SCAVENGING HYDROGEN SULFIDE FROM HYDROCARBON LIQUIDS

Abstract: For this purpose, the hydrogen sulfide in the liquid is contacted with iron oxide particles typically containing a crystalline phase of Fe<u3>uO<u4>u or Fe<u2>uO<u3>u and combinations thereof together with an amorphous Fe<u2>uO<u3>u portion, and having a surface area of at least 3.5m<s2>s/g. Where for example, substantially anhydrous kerosene contains hydrogen sulfide in an amount in excess of 20 ppm, such hydrogen sulfide content is reduced to less than 10 ppm, thereby rendering it safe and salable.

Description: -1- SCAVENGING HYDROGEN SULFIDE FROM HYDROCARBON LIQUIDS Technical Field: This invention relates to the use of particulate iron oxides for scavenging hydrogen sulfide from non-aqueous liquids such as liquid 5 hydrocarbons. Background Art: The presence of hydrogen sulfide in liquid kerosene, for example, is unacceptable even in small amounts. Yet as well as this Applicant can determine, little has been accomplished in developing any simple 10 scavenging treatment for such non-aqueous liquids. In U.S. Patent No. 4,008,775, issued February 22, 1977, there is described a process in which specific porous iron oxides are used in drilling muds, primarily aqueous drilling muds to scavenge hydrogen sulfide (H S) released from a well in the course of a drilling opera- 15 tion. These iron oxides are described as having an ideal composition of substantially Fe^ a particle size of about 1#5 t0 60 microns an( j a surface area of at least ten times as great as magnetite (Fe.,0.) parti¬ cles of equal size. It has been determined that the iron oxide de¬ scribed in said patent is further characterized as having an amorphous 20 Fe^O- (non-crystalline) moiety together with an Fe 3 0, crystalline phase. It is described in U. S. Patent No. 4,089,809, issued May 16, 1978, that H S can be removed from producer gas by passing the gas (at very high temperatures) through a bed of pellets composed of sil ca and Fe O-; and U. S. Patent No. 4,201,751, issued May 6, 1980, describes 25 that H„S can be removed from coke oven gas by contacting the gas with a fluidized bed of particles of perlite containing steel-making dust comprising Fe 0-, and an alkaline material such as lime under very turbulent conditions. However, applicant is unaware of any published information which teaches that H„S can be scavenged from substantially 30 non-aqueous liquid systems using iron oxides, much less the iron oxides which have been found to be useful in the practice of the present in¬ vention. Disclosure of Invention: The present invention provides a process for scavenging H 2 S from a substantially anhydrous non-aqueous liquid such as a hydrocarbon liquid containing same, which comprises intimately contacting such liquid with dry or substantially dry particles of hydrogen sulfide- 2 reactive iron oxide particles having a surface area of at least 3.5m /g and composed substantially of a crystall ne phase of Fe 2 0 3 , ■ r e 3 0. and combinations thereof together with an amorphous Fe^O, moiety or portion. The contacting should be such that the H^S in the liquid is contacted with such iron oxide particles. The amount of iron oxide particles used is generally such that the H^S content (generally above 20 ppm) (parts per million) of the liquid is reduced to a predetermined level, for example, less than 10 ppm and preferably to 4 ppm or less. The tem¬ perature of the liquid used is generally between 10°C. and 50°C. , but may be higher or lower depending primarily on the boiling point of the liquid at higher temperatures, and the viscosity of the liquid at lower temperatures. A variety of stable reaction products are formed in carrying out the process depending primarily on contact time, the properties of the specific iron oxide particles used and to some extent on the amount of water, if any, present in the liquid being treated and/or in the iron oxide particles. In general, if the iron oxide particles have an Fe,0. crystalline phase and an e^O, amorphous moiety, but no F^O., crystalline phase, the crystalline reaction product will be stable and comprise a mixture of FeS 2 (pyrite) and e 3 