3 and ~ by a distribution device 18 which is illustrated in~
Figure 3. It has been emphasized that the distributor illustrated in Figure 3 is designed to be mounted above section 3 of the column. The=corresponding distributor 18 positioned above the section 4 of packing material differs from t~a~ of section 3 by the absence of a collector ring 19, which will be better described as follows.
The distribution device 18 includes a support 20, which may conveniently be formed of upper and lower cross bars 20a rrnn~r~ by four support rods 20b. A
cylindrical body 21, and above it a ring 19, are fixed on the four support rods. The cylindrical body 21 has in particular a base 22 equipped with holes 23. It receives the liquid phases coming from above ( water in the case of section 4 an~ ammonia solution 9 plus liquid strea~m 17 in section 3 ) and it distributes the liquid phases uniformly onto the packed beas present in the sections 3 and 4.
i WO96/03198 2~ ~5~31 With the distributor device 18 installed above section 4 of column 2, the water stream 10 fed to section 4 i8 received directly by the cylindrical body 21 described above. A portion of the liquid stream fed to section 3 D~ the cclumn is received above the cylindrical body 21 by the previously-mentioned cellector ring 19, which has the functio~ of collecting that portion of the stream of li~uid 17 coming from section 4 that is near the wall of the column and distributing it into the body 21 below.
The ring 19 has a surface which is-~preferentially inrl;~ toward the center of the column so as to favor the collection~of~the liquid 17 which adheres to-the walls of the column and send it into the perforated cylindrical body 21 of the distributor 18. For this purpose the ring 19 advantageously has a larger diameter (for example 260 mm) than that of the body 21 below (for example 230 mml, the difference representing the surface left open for the passage of gas, which is equivalent to twenty to twenty-five percent of the total available area.
The distributor 18 is mounted on a ~o"tA; t grid 24.
The distribution device 18 illustrated in Figure 3 is particularly well adapted to flanged columns of less than 90o mm dfameter.
The fol~owing=examples are given to further illustrate the invention, without however limiting it to WO96/03198 2 1 9 5 6 3 1 ~ ;/CJ~
the details given.
Example 1 A column of diameter 300 mm had a first section 5 m high and a second section 3.3 m high. Both sections were equipped with 25 mm CASCAD~ MINI-Rr~GS~ packing material and were separated by a distributor of the type previously described. This distributor presented a collector ring having an external diameter of 300 mm.
The cylindrical body had an external ~ii t~r of 265 mm.
A seco~d distributor at the top of the column was identical to the former one, but without the collector ring. Into this column was fed 30D kg/h of gases having the following percentage composition by weight.
H2 6.6 . = ~== = =~ . ~=N2+O211.3 C1 29.1 C2 20.6 C3 15.4 C4 7.1 C5 1.2 C07 1 . 9 ~2S 6.8 Between the two sections of the column 100 kg/h of water solution were fed c~ti~in;ng twenty percent by weight of N'd3, while at the top of the column 800 kg/h of water were fed. At the top of the column a gas was obtained with a H2S content less than 1 ppm.
The gas pressure at the entrance of the column was measure,d at 1300 mbar, and the pressure at the top was 1290 mbar, giving a pressure drop of 10 mbar.
. .
~ WO96/03l98 r~ /C.~,~
Example 2 A column of diameter 450 mm had an upper section 4 m high and a lower section 5.50 m high. Both these sections were e~uipped with GEMPAK~ structured packing.
Between them a distributor was placed that was the same as the one described in Example 1, except that it had a cylindrical body having an external diameter of 390 mm and a collector ring having an external diameter of 450 mm.
At the top of the column there was placed a second distributor that was i~n~;~Al to the first one but was not supplied with a collector ring. Into this column was fed 700 kg/h of gas having the following composition by weight:
~ - -H2 3.8 ~2 1.2 C1 20.8 C2 12.3 C3 -11.8 C4 6.5 C6 Q.8 CO~
~ H2S 31.7 Between the two qen~ jnn~ of the column 1300 kg/h of water solution were fed cnn~A;ning nineteen percent by weight of NH3. At the top of the column 2200 kg/h of water were fed.
The gas obtained at the top of the desulfurization column had a H2S content leAs than 10 ppm.
WO96/03198 r~,lilJ.~. _ J9L~
2195~31 The gas pressure at the entrance of the column was measured at 135D mbar, and the pressure at the top was 1335 mbar, yielding a pressure drop of 15 mbar.
