METHOD AND SYSTEM FOR SELECTIVE REMOVAL OF CONTAMINATION FROM GAS FLOWS

Abstract: The invention relates to a method for selectively removing sulphur and/or sulphur containing contaminant compounds from a gas flow, which also comprises CO2, said method comprising the steps of: placing the gas flow into contact with a preselected metal ion at a pH lying in the range of between about -0.05 and about 7.0, wherein the metal ion and the contaminants react together in order to form a solid metal salt of the contaminants which precipitates out of the gas flow, wherein the lower pH limit of about -0.05 substantially ensures that the metal salt formed between the metal ion and the contaminants substantially exclusively is precipitated out of the gas flow, and wherein the upper pH limit substantially ensures that CO2 is not precipitated out of the gas flow as a metal carbonate salt.

Description: METHOD AND SYSTEM FOR SELECTIVE REMOVAL OF CONTAMINATION FROM GAS FLOWS The present invention relates to a method for removal of contaminants from gas flows, in particular the selective removal of sulphur and sulphur-containing compounds from gas flows. The invention further relates to a system of equipment for performing this process and to a process and system comprising this process, whereby sulphuric acid and/or sulphur dioxide is provided. Many industrial gases are contaminated with hydrogen sulphide (H 2 S) . The presence of H 2 S makes the direct application and/or use of these gases (for instance) natural gas, coal gas or biogas (impossible or at the very least) very hazardous. H 2 S must be removed because it is extremely toxic, causes environmental pollution after combustion and produces problems, for instance catalyst poisoning, in subsequent industrial processes. This means that a gas cleaning step is necessary to remove H 2 S in advance, before the resulting gases can be used. Gas separation processes are not only important for the reprocessing or purification of gases to thus make them suitable for subsequent process steps or (consumer) use, but to an increasing extent for the cleaning of (waste) gas flows which can be discharged into the atmosphere after treatment . In respect of the very damaging nature of H 2 S for the environment as well as in possible subsequent process steps (catalyst poisoning, corrosion) , attention has focussed for a long time on the removal of this gas, which is present in low concentration in many gas flows. Depending on the HS concentration present in the process flow, the set removal requirement, the process conditions at which the gas is supplied (pressure, temperature, flow rate) and must be delivered (pressure, temperature, flow rate) and the presence of other components in the gas, different alternatives have been developed for this gas separation or cleaning. These processes can be roughly divided into gas-solid and gas-liquid processes. These processes can be further sub-divided into reversible and irreversible processes. In the reversible processes the solid or liquid which is used to remove H 2 S (the absorbent) is regenerated in a separate process step, whereby in net terms no absorbent has to be added to the process. In irreversible processes net consumption of the absorbent does take place, whereby it must be supplied continuously. When processes are performed at high temperatures, in many cases no use can be made of gas- liquid processes due to the evaporation of the absorbent. For the application at lower temperatures (25-80°C) they are however extremely suitable due to the relatively high absorption capacity and absorption speed. These gas- liquid processes are frequently applied for removal of H 2 S from natural gas, biogas or coal gas, which are supplied at ambient temperature . Depending on the source from which it originates, the gas present in these different flows contains contents of H 2 S of 0.1-10% by volume for example. Since H 2 S is an acid gas, (regenerable) basic aqueous solutions of for instance (alkanol) amines or (non-regenerable) NaOH solutions are often used. When a regenerable (alkanol) amine is used the reactions are as follows : H 2 S(g) «♦ H 2 S(L) H Ϊ 22 SS((LL)) ++ AAnmine * HS " + AmineH + HS ~ + Amine «-» S ~ + AmineH + The regeneration can herein be provided by a temperature increase or a pressure decrease to be performed in a separate process step. During this regeneration is created concentrated H 2 S, which can subsequently be converted in a known Claus unit into marketable elementary sulphur. When the non-regenerable NaOH is used the reaction equations are: H 2 S(g) - H 2 S(L) H 2 S(L) + NaOH =» HS " + Na + + H 2 0 Along this route regeneration is impossible and an aqueous waste flow of NaHS will result. A drawback to the use of basic washing liquids is that the likewise acid carbon dioxide (C0 2 ) , which is present in considerable quantities in natural gas as well as biogas and coal gas, is also absorbed as according to similar acid-base reactions as occur for H 2 S . This so- called co-absorption results in a decreased efficiency of the absorption process, whereby an increase in the amount of chemicals needed during desulphurization is needed, leading to increased process complexity and costs. For this reason use is therefore made of redox processes where this co-absorption of C0 2 will be unable to occur. An example of this type of processes is the iron-chelate process wherein H 2 S is directly converted into elementary sulphur, wherein the oxidation of the iron complex reduced during the H 2 S absorption must be realized in a separate process step: absorption: 2 Fe 3+ . igand + H 2 S -» 2 Fe 2+ . igand + S + 2H + regeneration: 2 Fe 2+ .Ligand + X0 2 + 2H + •* 2 Fe 3+ . Ligand + H 2 0 Degeneration of this complex occurs during the regeneration of the iron complex whereby, depending on the degeneration speed, it must still be supplied continuously. Another drawback relative to a regenerable basic absorbent is that the sulphur which can be produced with this process route has a lower quality than can be achieved in the Claus process . The object of the present invention is to provide an improved process for the removal of contaminants from gas flows. According to a first aspect of the present invention, there is provided a method for the selective removal of undesired contamination, particularly in the form of sulphur and/or sulphur-containing compounds from gas flows, according to claim 1. In the method according to the present invention the hazardous and undesired contaminants can thus be selectively precipitated, wherein substantially no other gas components react together with the metal ion, whereby a