S, (greigite); the ratio of one to the other being primarily dependant on the contact time and the water con¬ tent of the liquid and/or particles. On the other hand, if the iron oxide particles used have a crystalline phase of Fe 2 0 3 and an amorphous Fe 2 0 3 moiety, but no crystalline Fe 3 0» phase, the crystalline reaction products will be stable and comprise primarily FeS 25 although some Fε 3 S 4 may also be formed. By "stable reaction products" is meant reaction products such as S°, FeS 2 , -^S Λ and other non-FeS species which do not readily regenerate hydrogen sulfide, but are at least 70?. stable, in the presence of strong common acids. Best Mode for Carrying Out the Invention: In carrying out the processes of the present invention, any sub¬ stantially anhydrous non-aqueous liquid containing H 2 S may be used al¬ though it is preferred to employ a substantially anhydrous hydrocarbon liquid, that is a liquid composed of one or more compounds consisting of carbon and hydrogen atoms, and such compound or compounds may be satura¬ ted or unsaturated, that is, contain -c=c or -c=c bonds. Hydrocarbon liquids such as those obtained from producing wells or earth formations often contain H 2 S in concentrations in excess of 20 ppm, and the present processes are designed to reduce the H 2 S content thereof to an accepta¬ ble level so that the liquid can be used in refining operations without poisoning catalytic materials or in combustion processes without emit¬ ting deleterious quantities of noxious S0 2 fumes. The terms "substantially anhydrous non-aqueous liquids" or "sub- stantially anhydrous hydrocarbon liquids" as used herein are intended to identify liquids which are free of water or which only contain the normal amounts of water present in the liquid as a result of low or high atmospheric humidity conditions existing during the storage of the liquid, and, therefore, such amounts will vary to some extent depending on the hydrophilic or hydrophobic characteristics of the liquid. In general, the water content of the liquid will seldom exceed 2% by weight, and in most cases will be in the range of from about 0.001.- to about 0.05% by weight of water. In accordance with the present invention, H 2 S can be successfully scavenged from non-aqueous liquids or hydrocarbon liquids even though they are essentially anhydrous or contain such small amounts of water. The liquid is preferably intimately contacted with the iron oxide particles by incorporating the particles into the liquid and subjecting the resulting mixture to high shear mixing or agitation so as to expose the surface area of the particles to as much solid-liquid interface as possible thereby enabling the particles to contact the H 2 S in the liquid. By operating in this manner, it is also possible to scavenge the H^S from the liquid as quickly and as efficiently as the reactivity of the particles permit. Generally, the contact time will be less than four hours, and usually satisfactory scavenging of the H 2 S will occur within a period of 30-150 minutes. As noted previously herein, the iron oxide particles employed are dry or substantially dry prior to incorporation in the li is meant that the particles only contain an amount of water such as the particles will have after manufacture and/or after storage in a low or high humidity atmosphere prior to use. In any event, even though the partic es may contain some water they are free-flowing, and appear and feel to be dry particulates of matter. In general, the water content of the particles will seldom be in excess of 8% by weight, and in most cases will be in the range of from about 0.001 to about λ % by weight. Usually, the water content of the iron oxide particles will be partially what may be termed "free" water; that is, water which is picked up from the atmosphere under storage conditions, and partially what may be termed "bound" water; that is, water contained in the particles after rather vigorous drying, for example, drying under a vacuum at 100-110°C. for 24 hours. The amount of "free" water is usually from about 1.5 to about 6 times greater than the amount of "bound" water. It has been found that