A latitude of;modification, change and substitution is intended in the foregoing disclosure and in some instances some features of the invention will be used without a:corresponding use of other features.
Accordingly, it is appropriate t~at the appended claims be construed broadly and in a manner consIstent with the scope of the invention therein. For example, the desulfurization column 2 could have a completely independent structure from the knock out drum 1.
~1 9563~
- D~SU~FURIZATION OF ~Nr~~()N1~N.~1s1.~. GASES
FROM THE VACU~M DISTILLATION OF CRUDE OIL
Backqround of the Tnvention This invention concerns apparatus and a process for the elimination of hydrogen sulfide from ;nrrln~pnr~ible gases derived f:rom the distillatio~ under vacuum of heavy fractions of~crude oil.
In the ma~ority of cases, these gases are burned directly in the furnaces o~ the same distillation column.
However, this mode of operation results in problems of atmospheric pollution, owing to sulfur dioxide which is formed during the com'oustion and which exits the furnace ! chimney. Moreover, the presence of humidity and of hydrug~ll sulfide in the gases is often the cause of l~ notaole p~Pn~ ~ of corrosion in the equipment concerned.
Increasingly stricter ;ntPrn~t;rn~l regnlati~nr concerning the control of gaseous wastes and the processing of crude oils, which are ever more rich in sulfur, make it imperative that the gase8 be treated, with the goal of eliminating the hydru~ll sulfide which, - in certain cases, can reach even up to fifty percent by weight.
On the other hand, different factors make it 2~ ;r111t to devise an efficient and convenient system for desulfurization. In fact, the use o~ amine washing WO96103198 .~ 5 ~
21 q~631 systems, normally used by refineries for that purpose, is in this case particularly hampered and maae 1~n~c~n~ ;c by the fact that oxygen (always present, often in appreciable quantity in the gaseous stream to be desulfurized) causes the degradation of the amines, with consequent formation and entrainment of foams.
Another dif_iculty is caused by the fact that the gases coming from the vacuum system are available at pressures only slightly above atmospheric, such that a desulfurlzation system must have extremely low pressure drop in order to allow the gas to be sent for combuetion, without the need to resort to the use of compression systems.
The use of ammonia solutions for the elimination of H2S from gaseous mixtures is a well-known process, which is based on the following reactions:
NH3 + H2S = NH4HS
2NH3 + ~2S ~ (NH4)2S
(NH4 )2S + H2S ~ 2NH4HS
Furth~ e, the practical realization of an ~ff;~;~nt and convenient process has until now been hampered by various operating difficulties. The currently known apparatus and processes for the abatement of H2S Fo within acceptable limits require the use of quantitie~ of NH3 in significant excess with respect to the stoichiometric ratio, the use of very dilute solutions to take into account the volatility of NH3 at temperatures normally used, and in any event the need to resort to quite high operating pressures Additionally, ~ W096/03198 2~ 9563I r~ r~
other processes resort to a high recir~ n flow rate of the washing solution, with a consequent increase in the investment cost and energy consumption. Finally, none of the treatment methods so far used is able to 5 guarantee that:the pressure drop is compatible with the requirements cited above Desc~i~tion of the Invention The invention now proposed overcomes the previously-cited limitations and problems of the earlier technology, making available desulfurization apparatus and procedure for gas which contains ~S by the use of ammonia solutions. The current invention is able to furnish recovery yields which are considerably higher with respect to those achievable by traditional methods.
An additional object of the invention is that of ro~l;7;ng desulfurization apparatus and process which enable the efficient removal of ~2S, even without the use of quantities of ammonia in excess of the stoichiometric amount.
The invention also achieves the goal of realizing desulfuri2ation apparatus and process with the use of ammonia solutions in which the desulfurized gases are completely ~ree o~ ~X3.
Another goal of the invention is that of rP~l i 7i n~
25 apparatus and process particularly adapted to obtain efficient desulfuri2ation of gases with an ammonia solution at a pressure that is substantially atmospheric.
W09~03198 ~ 2 1 q 5 6 3 1 The invention has additionally the goal of providing for the~efficient desulfurization of gases using a solution of ammonia, making available a proces~ and apparatus which does not cause~significant pressure drop in the gas stream that is being subjected ~o the desulfurization treatment.