very efficient system is provided. The inventors have demonstrated that the concentrations of S 2" and C0 3 2" in the liquid phase are dependent on the pH, wherein a good selective removal of S 2~ relative to C0 3 2" , in particular occurs with a pH of less than 7, i.e. wherein the method selectivity is enhanced. Furthermore the inventors have shown that by carrying out the process at a pH above about -0.05, preferably 0.0, other metal salts are substantially not precipitated out of the gas flow at the expense of the metal sulphide, i.e. wherein the method performance is enhanced. The inventors have accordingly demonstrated that via the method according the present invention, sulphur-containing compounds can be removed in a selective manner in relation to substantially non- hazardous gas components. The metal ion is preferably chosen such that the corresponding metal sulphide thereof is substantially non-soluble, wherein the metal is preferably chosen from the group substantially consisting of Zn, Fe, Cu, Ag, Pb, Cd, CO, Mg, Mn, Ni, Sn, and is preferably Fe, Zn or Cu, wherein it is recommended that the metal ion is placed in contact with the gas flow in the form of an aqueous salt solution. When an aqueous solution containing CuS0 4 is placed in contact with for instance an H 2 S-containing gas, the following reactions occur: H 2 S (g) ** H 2 S (L) H 2 S (L) + H 2 0 *» HS " + H 3 0 + HS " + H 2 0 ** S 2" + H 3 0 + Cu 2+ + S 2" ** CuS<- When the metal sulphide is very poorly soluble, these reactions can be considered practically irreversible, whereby a very effective H 2 S removal process is realized. Since the metal sulphide is chosen because it is very poorly soluble, a process efficiency decrease in the pH will substantially not occur because in solution the metal ions are virtually wholly consumed. The aqueous metal salt solution is preferably chosen from the group substantially consisting of metal nitrates, sulphates, phosphates, sulphites and nitrites and is most preferably a metal sulphate. A very good removal of sulphur-containing compounds from gas flows is obtained with copper sulphate. In the case of copper sulphate, the pH is preferably maintained in a range of between 0.25 and 7.0, since below about 0.25, solid copper sulphate may be precipitated at the expense of the metal sulphide. Furthermore, when using copper sulphate, the pH, on initially placing the gas flow in contact with the aqueous copper sulphate is preferably about 4.0 or above in order to provide a good efficiency. When the gas flow contains COS, it may be subjected to an initial or simultaneous step of hydrolysing COS → H 2 S + C0 2 , whereafter the H 2 S can be removed as above. In this way, COS can be very effectively removed from the gas stream. When for instance the metal ion is zinc, a pH of 6 or less, preferably 5 or less and most preferably in the range between 0.23 and 4.37 pH can be used in order to remove H 2 S from the gas flow in very selective manner relative to C0 2 . When the metal ion is for instance iron, a pH of about 6.7 or less can be chosen in order to provide a very good removal of H 2 S, and can lie between about 2.5 to 4.5 if a very good removal of H 2 S relative to C0 2 is desired. The method can comprise the further step of regenerating the metal sulphide into one or more of the following specii for instance: - the metal, - • the metal oxide, - the metal sulphate, wherein these regenerated specii can be fed back to the process . Regeneration of the metal can be carried out by treating the sulphide precipitation at higher temperature with hydrogen, wherein the pure metal and H 2 S are formed. The H 2 S can then be treated in for instance a Claus unit with the formation of elementary sulphur a highly marketable chemical . In addition, unused metal salt solution can also be fed back into the process wherein, before feedback of this unused metal salt solution, it can be supplied with an additional metal ion. The acid formed during the precipitation of the metal sulphide is preferably neutralized in order to cause the process to run well . The metal salt solution is preferably supplied by means of one or more of the following steps of: i) dissolving the metal by means of an electric current. Situated in the make-up unit, for instance, are a metal electrode and an inert electrode. These are connected to a circuit. The metal electrode becomes the positive pole, the inert electrode the negative pole. The following reactions will occur. The metal electrode will slowly dissolve as a result of: Λfe→Λfe 2 + +2 e " And on the inert electrode hydrogen will result in accordance with : 2H + +2 t or 2H 2 0+2 e- ♦ H, t + 20H ' In this method acid is consumed while metal is solubilized. This method had the following theoretical, critical aspect defined by the inventors, see later the system of equipment according to the present invention: 198 mol/hr of a divalent metal ion must be solubilized. This means that the total current must amount to 198 * 2 * 96500/3600 = 10600 ampere. If the current density [A/m 2 ] is too high, the following undesirable reaction can occur on the inert electrode . e 2+ +2e " → Meϊ The current density at which this phenomenon occurs determines the total required electrode surface. A driving force will further be required to solubilize the metal. The standard potentials for copper, zinc and iron are +0.34, -0.76 respectively -0.44 V. Zinc and iron will automatically solubilize, for copper it is necessary to apply a voltage. In order to increase the dissolving speed of zinc and iron a voltage can optionally be applied. At an applied voltage of 1 V the current consumption is 53.6 kWh/kmol . ii) adding a metal salt solution, for instance adding metal sulphate and neutralizing the acid separately. In the make-up unit the metal used up in the reaction is supplemented by dissolving metal sulphate. The formed acid will then have to be neutralized with for instance caustic soda. iii) dissolving a metal oxide or hydroxide, for instance dissolving Me(OH) 2 . In the make-up unit the metal used up in the reaction is supplemented by dissolving Me(OH) 2 . The formed acid will then be neutralized. During these steps sulphuric acid produced during the process is consumed while metal is solubilized. According to a second aspect, the present invention relates to a system of equipment for performing the above stated method. According to a third aspect of the present invention, a method and system of equipment is provided for providing sulphuric acid. The present invention will now be described with reference to the description and figures hereinbelow. Theoretical background of the chemistry of the method according to the present invention It is known that the sulphides of the metals zinc, iron, copper, silver, lead, cadmium, cobalt, magnesium, manganese, nickel and tin are very poorly soluble . Use can be made hereof for the removal of H S from gas flows. A sample reaction is: Zn 2+ + S 2" *» ZnS (1) The overall reaction, including the dissociation of H 2 S is A reaction wherein H„S reacts with Zn 2+ with the formation of zinc sulphide and acid. Liquid equilibriums When H 2 S or C0 2 is dissolved in water, it behaves as a divalent acid. H,S, HS " , S 2" , CO,, HCO and CO. will be present in the solution. The following equilibrium reactions will occur. The equilibrium constants of these reactions are σ ->iven at 25°C (K w , ' K 3 , ' K 4 ) or 18°C (K χ and K 2 ) . 