WO1996003198A1

WO1996003198A1 - Desulfurization of incondensible gases from the vacuum distillation of crude oil

Info

Publication number: WO1996003198A1
Application number: PCT/US1995/009290
Authority: WO
Inventors: Jiri Zachoval
Original assignee: Glitsch Inc
Current assignee: Glitsch Inc
Priority date: 1994-07-22
Filing date: 1995-07-20
Publication date: 1996-02-08
Anticipated expiration: 1997-01-22
Also published as: EP0772485A1; HUT76148A; AU3198895A; CA2195631A1; IT1276323B1; SK8397A3; JPH10506364A; ITMI941549A0; CN1159767A; KR970704499A; EP0772485A4; ITMI941549A1; CZ19497A3; PL318272A1

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

DESULFURIZATION OF INCONDENSIBLE GASES FROM THE VACUUM DISTILLATION OF CRUDE OIL

Background of the Invention

This invention concerns apparatus and a process for the elimination of hydrogen sulfide from incondensible gases derived from the distillation under vacuum of heavy- fractions of crude oil.

In the majority of cases, these gases are burned directly in the furnaces of- the same distillation column. However, this mode of operation results in problems of atmospheric pollution, owing to sulfur dioxide which is formed during the combustion and which exits the furnace chimney. Moreover, the presence of humidity and of hydrogen sulfide in the gases is often the cause of notable phenomena of corrosion in the equipment concerned.

Increasingly stricter international regulations concerning the control of gaseous wastes and the processing of crude oils, which are ever more rich in sulfur, make it imperative that the gases be treated, with the goal of eliminating the hydrogen sulfide which, in certain cases, can reach even up to fifty percent by weight .

On the other hand, different factors make it difficult to devise an efficient and convenient system for desulfurization. In fact, the use of amine washing systems, normally used by refineries for that purpose, is in this case particularly hampered and made uneconomic 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 difficulty is caused by the fact that the gases coming from the vacuum system are available at pressures only slightly above atmospheric, such that a desulfurization system must have extremely low pressure drop in order to allow the gas to be sent for combustion, 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 + H₂S = (NH₄)₂S

(NH₄)₂S + H₂S = 2NH₄HS

Furthermore, the practical realization of an efficient and convenient process has until now been hampered by various operating difficulties. The currently known apparatus and processes for the abatement of H₂S to within acceptable limits require the use of quantities 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, other processes resort to a high recirculation 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 guarantee that the pressure drop is compatible with the requirements cited above.

Description 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 H₂S 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 realizing desulfurization apparatus and process which enable the efficient removal of H₂S, even without the use of quantities of ammonia in excess of the stoichiometric amount .

The invention also achieves the goal of realizing desulfurization apparatus and process with the use of ammonia solutions in which the desulfurized gases are completely free of NH₃.

Another goal of the invention is that of realizing apparatus and process particularly adapted to obtain efficient desulfurization of gases with an ammonia solution at a pressure that is substantially atmospheric. The invention has additionally the goal of providing for the efficient desulfurization of gases using a solution of ammonia, making available a process and apparatus which does not cause significant pressure drop in the gas stream that is being subjected to 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.

Finally, 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 with a distribution device having an improved 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 incondensible 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. According to another characteristic of the apparatus of the invention the said means for wetting take the form of liquid distribution devices in the said sections of the desulfurizing column, each liquid distribution device being provided with a cylindrical body having a perforated base.

The apparatus of the invention is further characterized by the fact that the said distribution device may include a ring that is positioned 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 containing H₂S and which forms the initial gaseous mixture 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 contact with water, the aqueous solution resulting from the gas liquid contact in the said second stage being sent to the said first stage. 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 solution employed in the first stage contains the stoichiometric quantity of ammonia available for the reaction with the H₂S contained 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 10 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 offers the advantage of allowing the almost complete absorption of the said sulfur compound 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 furnishes desulfurized gases which are completely free of ammonia. The absence of excess quantities of liquid introduced into the column allows for a liquid stream leaving the desulfurization unit to have a total volume which can be treated by the downstream units of the apparatus, without the need to install new equipment of larger capacity than those originally installed. In view 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 of 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 incondensible 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 of 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 order to maintain the same area available for the passage of the gases, it has not been possible to obtain more than 60-65 irrigation points per square meter.