It is yet another goal of the invention to minimize the quantity of liquid used in the desulfurization treatment, such that the unit which carries out the successive separation of the gas from the liquid phase is not overloaded.
~ inally, an additional goal of the invention is that of realizing an apparatus provided with packing beds which are able to offer high mass transfer and also provided wlth a distribution device having an ; _ vv~d ability, with respect to traditional devices, to irrigate the packing beds in the column sections, while at the same time having simpler and more economical structure than the already known analogous devices.
These and other goals are achieved in the desulfurization of ;n~n~nc;hle gases coming from the vacuum distillation of heavy fractions of crude by providing a desulfurization column having first and second contact sections for the said gases. An ammonia solution is fed between the first and second sections.
Water is fed to the top of the column above the second section_ Suitable means are provided for promoting the wetting of the packed beds of the said first and second sections of the said column.
~ W096/03198 ~ 2 1 q5 63 i P~
According to another characteristic of the apparatus of the invention the said means for ~etting take the form of liquid distribution device6 in the said sectior,s of the desulfurizing column, each liquid distribution device being provided with a cylindrical body having a perforated base.
The apparatus oi the invention is further characte~ized by the fact that the said distribution device may include a ring that is ppsitioned above the said cylindrical body and that is suitable to collect and distribute the liquid stream fed to the said first section of the column.
Both of the two sections of the desulfurizing column preferably are filled by random or stacked packing material such as sold under the trademark CASCADE MINI-RINGS~ or by structured packing such as the type sold under the trademark GEMPAK~.
The current process provides:
a first stage in which gas c~nt~lnlng ~2S and which 2~ forms the initial gaseous mi~ture is brought into contact with fresh ammonia solution and with an aqueous solution coming from a second stage, and said second stage, in which a gaseous stream liberated from the first stage is brought into 2~ contact with water, the aqueous solution resulting from the gas liquid contact in:the said second stage being sent to the said ~irst stage.
21-95=631 The said aqueous solution resulting from the said second stage is an ammonia solution obtained by contact between the water fed to the.second stage and the ammonia entrained by the gas rising from the first stage. The ammonia solutior employed in the first stage contains the stoichiometric quantity of ammonia available for the reaction with the X2S ~nnt~ d in the said initial gas mixture~
The process of the invention is characterized further by the fact that the said initial gaseous mixture ~ contains up to 500,000 ppm by weight of H2S, and the desulfurized gas contains from less than 1 to I0 ppm by weight of residual H2S. The said process additionally is carried out at a pressure below 1500 mbar abs, and the pressure drop of the gaseous stream between the inlet and the outlet of the column is not above 15 mbar.
With respect to traditional processes for the removal of H2S from gaseous mixtures, that of the invention of~ers the advantage of allowing the almos~~
complete absorption of the said sulfur l ~_UIld by the use of a stoichiometric quantity of ammonia. _In this~
way, as well as avoiding the extra costs due to the traditional use of excess quantities of reactants, the process of the invention ~urnishes desulfurized gases which are completely free of ammonia. The absence of excess quantities o~ liquid irtroduced into the column allows for a liquid stream leaving the desulfurization unit to have a total volume which can be treated by ~he downstream units of the apparatusl without the need to install new equipment of larger capacity than those .
originally installed.
~ WO96/03198 P~~ ,~9b -- 21 q5631 In vlew of the current state of the art of available knowledge, the current invention provides the surprising and unexpected result of allowing the effective application of packed columns (of the type more fully described in the following) as desulfurization columns operating at a pressure slightly above atmospheric. In this way it has also been possible to obtain, downstream oi the desulfurization treatment, a gas that has not been subjected to substantial pressure drop and which can be used without the need for additional compression equipment. In such a way, the current invention is particularly adapted to perform the desulfurization of ;nnnn~n~ible gases coming from vacuum crude distillation units. These gases, after desulfurization, are reused in the furnaces of the same column.
The current invention, thanks to the presence o~ the previously-mentioned distribution device, offers the advantage of providing notable irrigation of the packing bed, with 300-400 irrigation points per square meter, while leaving an open area for the passage of the gases equal to twenty to twenty-five percent of the total cross-sectional area of the column. In traditional towers with riser-style distributors, in arder to r-int~in the same area available for the passage of the gases, it has not been possible to obtain more than 60-65 irrigation points per s~uare meter.