2H 2 0 H 3 0 + + OH " K W = [H 3 0 + ] * [OH " ] 10 -14 (3) H 2 S + H 2 0 *♦ H 3 0 + + HS " (4) [H 3 0 * ]*[HS-] K n = - 9.1-10- [H 2 S] HS " + H 2 0 *» H 3 0 + + S 2" (5) [H 3 Q + ]*[S 2 -] K 2 = = 1.1-10 -12 [HS " ] CO, + 2H.0 « • H,0 + + HCO " (6) K 3 = M^≡H, ,3, ^ HCO, H 2 ° H 3 0 + + CO, (7) [H 3 0 + ] * tHCOf " ] κ 3 = 5.6-10 -11 [HC0 3 " 1 Precipitation equilibriums When a metal is now present in ion form in the solution, the following precipitation reaction can occur if the solubility product K is exceeded. (8) m n+ + nX m~ ~ p M m/p X n/p KgpS3 P j r M n +] m* [χn - ] n The driving force for this reaction ΔG (The difference in Gibbs energy between starting substance and products) can be calculated with: Table 1 shows the solubility product K s at 25°C (4) for a number of combinations of anions and metals on which the research will be further concentrated. Table 1. solubility products For CuC0 3 and Cu(OH) 2 solubilities are known of 0.03 wt% respectively 0.0059 g/1 at 20 °C. Using the foregoing, it is possible to calculate whether the precipitation reaction represented in reaction equation (8) can take place. Using as example a gas composition of 10 volume ppm H 2 S and 30 volume % C0 2 and assuming that, gas and liquid phase are in mutual equilibrium the concentrations of S 2" and C0 3 2" can be calculated using equation (3) to (7) . Surprisingly, the inventors have found that these concentrations are shown to be greatly dependent on the pH. When the concentration [M π +] is set at 1 mol/1, it is possible to calculate using (9) whether the precipitation reaction (8) can take place (ΔG <0) . Precipitation reactions of copper and zinc In Figure 1 the ΔG r is shown as a function of the pH of the reactions which result in the formation of copper (II) sulphide, zinc (II) sulphide zinc (II) carbonate and zinc (II) hydroxide . Conclusions : On the basis of the above stated starting points, it is found that copper sulphide can always be formed - zinc sulphide can be formed if the pH is higher than 0.23 zinc carbonate can be formed if the pH is higher than 4.37 zinc hydroxide can be formed if the pH is higher than 5.80 If 0.23<pH<4.37 it is found that zinc sulphide can result, but not zinc carbonate. Precipitation reactions of iron In Figure 2 the ΔG is shown as a function of the pH of the reactions which result in the formation of iron (II) sulphide, iron (II) carbonate and iron (II) hydroxide . Conclusions : On the basis of the above stated starting points, it is found that iron sulphide can be formed if the pH is higher than 3.10 iron carbonate can be formed if the pH is higher than 4.03 iron hydroxide can be formed if the pH is higher than 5.85 If 3.10<pH<4.03 it is found that iron sulphide can result, but not iron carbonate. Experimental A number of experiments were performed with metal sulphates, with copper sulphate, iron sulphate and zinc sulphate being chosen as model substances. Experiments were performed in order to study the precipitation reactions with H 2 S (sulphide) and C0 2 (carbonate) . A reference experiment with caustic soda was also performed. Experimental arrangement Figure 3 shows a flow sheet of an arrangement . The core of the arrangement is formed by a bubble column 2 (Figure 4) . In the bubble column is situated an aqueous solution of the metal sulphate. The temperature of the bubble column is kept at 20 °C by means of a thermostat bath. A gas flow containing hydrogen sulphide is guided through bubble column 2. A part of the hydrogen sulphide reacts, after dissociation in water, with the metal ion to form an insoluble sulphide. After the treated gas leaves bubble column 2, a part (flow A) is guided to an analysis unit 4. The rest (flow B) , after passing through a scrubber (not shown) , is discharged to an extractor. Before the gas flow is analysed it is admixed in a 1 : 1 ratio with air. The gas flow is then guided through a tubular reactor 6. The tubular reactor is situated in an oven. The temperature of the oven is 400°C. In this tubular reactor the H 2 S with the 0 2 present in the air is converted into S0 2 . The gas flow is thereafter carried through a Maihak UNOR 610 IR S0 2 analyser. The absorption liquid in the bubble column is changed per experiment . The composition and quantity of the supplied gas mixture can be adjusted by means of mass flow controllers. Table 2. Dimensions bubble column 2 Diameter 0.03 m Height 0.62 m Experiment 1 H 2 S removal with copper sulphate: A quantity of 1M CuS0 4 , 200 ml, of solution was placed in the bubble column. The experiments were performed with a superficial gas velocity of 2 cm/s. At the start of the experiment 1% H 2 S was added to the entry gas flow. During the experiment the gas composition was varied between 1 and 4% H 2 S . During the experiment the formation of foam was found to occur in the bubble column. So as not to obstruct the progress of the experiment, antifoam (silicone oil/water emulsion) was repeatedly added, and after addition of the antifoaming agent the operation of the column was found to improve for a time. After 41 minutes it was found that the content of CuS was so high (± 1 W%) , that the CuS/CuS0 4 slurry prevented the formation of small gas bubbles. The experiment was ended after 80 minutes, 22% of the copper sulphate present in solution had then been converted into copper sulphide. Figure 5 shows the H 2 S conversion as a function of the time. Discussion With a 1M CuS0 4 solution it was possible to capture substantially all H 2 S from a gas flow initially containing 1% or 2% H 2 S, the pH of the solution varying between 3.2 and 1.4. The formed CuS had a tendency to flotate and cause foam formation. A high content (>1W%) of solid CuS in the column causes the operation hereof to deteriorate, the cause of this probably lying in the exchanging surface becoming smaller. From an experiment wherein at the