two classes of iron oxide particles have unexpectedly higher H 2 S reactive capacity and rates of reaction than other iron oxides within the scope of this invention, and, accordingly, are preferred. These preferred classes of iron oxide particles are as follows: (1 ) A class of iron oxide particles having a surface area of at 2 least 3.5 / , a kinetic "K" value of at least 1000 and which are composed of an Fe 3 0» crystalline phase, substantially free of crystalline Fe 2 0 3 , and an amorphous e 2 0 3 moiety. Said particles are described in said U. S. Patent No. 4,008,775. Particularly preferred are specific iron oxide particles, hereinafter designated Compound A, the pertinent properties of which are disclosed in the specific examples herein. This class of particles has the theoret¬ ical capacity to react with more H 2 S than any other iron oxides of which I am aware; and (2) A class of iron oxide particles having a surface area of at 2 least 3.5m / , a kinetic " " value of at least 2000 and which are composed of an Fe ? 0 3 crystalline phase, substantially free of crystalline F^O * and an amorphous Fe 2 0 3 moiety. Such particles are prepared by the conventional high temperature oxidation of ferrous sulfate. Particularly preferred are iron oxide particles, hereinafter designated Compound D, the pertinent properties of which are described in the specific examples herein. The temperature of the liquid during contactinα of with the irj oxide particles is not believed to be critical but is preferably such that a satisfactory reaction rate between the H 2 S and the particles is obtained and the reaction products are stable, that is, do not readily decompose to form H ? S, and so that the liquid is not so viscous as to preclude intimate mixing of the liquid and particles. A preferred tem¬ perature range for admixture of the liquid and particles is from about 15°C. to about 40°C. The following specific examples are given to illustrate the present invention and the practice thereof, but are not to be construed to limit the scope thereof. EXAMPLE I A. Description of Materials Used: (1) Hydrocarbon liquid used was kerosene having a boiling point range of 80-165°C. at 750 mm of pressure and a flash point range of 65-85°C. (2) Dry kerosene is the kerosene of (1) dried with molecular sieve material to a water content of 48 mg per kilogram of kerosene or 0.0048 water by weight. (3) Wet kerosene is the kerosene of (1) mixed with deionized water and allowed to separate into two layers from which the water layer was removed giving a kerosene containing 89 mg water per kilogram of kerosene or 0.0089% water by weight. (4) Compound A is composed of iron oxide particles having a 2 particle size of 6-8 mm, a surface area of 10 m / , a kinetic "K" value (determined as hereinafter described) of 2000 and containing a crystalline phase of F23O4, substantially free of Fe^O., crystalline phase, and an amorphous Fe 2 0 3 moiety. This material had a water content of 2940 mg per kilogram of iron oxide or 0.29% water by weight. (5) Dry Compound A is the same as Compound A except that it has been dried in a circulating oven at 100-110°C. for 48 hours to a moisture content of 60 mg per kilogram of iron oxide or 0.006.. by weight of water. B. Description of Equipment Used: Slurry Reactor: All reactions described herein were performed in a water-cooled, glass blender reactor (Lab Glass, Inc., Vinelane, NJ) attached to a Waring blender. The reactor had an internal diameter of 3 1/8" and was c?.,?ι 101/2" high. The blender reactor was fitted with a gasketed lid sup¬ plied with various ground glass fittings. The blender contents were mixed by a four blade turbine assembly, located at the base of the reactor, at 10000 rpm. Hydrogen sulfide gas was supplied to the reactor 2 from a lecture bottle regulated to 0.42 kg/cm (6 psig). A flowmeter was used to control the delivery of the gas to the reactor discharge tube. The tube outlet was located below the surface of the blender contents. Gas exiting the reactor was measured by a flowmeter and excess hydrogen sulfide was absorbed in a caustic trap. Infusion rates of hydrogen sulfide gas were controlled