The distributor described herein offers in addition the advantage of having a very simple structure, which allows it to be inserted as a single cartridge into the column without requiring the internal supports or intermediate flanges normally necessary in traditional equipment .

Description of the Drawings

The brief 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 nonetheless illustrative embodiments in accord with the present invention when taken in conjunction with the accompanying drawings wherein:

Figure 1 illustrates a flow scheme of the invented apparatus.

Figure 2 illustrates in longitudinal cross-section the details of the desulfurization column of the apparatus in Figure 1.

Figure 3 illustrates the detail of the distribution device used in the column in Figure 2.

Description of the Preferred Embodiments

Figure 1 shows a knock out drum 1 for the separation of the liquid phase which generally is entrained in the gas stream 8 coming from a vacuum crude distillation column and from which it is desired to eliminate 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. Inside 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 one above the other. Each of the sections is characterized by a portion containing 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 under the 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 effects the first stage of desulfurization, in which gas stream 14 from the knock out drum 1 is brought into countercurrent contract with a fresh ammonia solution 9. Solution 9 contains a stoichiometric quantity of NH₃ that reacts with the H₂S contained 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 countercurrent contact with a stream of water 10, again in a bed of packing material like that in section 3.

The ammonia entrained by the gas 15 which comes from section 3 of the column, by contact with the water stream in the packing of section 4, forms a weak ammonia 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 10 and the gas stream 15 previously described, makes liquid stream 17 which in turn falls back into section 3 below, combining with that produced by the stream of ammonia solution 9. The total sulfur ammonia liquid 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 achieved by using a quantity of ammonia (present in 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 content of H₂S ranging from less than 1 ppm up to a maximum of 10 ppm by weight. Added to this is the fact that the desulfurized gas exiting from the column 2 does not contain 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 gas always contains a certain quantity of NH₃, the elimination of which, as well as being necessary, is made particularly difficult due to the simultaneous presence of significant quantities 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 sufficient 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 auxiliary compressors for the feeding of the desulfurized gas to the burners.

From the bottom of the knock out drum 1 there exits therefore a liquid 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 liquid phase 16 which comes from the desulfurization column 2 does not exceed usually ten percent of the total rate of the liquid 12 exiting the knock out drum. In this way, as already explained, the liquid stream 12 exiting the knock out drum 1 and being sent to the stripper 5 has a volume which does not exceed the design capacity of the latter, even in apparatus that existed prior to the installation of the column 2. The gas fraction 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 4 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 that 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 connected 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 and ammonia solution 9 plus liquid stream 17 in section 3 ) and it distributes the liquid phases uniformly onto the packed beds present in the sections 3 and 4. With the distributor device 18 installed above section 4 of column 2, the water stream 10 fed to section 4 is received directly by the cylindrical body 21 described above. A portion of the liquid stream fed to section 3 of the column is received above the cylindrical body 21 by the previously-mentioned collector ring 19, which has the function of collecting that portion of the stream of liquid 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 inclined 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 mm) , 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 containment grid 24.

The distribution device 18 illustrated in Figure 3 is particularly well adapted to flanged columns of less than 900 mm diameter.

The following examples are given to further illustrate the invention, without however limiting it to 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 CASCADE MINI-RINGS^® 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 diameter of 265 mm. A second distributor at the top of the column was identical to the former one, but without the collector ring. Into this column was fed 300 kg/h of gases having the following percentage composition by weight.

^H2 6.6 N₂+0₂ 11.3

Cl 29.1

C2 20.6

C3 15.4

C4 7.1

C5 1.2 co₂ 1.9

H₂S 6.8

Between the two sections of the column 100 kg/h of water solution were fed containing twenty percent by weight of NH₃, 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 measured at 1300 mbar, and the pressure at the top was 1290 mbar, giving a pressure drop of 10 mbar. 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 equipped 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 identical 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

^N2 7.3

°2 1.2

Cl 20.8

C2 12.3

C3 11.8

C4 6.5

C5 2.7

C6 0.8 co₂ 1.1

H₂S 31.7

Between the two sections of the column 1300 kg/h of water solution were fed containing 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 less than 10 ppm. The gas pressure at the entrance of the column was measured at 1350 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 that 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

What is claimed is:

1. Apparatus for the desulfurization of incondensible gases coming from vacuum distillation of crude heavy fractions of the type including a desulfurization column (2) provided with first (3) and second (4) sections in which said gases are brought into contact respectively with an ammonia solution (9) fed between the said sections and with water (10) fed to the top of the column, characterized by the fact of providing means (18) suitable to promote the wetting of the packing beds of said first and second sections of said desulfurization column.