start of the experiment 4% H 2 S is added to the ingoing gas flow, it is found that it is possible to capture all H 2 S from a gas flow using a 1M CuS0 4 solution. Figure 5 shows the H 2 S absorption in copper sulphate. Experiment 2 H 2 S removal with zinc sulphate: A quantity of 1M ZnS0 4 (see Figure 6) solution was placed in the column. A gas flow was then guided through the column. The superficial gas velocity was 2 or 4 cm/s. At the start of the experiment 10 mmol NaOH was added to the solution. The pH of the solution is then 5.8. A determined concentration of H 2 S was thereafter added to the ingoing gas flow. The pH of the liquid decreased as more Zn 2+ ions were replaced by H + ions. The pH of the ZnS0 4 solution in the bubble column was found to have a great influence on the operation of the scrubber. When a pH of ± 2 was reached, NaOH is again added to the solution to bring the pH back to 5.8. Another concentration of H 2 S was then added to the ingoing gas flow. In this manner the percentage of H 2 S in the gas was varied between 1 and 4%. Figure 6 shows the H 2 S conversion as a function of the pH. Discussion With a 1M ZnS0 4 solution it is possible to capture more than 99% of the H 2 S from a gas flow initially containing 1 tot 4% H 2 S, provided the pH is not lower than 5.8. The pH of the ZnS0 4 solution in the bubble column is of great influence on the operation of the scrubber. Experiment 3 H 2 S removal with iron sulphate : A quantity of 1M FeS0 4 solution was placed in the column. A gas flow was then guided through the column. The superficial gas velocity was 2 cm/s. At the start of the experiment 10 mmol NaOH was added to the solution. The pH of the solution is then ± 7. A determined concentration of H 2 S was thereafter added to the ingoing gas flow. The pH of the liquid decreased as more Fe 2+ ions were replaced by H + ions . The pH of the FeSO, solution in the bubble column was found to be of great influence on the operation of the scrubber. When a pH of ± 4 was reached, NaOH was again added to the solution to increase the pH once again. Another concentration of H 2 S was then added to the ingoing gas flow. In this manner the percentage of H 2 S in the gas was varied between 1 and 4%. Figure 7 shows the H 2 S conversion as a function of the pH. Discussion With a 1M FeS0 4 solution it is possible to capture more than 99% H 2 S from a gas flow initially containing between 1% and 4% H 2 S, provided the pH is not lower than 6.7. The pH of the FeS0 4 solution in the bubble column is of great influence on the operation of the scrubber . Experiment 4 H 2 S removal with caustic soda as control: A quantity 0.1M NaOH solution was placed in the column. A gas flow was then guided through the column. The superficial gas velocity was 2 cm/s. At the start of the experiment the pH of the solution was 13. A determined concentration of H 2 S was thereafter added to the ingoing gas flow. The pH of the liquid decreased in time. The pH of the solution in the bubble column was found to be of great influence on the operation of the scrubber. When a pH of ± 8 was reached, NaOH was again added to the solution to increase the pH once again. Another concentration of H 2 S was then added to the ingoing gas flow. In this manner the percentage of H 2 S in the gas was varied between 1 and 4%. Figure 8 shows the H 2 S conversion as a function of the pH. Discussion With a 0.1M NaOH solution it is possible to capture more dan 99% H 2 S from a gas flow initially containing between 1% and 4% H 2 S, provided the pH is no lower than ± 10. At a pH greater than 12 the conversion is not found to be a function of the pH. CO absorption in metal sulphates: Experiment 5 i) Copper sulphate 200 ml 1M CuS0 4 was placed in the column. A gas flow of 14 ml/s C0 2 was then guided through the column. No precipitation was found to occur. Experiment 6 ii) Zinc sulphate 200 ml 1M ZnS0 4 was placed in the column. A gas flow of 14 ml/2 C0 2 was then guided through the column. The pH of the solution amounted to 4.2, no precipitation occurred. After addition of 2 mmol NaOH, the pH amounted to 5, and a precipitation occurred locally which is found to dissolve again. By adding more NaOH the pH was brought to 5.8. A precipitation now occurs locally which does not dissolve again. The resulting suspension was filtered and 2 M H. ASO Λ 4 was added to the residue (solid ZnCO,3 or Zn(OH) 2 . The residue was found to dissolve while forming a gas. It can be concluded herefrom that the precipitation most probably consists of zinc carbonate. Experiment 7 iii) Iron sulphate 200 ml 1M FeS0 4 was placed in the column. A gas flow of 14 ml/s C0 2 was then guided through the column. No precipitation was found to occur. The pH of the solution was 3.4. By adding NaOH the pH was brought to 4.9. A precipitation now occurs locally which does not dissolve again. Experiments 8-15 have been carried out in a stirred cell (figure 13) . Experiment 8 300 ml aqueous solution of 74.9 gram of CuS0 4 .5H 2 0 were brought into the stirred cell. The temperature of the cell was kept constant at 20°C. A gas stream of 3.5 ml/s containing 5 vol% H 2 S, 10 vol% C0 2 , balance nitrogen was applied to the reactor. Both gas and liquid phase in the reactor were continuously stirred. Measurements of the H 2 S and C0 2 concentrations and the total gas volume flow at the exit of the reactor showed that (see also figure 14) : • More than 99% of all hydrogen sulfide applied to this specific reactor is absorbed by the copper sulfate solution • In steady state condition no absorption of carbon dioxide occurred. An overview of calculated pH values assuming ideal behavior of the solution and a dissociation constant (pK of 1.9 for the second dissociation step of sulfuric acid yields the following table of pH's as a function of time during the experiment. Time (min) pH 2 4 . 18 16 3 . 25 26 3 . 03 Experiment 8 demonstrated that hydrogen sulfide can be selectively and to a substantial degree be removed from a gas stream containing carbon dioxide using a washing liquor containing metal ions. Experiment 9 300 ml aqueous solution of 7.5 gram of CuS0 4 .5H 2 0 was brought into the stirred cell. The temperature of the cell was kept constant at 20°C. A gas stream of 3.5 ml/s, 10 vol% C0 2 , balance nitrogen was applied to the reactor. When a steady state condition was reached the experiment was started: A gas stream of 3.5 ml/s containing 5 vol% H 2 S, 10 vol% C0 2 , balance nitrogen was applied to the reactor. Both gas and liquid phase in the reactor were continuously stirred. Measuring the H 2 S and C0 2 concentrations and the total gas volume flow at the exit of the reactor showed that (see also figure 15) : • More than 97% of all hydrogen sulfide applied to this specific reactor was absorbed by the acidified cupric sulfate solution. When the cupric sulfate solution is depleted the hydrogen sulfide conversion in the reactor drops dramatically • During the entire experiment no absorption of carbon dioxide was observed. An overview of calculated pH values assuming ideal behavior of the solution and a dissociation constant (pK a ) of 1.9 for the second dissociation step of sulfuric acid yields the following table of pH's as a function of time during the experiment. Time (min) ϋ 2 3 . 