The distributor described herein offers in addition the advantage of havin~ a very simple structure, which allows it to be inserted as a single cartridge into the column without requiring the internal supports or WO96/03198 r~
~2 ~ q563 1 intermediate flanges normall~y necessary in traditional equipment.
DescriQtiQn of the Drawinqs The brie~ description above, as well as further objects, features and advantages of the present invention will be more fully appreciated by reference to~the following detailed description of.presently preferred but ~nn~th~less illustrative embodiments in accord with the present inventiQr when taken in conjunction with the 0 A~l _ ying drawings wherein: ~ :
Figure l illustrates a flow scheme of the invented apparatus.
Fiqure 2 illustrates in longitudinal cross-section the details of the desulfurization column of the apparatus in ~igure l. :: ~
Figure 3 illustrates the-detail of the distribution device used in the column in Figure 2.
~escriQtion of the Preferred Embodiments Figure 1 shows a knock out drum I for the~separation of the liquid phase which generally is entrained in the gas stream 8 coming from a vacuum crude dist;ll~t;nn column and from which it is desired to eliminaFe the H2S.
Above the knock out drum 1, mounted directly on top, is a desulfurization column 2. For the treatment of a refinery gas coming from apparatus processing 3,000,000 tons/year of crude oil, this column would typically have a diameter varying between 200 and 300 mm.
~ WO96/03198 2 1 ~ 5 ~ 3 ~ , 5 ~L~0 Inslde column 2 are two distinct sections, each having a single packed bed. A lower or first section 3 and an upper or second section 4 are positioned in cascade o~e above the other. Each of the sections is characterized by a portion ~ntA;n;ng a packing material.
The preferred packing material is the metal version of a type shown in patents GB 1 385 672 and GB 1 385 673. It is sold underRthe trademark CASCADE MINI-RINGS~. An alternative but also suitable type of packing material would be structured packing of the type sold under the trademark GEMPAK~
The first or lower section 3 of the column 2 ef~ects the first stage of desulfurization, in which gas stream 14 from the knock out drum 1 is brought into count~l~uLL~-lt contract with a fresh ammonia solution g Solution 9 c~nt~;nq a stoichiometric quantity of NH3 that reacts with the H2S ~ntA;n~d in the initial gas mixture.
In this first stage an initial desulfurization of the gas to be treated is effected.
The gas stream 15 liberated by section 3 still contains a certain quantity of H2S. Stream 15 also entrains part of the ammonia with which it entered into contact in the packing material of the first section 3.
The gas stream so composed enters the upper section 4 of the column 2, where it enters into countel~uLL~llt contact with a stream of water lQ, again in a bed of packing material like that in section 3.
The ammonia entrained by the gas 15 which comes from section i of the column, by contact with the water stream in the packing of section 4, forms a weak ammonia W096/03198 .~ ,~0 solution which in practice contains the stoichiometric quantity of NH3 that was not reacted in the first section of the column 2. In this way in the second section 4 the H2S not removed=in the first stage is absorbed, with the use of a quantity of ammonia which corresponds stoichiometrically to the composition of H2S in the gas stream 15 liberated from section 3 of the desulfurization column. The sulfur-ammonia solution generated=by section 4 of the column, by contact between the water lQ and the gas stream 15 previously described/ makes liquid stream 1~ which in turn falls back into section 3 below, combining with that produced by the stream of ammonia solution 9 The total sulfur ammonia liqu~id stream 16 exiting from the bottom of the column 2 falls into the knock out drum 1.
In effect therefore, due~to a particular feature of the invention, the upper section 4 of the column realizes the final desulfurization of the initial gas mixture, eliminating the traces of H2S~not absorbed by the first stage 3. This absorption is additionally achievea by using a quantity of ammonia ~present ir, gas stream 15) which comes directly from the first stage and which for this reason is that which corresponds exactly, from the stoichiometric point of view, to the concentration of H2S
in the gas exiting from the lower section 3 of the desulfurization column.
In this way the desulfurized gas 11 which exits finally from the top of the column 2 has a con:tent of~ H2S
ranging from less than 1 ppm up to a maximum of 10 ppm by weight.
~ WO96/03198 2 1 9 5 6 3 1 E~llu~
. ~ . .
Added to this is the fact that the desulfurized gas exiting from the column 2 does nrt rnntA;n any trace of NH3 because it has reacted completely with~the H2S in the initial gas mixture. In traditional methods for desulfurization treatment the final gae always rrn~A;n~ a certain ~uantity of NH3, the elimination of which, as well as being necessary, ie made particularly difiicult due to:the simultaneous presence of significant rluantities of residual H2S in the treated gas mixture.