2. Apparatus according to claim 1, characterized by the fact that the said wetting means comprise liquid distribution devices (18) respectively disposed above said first and second sections (3,4) of the desulfurization column (2) , at least one of said distillation devices comprising a cylindrical body (21) with a base (22) perforated with holes (23) .

3. Apparatus according to claim 2, characterized by the fact that one of said distribution devices (18) comprises a collector ring (19) , positioned above said cylindrical body (21) , designed to collect and distribute a part of the liquid stream fed to the section (3) of the column (2) .

4. Apparatus according to claim 3, characterized by the fact that said ring (19) has a surface inclined toward the center of the column (2) , the outside diameter of said ring (19) being greater than that of said cylindrical body (21) .

5. Apparatus according to claim 2, characterized by the fact that the said cylindrical body (21) has a diameter less than that of said desulfurization column (2) , a height of about to 250 mm, and a base (22) perforated with holes (23) of about 5 mm diameter.

6. Apparatus according to claim 2, characterized by the fact that the said distribution device (18) provides 300- 400 irrigation points per square meter and leaves an open area for the passage of gas having a dimension equal to thirty to thirty-five percent of the total of the area available.

7. Apparatus according to claim 2, characterized by the fact that said collector ring (19) and said cylindrical body (21) are supported by a support (20) which gives to said distributor (18) a structure which can be inserted as a single cartridge inside the desulfurization column (2) .

8. Apparatus according to claim 1, characterized by the face that the said desulfurization column (2) is a countercurrent packed column, said first and second sections (3,4) being positioned in cascade with respect to each other and being sections comprising single beds of gas-liquid contact packing materials.

9. Apparatus according to claim 1, characterized by the fact that each of the said first and second sections (3,4) of the desulfurization column 2 contains random packing material .

10. Apparatus according to claim 1 characterized by the fact that each of said first and second sections (3,4) of the desulfurization column 2 contains structured packing.

11. Apparatus according to claim 9 or 10 characterized by the fact that the said column (2) has a diameter of between 200 and 900 mm and is filled with metal packing material .

12. Apparatus according to clam 1 characterized by the fact that the gaseous stream flowing through the column (2) has a pressure drop not greater than 15 mbar.

13. Apparatus according to claim 1, characterized by the fact that the said desulfurization column (2) is mounted on a knock out drum (1) for the removal of the liquid phase entrained by the said gas mixture, forming a single shell with said knock out drum.

14. A process of desulfurization of incondensible gas coming from vacuum distillation of the heavy fraction of crude, characterized by the fact to be implemented by the apparatus according claim 1.

15. A process for desulfurizing an initial gaseous mixture having the form of an incondensible gas that contains hydrogen sulfide and that resulted from the vacuum distillation of the heavy fraction of crude oil, comprising the steps of: providing a gas-liquid contact column;

introducing said initial gaseous mixture into a first section of said column;

introducing a fresh ammonia solution into said first section of said column, said fresh ammonia solution containing the stoichiometric quantity for reacting with the amount of hydrogen sulfide present in said initial gaseous mixture;

passing a second ammonia solution from a second section of said column into said first section;

in said first section of said column, contacting said initial gaseous mixture with said fresh ammonia solution and with said second ammonia solution;

allowing a gaseous stream to be liberated from said first section of said column and to enter said second section of said column;

in said second section, contacting said liberated gaseous stream with water, thereby producing said second ammonia solution; and

recovering a desulfurized gas from said second section of said column.

16. A process according to claim 15, characterized by the fact that said initial gaseous mixture has up to 500,000 ppm by weight of H₂S, the desulfurized gas containing from less than 1 ppm up to 10 ppm by weight of residual H₂S.

17. A process according to claim 15, characterized by the fact that the pressure in the desulfurization treatment of the gas is less than 1500 mbar abs.

18. A process according to claim 15, characterized by the fact that the pressure drop of the gaseous stream between the inlet and the outlet of the said column is less than 15 mbar.