10 6 2 . 68 10 2 . 41 20 1 . 99 40 1 .43 66 1 . 02 70 0 . 97 This demonstrated that hydrogen sulfide can be selectively and to a substantial degree be removed from a gas stream containing carbon dioxide using a washing liquor containing metal ions, even at very low metal ion concentrations . Experiment 10 300 ml aqueous solution of 7.5 gram of CuS0 4 .5H 2 0 and 30 grams of H 2 S0 4 were brought into the stirred cell. The temperature of the cell was kept at 20°C. A gas stream of 3.5 ml/s, 10 vol% C0 2 , balance nitrogen was applied to the reactor. When a steady state condition was reached the experiment was started: A gas stream of 3.5 ml/s containing 5 vol% H 2 S, 10 vol% C0 2 , balance nitrogen was applied to the reactor. Both gas and liquid phase in the reactor were continuously stirred. Measuring the H 2 S and C0 2 concentrations and the total gas volume flow at the exit of the reactor showed that (see also figure 16) : • More than 96% of all hydrogen sulfide applied to this specific reactor was absorbed by the acidified cupric sulfate solution. When the cupric sulfate « solution was depleted the hydrogen sulfide conversion in the reactor drops dramatically • During the entire experiment no absorption of carbon dioxide occurred. An overview of calculated pH values assuming ideal behavior of the solution and a dissociation constant (pK a ) of 1.9 for the second dissociation step of sulfuric acid yields the following table of pH's as a function of time during the experiment. Time (min) 0 0 . 04 20 0 . 01 40 - 0 . 01 70 - 0 . 04 This demonstrated that hydrogen sulfide can be selectively and to a substantial degree be removed from a gas stream containing carbon dioxide using an acidified washing liquor containing metal ions, even at very low metal ion concentrations. Experiment 11 300 ml aqueous solution of 7.5 gram of CuS0 4 .5H 2 0 and 30 grams of H 2 S0 4 were brought into the stirred cell. The temperature of the cell was kept at 20°C. A gas stream of 3.5 ml/s, 10 vol% C0 2 , balance nitrogen was applied to the reactor. When a steady state condition (C0„ 2out-. = CO- 2,ι.n) was reached the exp c eriment was started . A gas stream of 3.5 ml/s containing 0.05 vol% H 2 S, 10 vol% C0 2 , balance nitrogen was applied to the reactor. Both gas and liquid phase in the reactor were continuously stirred. Measuring the H 2 S and C0 2 concentrations and the total gas volume flow at the exit of the reactor shows that (see also figure 17) : • More than 95% of all hydrogen sulfide applied to this specific reactor was absorbed by the acidified cupric sulfate solution. An overview of calculated pH values assuming ideal behavior of the solution and a dissociation constant (pK ) of 1.9 for the second dissociation step of sulfuric acid yields the following table of pH's as a function of time during the experiment. Time (min) pH 0 0.04 100 0.04 This demonstrated that hydrogen sulfide can be selectively and to a substantial degree be removed from a gas stream containing carbon dioxide using an acidified washing liquor containing metal ions, even at very low hydrogen sulfide concentrations. Experiment 12 A control experiment with sodium hydroxide as washing liquor. 300 ml aqueous solution of 12 gram of NaOH was brought into the stirred cell. The temperature of the cell was kept at 20°C. A gas stream of 3.5 ml/s, 10 vol% C0 2 , balance nitrogen was applied to the reactor. After 50 minutes the composition of the gas stream was changed to 5 vol% H 2 S, 10 vol% C0 2 , balance nitrogen. The total gas volume flow was not changed. Both gas and liquid phase in the reactor were continuously stirred. Measuring the H 2 S and C0 2 concentrations and the total gas volume flow at the exit of the reactor showed that (see also figure 18) : • More than 99% of all hydrogen sulfide applied to this specific reactor was absorbed by the sodium hydroxide solution. • Approximately 90% of all carbon dioxide applied to this specific type of reactor was absorbed by the sodium hydroxide solution. The pH value was, throughout the entire experiment between 14 and 13.95. Experiment 13 Control experiment with metal sulfate solution as washing liquor. 300 ml aqueous solution of 74.9 gram of CuS0 4 .5H 2 0 was brought into the stirred cell. The temperature of the cell was kept at 20°C. A gas stream of 3.5 ml/s, 10 vol% C0 2 , balance nitrogen was applied to the reactor. After 50 minutes the composition of the gas stream was changed to 5 vol% H 2 S, 10 vol% C0 2 , balance nitrogen. The total gas volume flow was not changed. Both gas and liquid phase in the reactor were continuously stirred. Measuring the H 2 S and C0 2 concentrations and the total gas volume flow at the exit of the reactor showed that (see also figure 19) : • More than 96.5% of all hydrogen sulfide applied to the reactor is absorbed by the cupric sulfate solution. An overview of calculated pH values assuming ideal behavior of the solution and a dissociation constant (pK a ) of 1.9 for the second dissociation step of sulfuric acid yields the following table of pH's as a function of time during the experiment. Time (min) ι BH 2 4 . 17 16 3 . 25 26 3 . 03 46 2 . 72 64 2 . 59 80 2 . 45 100 2 . 