Thanks to the use of the packed tower previously described and also due to the contribution of the direct connection between the column 2 and the knock out drum 1, the desulfurized gases 11 still have snff;riPnt pressure to be sent to the vacuum crude tower furnaces. The method of construction indicated above has the advantage of reducing to the minimum the pressure drop (the reduction in pressure is in general less than 15 mbar) so as to make unnecessary the use of All~; 1; Ary compressors for the feeding of the desulfurized gas to the burners.
2D ~rom the bottom of the knock out drum 1 there exits therefore a liriuid phase 12 which contains the condensate separated from the gas stream 8 coming from the vacuum column, plus the sulfur-ammonia solution 16 composed of monosulfide and bisulfide of ammonia, exiting from the bottom of the desulfurization column 2. In particular, due to the invention, the quantity of the li~uid phase 16 which comes from the desulfurization column 2 does not exceed usually ten percent of the total rate of the li~uid lZ exiting the knock out drum. In this way, as already explained, the liriuid stream 12 exiting the knock out drum 1 and being sent to the stripper 5 has a volume .
WO96103198 P~
21 9~631 which does not exceed the design capacity of t~e latter, even in apparatus that exlsted prior to the installation of the column 2. The gas fractio~ 13 separated by the stripper 5 is finally sent to the Claus unit for the recovery of the sulfur.
As better seen in Figure~2, the desulfurization column 2 has inlets 6 and 7~for the input of ammonia solution 9 to section 3 and the water stream 10 to section 4 respectively. These liquid streams 9 and 10 are in turn received within the respective sections 3 and ~ by a distribution device 18 which is illustrated in~
Figure 3. It has been emphasized that the distributor illustrated in Figure 3 is designed to be mounted above section 3 of the column. The=corresponding distributor 18 positioned above the section 4 of packing material differs from t~a~ of section 3 by the absence of a collector ring 19, which will be better described as follows.
The distribution device 18 includes a support 20, which may conveniently be formed of upper and lower cross bars 20a rrnn~r~ by four support rods 20b. A
cylindrical body 21, and above it a ring 19, are fixed on the four support rods. The cylindrical body 21 has in particular a base 22 equipped with holes 23. It receives the liquid phases coming from above ( water in the case of section 4 an~ ammonia solution 9 plus liquid strea~m 17 in section 3 ) and it distributes the liquid phases uniformly onto the packed beas present in the sections 3 and 4.
i WO96/03198 2~ ~5~31 With the distributor device 18 installed above section 4 of column 2, the water stream 10 fed to section 4 i8 received directly by the cylindrical body 21 described above. A portion of the liquid stream fed to section 3 D~ the cclumn is received above the cylindrical body 21 by the previously-mentioned cellector ring 19, which has the functio~ of collecting that portion of the stream of li~uid 17 coming from section 4 that is near the wall of the column and distributing it into the body 21 below.
The ring 19 has a surface which is-~preferentially inrl;~ toward the center of the column so as to favor the collection~of~the liquid 17 which adheres to-the walls of the column and send it into the perforated cylindrical body 21 of the distributor 18. For this purpose the ring 19 advantageously has a larger diameter (for example 260 mm) than that of the body 21 below (for example 230 mml, the difference representing the surface left open for the passage of gas, which is equivalent to twenty to twenty-five percent of the total available area.
The distributor 18 is mounted on a ~o"tA; t grid 24.
The distribution device 18 illustrated in Figure 3 is particularly well adapted to flanged columns of less than 90o mm dfameter.
The fol~owing=examples are given to further illustrate the invention, without however limiting it to WO96/03198 2 1 9 5 6 3 1 ~ ;/CJ~
the details given.
Example 1 A column of diameter 300 mm had a first section 5 m high and a second section 3.3 m high. Both sections were equipped with 25 mm CASCAD~ MINI-Rr~GS~ packing material and were separated by a distributor of the type previously described. This distributor presented a collector ring having an external diameter of 300 mm.
The cylindrical body had an external ~ii t~r of 265 mm.
A seco~d distributor at the top of the column was identical to the former one, but without the collector ring. Into this column was fed 30D kg/h of gases having the following percentage composition by weight.