to allow a minimum of 4.0 g H 2 S/hour to enter the reactor. The reactor contained 500 ml of kerosene and 28.4 g of iron oxide material (20 Ibs/bbl), and the contents were maintained at a temperature of 22° C. to 25°C. Several combinations of iron oxide materials were used with the dry and wet kerosene. All test conditions were carried out in duplicate. To determine the completion of each run, the gas exiting the reac¬ tor was measured by a flowmeter. The reaction was stopped when the exit hydrogen sulfide flow was equal to the inlet hydrogen sulfide flow. At this point, the reaction was considered to have reached capacity.. At capacity, a sample of slurry was removed from the reactor and diluted ten-fold with dry kerosene, and the sample was placed in a sealed container. This dilution lowered the H 2 S partial pressure in the sample container and provided a convenient method to retain the sample for analysis. The delay between sampling and analysis was less than 30 minutes. Three samples were analyzed for hydrogen sulfide. One sample contained slurried solids and hydrocarbon from the reactor. _ A second sample was centrifuged and the supernatent was analyzed. A third sample was taken from the caustic trap. These analyses were used to obtain a material balance and determine the quantity of hydrogen sulfide reacted with the iron oxide. After the reaction, a large portion of the reacted solids were separated by centrifugation and rinsed three times with acetone to remove residual kerosene. The solids were then dried at 100 o -110°C. for 24 hours and analyzed for reaction products by x-ray crystallography Table I, which follows, shows the conditions used in the equipment for scavenging H ? S employing various combinations of dry kerosene, wet kerosene, Compound A and dry Compound A, and the H ? S reactive capacities of Compound A under these conditions. CMPI y t V.7PO Table 2, which follows, shows the analytical results obtained with regard to unreacted iron oxide and x-ray diffraction analysis of the reaction products obtained in the experimental runs of TABLE 1. TABLE 2 RiMctnut Remaining FeS, res. Ratio /•* Capacity Combination Iron Oxi e ) 2 Total Sulfur Total Sulfur (* ; ) Feb 2 in Crystalline (Amorphous and g Cβ A' Products Crystalline) FXP. N0._ 1 * <10 r - 19-2 5 ** 20/80 12.4 40.0 0.56 + 2 * 25-35". 13-2 17** 55/45 14.4 27.9 0.4G 3 * 35 ' .** 13-2 17** 55/45 14.4 35.5 0.47 •1 50-55'. 31-1 13** 30/70 22.4 • 27.7 0.45 5 20. ' ,** 33-3 28** 45/55 30 3C.9 0.43 6 20:;** 34-1 32** 50/50 32.3 30.3 0.40 0 50"** 21-2 17** 45/L5 18.7 2R.9'.* 0.40 1(1 !)'- 70-2 20** 20/ BO 50.7 AA -- O.Cύ It will be noted from the experimental results of TABLES 1 and 2 that the H S reactive capacity of iron oxide containing free water (Experiments 13) is higher than that of the dried oxide (Experiments 4 and 8), with the exception of Experiment 10 in which a larger amount of ^S was infused, whereas an increase in water content of the kerosene actually lowers the reactive capacity of such oxide (compare Experiment 1 and Experiments 2 and 3). On the other hand, the f- S reactive capac¬ ity of either Compound A or dry Compound A is of somewhat the same magnitude whether the kerosene contains more or less water (Experiments 2 and 6). The analytical results indicate that both FeS 2 and Fe 3 S, are formed in varying amounts depending on the reactant combinations used. However, both of these products are stable and do not release FLS in the presence of air and are also "acid stable". EXAMPLE II A. Description of Materials Used: (1) The kerosene used was the same as described in items (1), (2) and (3) of Example I. (2) Compound D is composed of iron oxide particles having a parti¬ cle size somewhat smaller than Compound A (of Example I), a surface area of 4m / , a kinetic " " value of 4000 and containing a crystalline phase of Fe o O,, substantially free of crystalline Fe 3 0,, and an amorphous e^O, moiety. This material has a water content of 250 mg per kilogram of iron oxide or 0.025.. by weight of water. (3) Dry Compound D is the same as Compound D except that it was dried prior to use at 105°C. for 24 hours to a water content of 170 