35 Experiment 14 300 ml aqueous solution of 3.0 gram of ZnAc.2H 2 0 and 6.0 grams of ZnO were brought into the stirred cell. The temperature of the cell was kept at 20°C. After this all gasses were removed from the cell using a vacuum pump. Then the gas and the liquid phase of the cell were continuously stirred. The gas phase and the liquid phase of the cell were operated batchwise. Monitoring the degree of carbonyl sulfide conversion in time showed that (see also figure 20) : • The hydrolysis reaction of COS to H 2 S and C0 2 in aqueous solutions of zinc acetate takes place at a 4 to 5 times higher rate than the hydrolysis reaction of COS in pure water in an identical reactor keeping all other parameters constant . This demonstrated that the hydrolysis of carbonyl sulfide to hydrogen sulfide and carbon dioxide in aqueous solutions can be substantially enhanced by the presence of zinc acetate in this solution. Experiment 15 300 ml aqueous solution of 2.5 gram of CuAc .2H 2 0 and 6.0 grams of CuO were brought into the stirred cell. The temperature of the cell was kept at 20°C. After this all gasses were removed from the cell using a vacuum pump . Then a predetermined amount of gaseous carbonyl sulfide was brought into the cell. The gas and the liquid phase of the cell were continuously stirred. The gas phase and the liquid phase of the cell were operated batchwise. Monitoring the degree of carbonyl sulfide conversion in time showed that (see also figure 21) : • The hydrolysis reaction of COS in aqueous solutions of copper acetate takes place at a 3 to 4 times greater rate than the hydrolysis reaction of COS in pure water in an identical reactor keeping all other parameters constant . This demonstrated that the hydrolysis of carbonyl sulfide to hydrogen sulfide and carbon dioxide in aqueous solutions can be substantially enhanced by the presence of copper acetate in this solution. The inventors have furthermore investigated the solubility of copper sulphate in aqueous sulphuric acid at various temperatures and as a function of pH, the results of which are shown in figure 22. A graphical representation of the capacity of an cupric sulfate solution acidified with sulfuric acid vs acidity (pH) clearly shows a substantial reduction of the capacity of the solvent at two pH values. 1. at a pH of approximately 4 2. at a pH of approximately 0.25 System of equipment according the present invention: A system 1 for cleaning gas flows according to the present invention is also shown schematically in figure 9. This system 1 consists of a scrubber 2, a filter 4 and a metal salt make-up unit 6. The gas for cleaning is fed in at the bottom (flow A) of scrubber 2 (packed column) and brought into contact in scrubber 2 with the cleaning liquid. The cleaned gas subsequently leaves scrubber 2. The metal sulphate flows (flow C) in counterflow with the gas. The hydrogen sulphide reacts with the metal sulphate in accordance with the precipitation reaction : Me 2 + +SO ~ +H 2 S MeSl +2H + +Sθl ~ Wherein sulphuric acid is also formed in addition to metal sulphide. The formed metal sulphide is separated (flow D) in a filter 4. The packing, column height, column diameter and other aspects of the system according to the present invention were theoretically determined as follows: Packing The column diameter D of bubble column 2 was estimated at 0.41 m. For column diameters smaller than 0.6 m a discharged packing is recommended. For column diameters between 0.3 and 0.9 m a packing diameter of between 25 and 38 mm is recommended. In respect of the highest possible wetted area, polypropylene Pall rings are chosen with a diameter of 25 mm. Several properties of these Pall rings are given in Table 3. Table 3. Properties of Pall rings Column height The column height can be determined with (10) id 'G,e ka a w 'G, ui t The parameters k G and a w are determined with correlations as published by Onda (11 and 12) (12) 1/3 ^G _ = 2.0 aD,, [ a,d p] Wherein the diffusion coefficient D v of H 2 S in the gas phase is estimated with a correlation published by Fuller: Wherein Σ V ι is the summation of the diffusion volumes for components A and B . Table 4. Diffusion volume increase per atom Σ V ± of H 2 S is thus 17.0 + 2 * 1.98 = 20.96. The diffusion coefficient of H 2 S in methane at room temperature is therefore 1.8*10 "5 m/s. The viscosity of methane is used for the viscosity μ v of the gas for cleaning. The viscosity μ v becomes 1.23*10 "5 Pa.s. The density of a methane/carbon dioxide mixture is used for the density p v of the gas for cleaning. The density p amounts to 1.1 kg/m 3 . The gas mass flow V w [ 2.7 kg/m 2 s] can now be calculated. The critical surface tension σ c amounts to 33 mN/m for polypropylene. The physical constants of water are used for the physical constants of the washing liquid. The surface tension σ τ then becomes 72 mN/m, the viscosity μ L becomes 10 "3 Pa.s, the density p L then becomes 1000 kg/m 3 . In order to keep the pressure drop over the column as low as possible, a low value is chosen for the washing liquid mass flow L w . It is recommended not to go below 2.7 kg/m 2 s . This value is chosen. This gives for k Q a value of 0.045 m/s, and for a/a a value of 0.297. The specific wetted area a then amounts to 61.5 m 2 /m 3 . The concentration of hydrogen sulphide in the gas flow for cleaning is 10000 ppm, the design specification of the scrubber amounts to 180 ppm. The required column height of the scrubber can be calculated with (10) and is found to amount to 1.52 m. For a design specification of the scrubber of 50 and 10 ppm H 2 S the required column height is found to amount to 2.01 respectively 2.62 m. Column diameter The column diameter D depends on the pressure drop over the column. The pressure drop must be high enough to guarantee a good distribution of gas and liquid flows. A guideline for the pressure drop over packed columns used as absorber is 15 to 50 mm water column per metre of packing. In the case of foam formation these values must be halved. A relation between pressure drop, gas and liquid quantities and physical properties of gas and liquid summarized in figure 10, in which and Filling in 5.6 and 5.7 gives K 4 =0.68 and F LV =0.077, the pressure drop is determined graphically and is found to amount to 21 mm water column per metre of packing. The column diameter of 0.41 m appears to have been well chosen. Critical aspects In addition to determining the main dimensions, the following has also been checked in the designing of the scrubber: - Exhaustion of the liquid phase - Liquid phase limiting - pH fall due to H 2 S absorption Exhaustion of the liguid phase Sufficient Me 2+ must be present in the liquid to capture all H 2 S . The gas throughput amounts to 500 Nm 3 /hr. The composition of the gas for cleaning is 1 V% H 2 S, the H 2 S specification for the cleaned gas amounts to 180 ppm. The quantity of H 2 S for capturing can then be calculated with: φ *p (16) φH,S= _2 r2>£rrr_-_ * (-" y- HH 2 ,SS,, ee - ■• "y Λ■ HH 2 sS,, uil tt' / Φ H2S = 198 mol/hr The quantity of Me 2+ which is fed in with the liquid follows from ( 17 ) φ , + =_ L„πD 2 ^ e 2+ A *c- Me 2 + Φ me2+ = 0.35 mol/s = 1283 mol/hr at a metal sulphate concentration of 1 kmol/m 3 . The concentration of Me 2+ on leaving the reactor is then 850 mol/m 3 . Liquid phase limiting Sufficient Me 2+ must be supplied by the liquid phase to allow all H 2 S supplied by the gas phase to be used up in the reaction. The maximum quantity of H 2 S supplied by the gas phase amounts to: (18) » 2 s _ =0. n 04 Λ 5 r .