H2 6.6 . = ~== = =~ . ~=N2+O211.3 C1 29.1 C2 20.6 C3 15.4 C4 7.1 C5 1.2 C07 1 . 9 ~2S 6.8 Between the two sections of the column 100 kg/h of water solution were fed c~ti~in;ng twenty percent by weight of N'd3, while at the top of the column 800 kg/h of water were fed. At the top of the column a gas was obtained with a H2S content less than 1 ppm.
The gas pressure at the entrance of the column was measure,d at 1300 mbar, and the pressure at the top was 1290 mbar, giving a pressure drop of 10 mbar.
. .
~ WO96/03l98 r~ /C.~,~
Example 2 A column of diameter 450 mm had an upper section 4 m high and a lower section 5.50 m high. Both these sections were e~uipped with GEMPAK~ structured packing.
Between them a distributor was placed that was the same as the one described in Example 1, except that it had a cylindrical body having an external diameter of 390 mm and a collector ring having an external diameter of 450 mm.
At the top of the column there was placed a second distributor that was i~n~;~Al to the first one but was not supplied with a collector ring. Into this column was fed 700 kg/h of gas having the following composition by weight:
~ - -H2 3.8 ~2 1.2 C1 20.8 C2 12.3 C3 -11.8 C4 6.5 C6 Q.8 CO~
~ H2S 31.7 Between the two qen~ jnn~ of the column 1300 kg/h of water solution were fed cnn~A;ning nineteen percent by weight of NH3. At the top of the column 2200 kg/h of water were fed.
The gas obtained at the top of the desulfurization column had a H2S content leAs than 10 ppm.
WO96/03198 r~,lilJ.~. _ J9L~
2195~31 The gas pressure at the entrance of the column was measured at 135D mbar, and the pressure at the top was 1335 mbar, yielding a pressure drop of 15 mbar.
A latitude of;modification, change and substitution is intended in the foregoing disclosure and in some instances some features of the invention will be used without a:corresponding use of other features.
Accordingly, it is appropriate t~at the appended claims be construed broadly and in a manner consIstent with the scope of the invention therein. For example, the desulfurization column 2 could have a completely independent structure from the knock out drum 1.
Claims (30)
1. An apparatus for treating a gas stream within a gas/liquid contact column comprising:
a section of packing material substantially filling a length of the column, for contacting a liquid with the gas stream to remove at least a portion of a hydrogen sulfide fraction of the gas stream;
a distribution reservoir having a perforated baseplate, the reservoir disposed within the column and above the section of packing material for collecting the liquid and dispensing the liquid in a substantially even distribution onto the packing material;
a collector ring positioned above the reservoir for directing a portion of the liquid into the reservoir, the collector ring having a surface declining toward the center of the reservoir, and at least one passage for directing the gas stream within the column and past the distribution reservoir without passing through the liquid collected within the reservoir.
a section of packing material substantially filling a length of the column, for contacting a liquid with the gas stream to remove at least a portion of a hydrogen sulfide fraction of the gas stream;
a distribution reservoir having a perforated baseplate, the reservoir disposed within the column and above the section of packing material for collecting the liquid and dispensing the liquid in a substantially even distribution onto the packing material;
a collector ring positioned above the reservoir for directing a portion of the liquid into the reservoir, the collector ring having a surface declining toward the center of the reservoir, and at least one passage for directing the gas stream within the column and past the distribution reservoir without passing through the liquid collected within the reservoir.
2. The apparatus according to claim 1, wherein the distribution reservoir dispenses liquid under a gravitational force.
3. The apparatus according to claim 1, further comprising a frame supporting said distribution reservoir.
4. The apparatus according to claim 1, wherein said collector ring has an insideperimeter that is smaller than an outside perimeter of said distribution reservoir.
5. The apparatus according to claim 1, wherein said reservoir has a cross-sectional area that is smaller than a cross-sectional area of said section said reservoir cross-section and said section cross-section are parallel planes that are perpendicular to an internal wall of said column.
6. The apparatus according to claim 1, wherein said baseplate has a plurality ofperforations that are approximately the same size and shape.
7. The apparatus according to claim 1, wherein a cross-sectional area of said gas passage equals at least 20% of a cross-sectional area of said column, said gas passage cross-section and said column cross-section are parallel planes taken where said reservoir is disposed within said column.
8. The apparatus according to claim 1, further comprising a second section of packing material filling a second length of the column.