*- 0.01*10 5 ^ H2S k G C H Sι e G =0.018 ol/ 2 s RT 8.314*298 The maximum quantity of Me 2+ supplied by the liquid phase amounts to: The parameter k χ is estimated with a correlation such as published by Onda (3) Wherein the diffusion coefficient D L of Me 2+ in the liquid phase is estimated with a correlation published by Wilke Chang: The molar volume of the metal (in this case zinc) amounts to 0.0204 m 3 /kmol . The association factor φ amounts to 2.6 for water. The molar mass of zinc is 63 jgram/mol. The diffusion coefficient D τ of Zn 2+ in the liquid then becomes 2.24.10 "9 m 2 /s. The value for k τ then amounts to 1.24.10 "4 m/s. The molar masses of Cu 2+ , Fe 2+ and Zn 2+ are reasonably similar, so it may be expected that the diffusion coefficients will not differ very much. At a C Zn2+ of 850 mol/m 3 , the maximum quantity of Zn 2+ supplied by the liquid phase amounts to 0.105 mol/m 2 s, this being abundantly more than the maximum quantity of H 2 S supplied by the gas phase. From the foregoing it was concluded that with a gas throughput of 500 Nm 3 /hr and a composition of the gas for cleaning of 1V% H 2 S, 30 V% C0 2 .and 69 V% CH 4 , wherein the H 2 S specification of the cleaned gas varied between 10 and 180 Vppm H 2 S, the following dimensions of the scrubber 2 are recommended: Column diameter 0.41 m Packing 25 mm Pall rings (discharged) k G 0.045 m/s pressure drop 21 mm water column/metre packing Using the above stated system it was calculated that a total of 198 mol H 2 S is absorbed per hour in 1.28 m 3 metal sulphate. According to reaction equation 5.1, 198 mol H 2 S0 4 herein results. The solution which leaves the scrubber would then have a pH of about 0.5. Pump 198 mol MeS will be produced per hour. At a mol weight of 63 for the metal, this means that 19 kg MeS is produced per hour. The pump will then have to pump a solution containing 1.5 W% MeS. It is not expected that this will cause problems. Filter The filter will have to separate 19 kg MeS per hour from 1.283 3 solution. Depending on the settling behaviour of the metal sulphide, it will be possible to suffice with a settling tank. Another embodiment (figure 11) of the system according to the present invention consists of a scrubber 10, a filter unit 12 and a make-up unit 14, wherein metal sulphate/sulphuric acid solution is processed to enable it to be fed back to scrubber 10. In use the gas flow for cleaning (A) is guided into scrubber 10, wherein it encounters for instance a copper sulphate counterflow (B) . The copper sulphate/sulphuric acid solution (C) which leaves scrubber 10 is subsequently separated from copper sulphide in filter unit 12. This copper sulphate/sulphuric acid solution (flow D) is subsequently fed back to make-up unit 14. Here either copper oxide (G) can be dissolved in the acid formed during the absorption step or copper (G) using electric current. In this latter case, hydrogen (flow E) is made. The copper sulphide (flow E) leaving filter unit 12 can be converted into either copper oxide or metallic copper. The cleaned gas flow F is guided out of the scrubber. Yet another embodiment of the system according to the present invention (figure 12) contains a first scrubber 20, a second scrubber 22, a first filter unit 24, a second filter unit 26 and a make-up unit 28. In use the gas flow to be cleaned (A) is guided into scrubber 20 and subsequently into scrubber 22, whereafter cleaned gas flow (B) flows from this scrubber 22. A counterflow (C) of metal sulphate solution, for instance copper sulphate solution, is guided through both scrubber 22 and scrubber 20. The copper sulphate/sulphuric acid solution leaving scrubber 22, is divided into a larger flow D and subsequently separated from copper sulphide in filter unit 26 in order to give a sulphuric acid copper sulphate solution flow (E) and a copper sulphide flow (F) . A smaller flow is guided through scrubber 20 wherein the metal ion is fully precipitated, whereafter the sulphuric acid and the precipitated copper sulphide is guided out of scrubber 20 into a second filter unit 24 (flow G) . In this filter unit 24 sulphuric acid (flow H) is separated from copper sulphide (flow I) . Flow E is subsequently guided into make-up unit 28 wherein the copper sulphate is dissolved in water (flow J) while the sulphuric acid is neutralized. Flow C is then fed back from this make-up unit 28 into scrubbers 22 and 20. In this embodiment of the system according to the present invention, sulphuric acid is provided (flow H) . In the system according the present invention a continuous absorption process (H 2 S removal process) can therefore be obtained in two ways by adding either a metal oxide or a metal hydroxide flow (see for instance flow G, figure 11) whereby both the H+ generation occurring during the H 2 S absorption and the metal ion consumption occurring during the precipitation reaction are compensated precisely. The precipitated metal sulphide can be removed periodically and can be converted externally via a conversion process with hydrogen into concentrated H 2 S and the elementary metal (for instance flow E, figure 11, flow 1, figure 12) . In a second method a block of the elementary metal serving as electrode can be suspended in the makeup unit. A counter electrode of for instance platinum can also be arranged in the system whereby, by applying a counter voltage over both electrodes, the following reactions take place in the case of copper as sample metal: Cu =* Cu 2+ + 2e metal electrode 2H + + 2e ✓ H 2 Ϊ platinum electrode The decrease in concentration of Cu 2+ associated with the precipitation formation as well as the pH decrease associated with the absorption of H 2 S is nullified by both (linked) reactions. By variation of the potential difference over the electrodes the pH of the solution, and thereby the S_,_ concentration, can be adjusted, whereby the possibility also exists of adjusting the equilibrium concentration of H 2 S in the liquid. By adjusting the potential difference over the electrodes the (average) driving force for H 2 S absorption from the gas phase to the liquid phase can also be determined, which again influences the performance of the H 2 S removal. In this continuous operation the metal block must be replaced after a time and the formed metal sulphide removed. When the process is performed on large scale via this route, it is possible to regenerate the formed metal sulphide with the formed hydrogen on-site, wherein once again the elementary metal is then formed which can be re-used as electrode. The present invention is not limited to the above description, the rights being defined by the following claims.