9. The apparatus according to claim 1, wherein said section includes a random packing material.
10. The apparatus according to claim 1, wherein section includes a structured packing material.
11. The apparatus according to claim 1, wherein said section includes a metal packing material.
12. The apparatus according to claim 1, wherein gas stream experiences a pressure drop not greater than 15 mbar when said gas stream is brought into contact with said liquid in said section.
13. The apparatus according to claim 1, wherein said column (2) is mounted on a knock out drum.
14. The apparatus according to claim 1, wherein the gas stream includes carbon dioxide.
15. A process for desulfurizing an initial gas stream that includes hydrogen sulfide comprising the steps of: providing a first and second gas-liquid contact surface, said first surface separated from said second surface;
introducing a first ammonia solution between said first surface and said second surface;
wetting said first surface by introducing said first ammonia solution thereto;
introducing said initial gas stream into contact with said first surface to generate a reacted gas stream and an ammonium salt solution, said reacted gas stream including an amount of hydrogen sulfide and a concentration of ammonia;
wetting said second surface by introducing a supply of water thereto, said water supply sufficient to react with said concentration of ammonia in said reacted gas stream to form sufficient ammonium hydroxide at said second surface to react with said amount of acid gas in said reacted gas; and introducing said reacted gas stream into contact with said wetted second surface to produce a second ammonia solution, said second ammonia solution reacts with and removes aquantity of hydrogen sulfide from said reacted gas stream.
introducing a first ammonia solution between said first surface and said second surface;
wetting said first surface by introducing said first ammonia solution thereto;
introducing said initial gas stream into contact with said first surface to generate a reacted gas stream and an ammonium salt solution, said reacted gas stream including an amount of hydrogen sulfide and a concentration of ammonia;
wetting said second surface by introducing a supply of water thereto, said water supply sufficient to react with said concentration of ammonia in said reacted gas stream to form sufficient ammonium hydroxide at said second surface to react with said amount of acid gas in said reacted gas; and introducing said reacted gas stream into contact with said wetted second surface to produce a second ammonia solution, said second ammonia solution reacts with and removes aquantity of hydrogen sulfide from said reacted gas stream.
16. The process according to claim 15, wherein said initial gas stream is introduced into said surface at a pressure that is not greater than 1500 mbar.
17. The process according to claim 15, wherein the initial gas stream experiences a pressure drop not greater than 15 mbar when said initial gas stream is brought into contact with said first surface and second surface respectively.
18. The process according to claim 15, further comprising the step of removing said reacted gas stream from said second surface after said quantity of hydrogen sulfide has been removed from reacted gas.
19. The process according to claim 15, further comprising the step of providing a distribution reservoir for wetting at least one gas/liquid contact surface, wherein said reservoir is placed above said surface to be wetted.
20. The process according to claim 19, wherein said reservoir has a perforated baseplate for dispensing liquid onto the surface to be wetted in a substantially even distribution.
21. The process according to claim 19, wherein said reservoir is placed above both said first surface and second surface.
22. The process according to claim 15, further comprising the steps of:
collecting said first and said second ammonia solutions into a distribution reservoir placed above said first surface; and dispensing said collected first and said second ammonia solutions onto said first surfaces in a substantially even distribution.
collecting said first and said second ammonia solutions into a distribution reservoir placed above said first surface; and dispensing said collected first and said second ammonia solutions onto said first surfaces in a substantially even distribution.
23. The process according to claim 15, wherein at least one of said gas-liquid contact surfaces comprises a random packing material.
24. The process according to claim 15, wherein at least one of said gas-liquid contact surfaces comprises a structured packing material.
25. The process according to claim 15, wherein said first and said second surfaces are vertically aligned in a column and are liquid permeable.
26. The process according to claim 25, further comprising the step of removing a stream of liquid from said first surface after contacting said liquid stream with said initial gas stream, said liquid stream introduced to said to said first surface from above said first surface.
27. The process according to claim 26, further comprising the step of collecting said liquid stream into a knock out drum.
28. The process of claim 15, wherein said first ammonia solution comprises at least 19%
ammonia.
ammonia.
29. The process of claim 15, wherein said initial gas stream includes oxygen.
30. The process according to claim 15, wherein said initial gas stream is brought into contact with said wetted first surface and said wetted second surface to generate a desulfurized gas comprising less than 10 ppm by weight of H2S.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI94A001549 | 1994-07-22 | ||
| IT94MI001549A IT1276323B1 (en) | 1994-07-22 | 1994-07-22 | PROCESS AND DESULFURATION PLANT OF GASES CONTAINING H2S |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2195631A1 true CA2195631A1 (en) | 1996-02-08 |
Family
ID=11369335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002195631A Abandoned CA2195631A1 (en) | 1994-07-22 | 1995-07-20 | Desulfurization of incondensible gases from the vacuum distillation of crude oil |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0772485A4 (en) |
| JP (1) | JPH10506364A (en) |
| KR (1) | KR970704499A (en) |
| CN (1) | CN1159767A (en) |
| AU (1) | AU3198895A (en) |
| CA (1) | CA2195631A1 (en) |
| CZ (1) | CZ19497A3 (en) |
| HU (1) | HUT76148A (en) |
| IT (1) | IT1276323B1 (en) |
| PL (1) | PL318272A1 (en) |
| SK (1) | SK8397A3 (en) |
| WO (1) | WO1996003198A1 (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2878099A (en) * | 1955-07-22 | 1959-03-17 | Ruhrstahl Ag Fa | Method of deacidifying gases |
| US4263021A (en) * | 1972-12-05 | 1981-04-21 | The Babcock & Wilcox Company | Gas-liquid contact system |
| US4297329A (en) * | 1977-12-22 | 1981-10-27 | Union Carbide Corporation | Vapor-liquid contacting system |
| DE2901935C2 (en) * | 1979-01-19 | 1986-01-09 | Linde Ag, 6200 Wiesbaden | Heat and mass transfer column |
| CH642566A5 (en) * | 1979-10-25 | 1984-04-30 | Sulzer Ag | TROUGH DEVICE FOR COLLECTING AND DISTRIBUTING THE LIQUID IN A COUNTERFLOW COLUMN. |
| DE3022180A1 (en) * | 1980-06-13 | 1981-12-24 | Dr. C. Otto & Comp. Gmbh, 4630 Bochum | METHOD FOR WASHING H (DOWN ARROW) 2 (DOWN ARROW) S FROM COOKING GAS |
| DE3208961A1 (en) * | 1982-03-12 | 1983-09-22 | Carl Still Gmbh & Co Kg, 4350 Recklinghausen | METHOD FOR DESULFURING COOKING GAS |
| US5389351A (en) * | 1992-11-04 | 1995-02-14 | Hasebe; Nobuyasu | Method for desulfurizing a gas |
-
1994
- 1994-07-22 IT IT94MI001549A patent/IT1276323B1/en active IP Right Grant
-
1995
- 1995-07-20 SK SK83-97A patent/SK8397A3/en unknown
- 1995-07-20 WO PCT/US1995/009290 patent/WO1996003198A1/en not_active Application Discontinuation
- 1995-07-20 HU HU9700187A patent/HUT76148A/en unknown
- 1995-07-20 CN CN95194824A patent/CN1159767A/en active Pending
- 1995-07-20 CZ CZ97194A patent/CZ19497A3/en unknown
- 1995-07-20 EP EP95928114A patent/EP0772485A4/en not_active Withdrawn
- 1995-07-20 CA CA002195631A patent/CA2195631A1/en not_active Abandoned
- 1995-07-20 AU AU31988/95A patent/AU3198895A/en not_active Abandoned
- 1995-07-20 KR KR1019970700411A patent/KR970704499A/en not_active Application Discontinuation
- 1995-07-20 PL PL95318272A patent/PL318272A1/en unknown
- 1995-07-20 JP JP8505898A patent/JPH10506364A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ITMI941549A1 (en) | 1996-01-22 |
| KR970704499A (en) | 1997-09-06 |
| EP0772485A4 (en) | 1997-08-06 |
| WO1996003198A1 (en) | 1996-02-08 |
| HUT76148A (en) | 1997-07-28 |
| CN1159767A (en) | 1997-09-17 |
| SK8397A3 (en) | 1997-07-09 |
| IT1276323B1 (en) | 1997-10-28 |
| JPH10506364A (en) | 1998-06-23 |
| EP0772485A1 (en) | 1997-05-14 |
| PL318272A1 (en) | 1997-05-26 |
| AU3198895A (en) | 1996-02-22 |
| CZ19497A3 (en) | 1997-07-16 |
| ITMI941549A0 (en) | 1994-07-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 20000720 |