Claims: CLAIMS 1. Method for selectively removing sulphur and/or sulphur containing contaminant compounds from a gas flow, which may also comprise C0 2 , said method comprising the steps of : - placing the gas flow into contact with a preselected metal ion solution at a pH lying in the range of between about -0.05 and about 7.0, wherein the metal ion and the contaminants react together in order to form a solid metal salt of the contaminants which precipitates wherein the lower pH limit of about -0.05 substantially ensures that the metal salt formed between the metal ion and the contaminants substantially exclusively is precipitated, and wherein the upper pH limit substantially ensures that non-contaminants are not precipitated out of the gas flow as metal salts. 2. Method according to claim 1 wherein the gas flow contains H 2 S and/or COS . 3. Method according to claims 1 or 2, wherein the metal is chosen such that the corresponding metal sulphide thereof is substantially non-soluble. 4. Method according to claim 3, wherein the metal is chosen from the group substantially consisting of Zn, Fe, Cu, Ag, Pb, Cd, CO, Mg, Mn, Ni, Sn, and is preferably Fe, Zn or Cu. 5. Method according to any of the foregoing claims, wherein the metal is placed into contact with the gas flow in the form of an aqueous salt solution. 6. Method according to claim 5, wherein the aqueous metal salt solution is chosen from the group substantially consisting of metal nitrates, sulphates, phosphates, sulphites and nitrites and is most preferably a metal sulphate. 7. Method according to claim 6, wherein the metal sulphate is copper sulphate. 8. Method according to claim 7, wherein the pH range lies between about 0.0 and 7.0, preferably 0.25 and 7.0. 9. Method according to claim 8, wherein the pH range lies between about 0.25 and about 6.0. 10. Method according to claim 9, wherein the start pH on initially placing the gas flow in contact with the aqueous copper sulphate is about .0 or above. 11. Method according to any of the claims 1-6, wherein, when the metal comprises zinc, a pH of about 6 or less, preferably 5 or less is maintained. 12. Method as claimed in claim 11, wherein the pH lies in the range between 0.23 and about 4.37. 13. Method as claimed in any of the claims 1-6, wherein, when the metal comprises iron, a pH of about 6.7 or less is maintained, wherein the pH preferably lies in the range between about 2.5 and about 4.5. 14. Method as claimed in any of the foregoing claims, wherein a buffer is added. 15. Method according to any of the preceding claims further comprising an initial or simultaneous step of transforming COS in the gas flow to H 2 S, before the removal thereof by means of exposing the gas flow to a metal ion for converting COS into ' H 2 S, preferably being a metal acetate compound, in particular being selected from the group consisting of zinc acetate and copper acetate. 16. Method as claimed in any of the foregoing claims, comprising the further step of regenerating the metal sulphide into one or more of the following specii: - the metal, - the metal oxide, - the metal sulphate. 17. Method as claimed in claim 16, comprising the further step of feeding one or more of the regenerated specii back into the metal ion solution. 18. Method as claimed in any of the foregoing claims, wherein substantially unused metal salt solution is fed back into the gas flow. 19. Method as claimed in any of the claims 13-15, wherein regeneration of the aqueous metal ion takes place by means of at least one of the following steps of: i) dissolving the metal by means of an electric current, ii) adding a metal salt, iii) dissolving a metal oxide or hydroxide. 20. Method as claimed in any of the foregoing claims, wherein sulphuric acid is provided. 21. System of equipment for performing the method as claimed in any of the foregoing claims, comprising: - a scrubber column in which the gas flow for cleaning can be brought into contact with a metal salt solution, and - a filter unit for separating precipitated metal sulphide. 22. System as claimed in claim 21, further comprising a regeneration unit in which metal can be regenerated. 23. System as claimed in claim 21 or 22 for providing sulphuric acid and/or sulphur dioxide.

Inventors: TER MAAT HENDRIK, VERSTEEG GEERT FREDERIK, TER MAAT, HENDRIK, VERSTEEG, GEERT, FREDERIK
Applicants: PROCEDE TWENTE B V, TER MAAT HENDRIK, VERSTEEG GEERT FREDERIK, PROCEDE TWENTE B.V., TER MAAT, HENDRIK, VERSTEEG, GEERT, FREDERIK
Application year: 1998
Main classification: B01D53
IPC codes: B01D53, C01B17, C22B3, C22B15