mg per kilogram of iron oxide or 0.017% by weight of water. B. Description of Equipment Used: The equipment used was the same as described in Example I. Table 3, which follows, shows the conditions used in the equipment for scavenging H S employing various combinations of dry kerosene, wet kerosene, dry Compound D, and the H 2 S reactive capacities of Compound D under these conditions. TABLE 3 Exp, . Reactant Infused Unreacted Reacted Time Infusion Capacity No. Combina- l- S H 2 S in H 2 S at Rate gπ 2 s tions Slurry and capacity (gcpd ) (g) Trap (g) (g) (hours) (g/h) ero- Compound sene D 11. D™ D< 3 > 19.6 1.41 18.2 4.89 4.79 0.64 12. W^ D 22.2 1.5 20.7 4.43 5.01 0.73 0) D is dry kerosene (2) is wet kerosene (3) D is dry Compound D Note: Although no experiment was run using Compound D prior to drying, an experiment essentially identical to Experiment 11 but utilizing 5.. of water, based on kerosene, gave a capacity of 0.62 indicating that free moisture in the particles would not influence reactivity significantly. Table 4, which follows, shows the analytical results obtained with regard to unreacted iron oxide and x-ray diffraction analyses of the reaction products obtained in the experimental runs of Table 3. TABLE 4 Exp. R ty No. I 11 20 46-5 4-5' 10/90 22.4 0.64 12. 25-40 44-5 10/90 26.3 0.73 *About -l i ¬ lt will be noted from Table 3 and Table 1 that Compound D has a higher l-LS reactive capacity than Compound A even though the theoretic reactive capacity of Compound A is higher than that of Compound D. Al the experimental runs indicate that the H ? S reactive capacity of Com- pound D is not significantly affected by the water content therein, and that, in contrast to Compound A, the capacity of Compound D is increase somewhat if the water content of the kerosene is higher. Further, Tabl 4 shows that the reaction product formed when using Compound D under various water content conditions is substantially FeS 2 whereas the reaction products obtained with Compound A (Table 2) contain varying amounts of FeS~ and Fe 3 S. under such conditions. EXAMPLE III A. Description of Materials Used: (1) The kerosene used was the same as described in items (1), (2) and (3) of Example I. (2) Compound C is composed of iron oxide particles having a parti cle size somewhat smaller than Compound A (of Example I), a surface are 2 of 4 m / , a kinetic "K" value of 100 and containing an e 2 0 3 and Fe 3 0. crystalline phase and an amorphous Fe 2 0 3 moiety. This material has a water content of 676 mg per kilogram of iron oxide or 0.068% by weight of water. These iron oxide particles are iron oxide waste dusts from open hearth or basic oxygen furnace steel making operations. (3) Dry Compound C is the same as Compound C except that t was dried at 100-110°C. for 24 hours prior to use, and has a water content of 560 mg per kilogram of oxide or 0.055% by weight of water. (4) Magnetite is magnetite ore particles which are composed sub¬ stantially of an Fe 3 0. crystalline phase and an amorphous Fe 3 0 4 moiety and have a surface area of about 1 m / and a kinetic " " value of less than 1.0. This material was received as a water slurry, centrifuged to remove as much water as possible and dried in vacuum at 100-110°C. for 24 hours prior to use. It has a water content of 100 mg per kilogram o magnetite or 0.001% by weight of water. B. Description of Equipment Used: The equipment used was the same as that described in Example I. Table 5, which follows, shows the conditions used in the equipment for scavenging f- S employing various combinations of wet kerosene, dry kerosene, όry Compound C and magnetite, and the H 2 S reactive capacities of these iron oxides under these conditions. TABLE 5 Exp. Reactant Infused Unreacted 1-LS Reacted Time Infusion Capacit No . Combina- H 2 S in Slurry and H 2 S at Rate nations Trap Capacity tg) (g) (g) (hours) (g/h) oxid Kero- Iron sene Oxide 13. D Dry 8.5 4.17 4.33 1.67 5.1 0.15 Cpd.C 14. D Magnetite 15.1 2.76 10.78 2.54 5.93 0.38 15. W^ Magne- 3.5 2.27 1.28 0.84 4.2 0.05 tite (1) D represents dry kerosene (2) W represents wet kerosene An experiment was also run as in Experiment 13 but adding 5% by weight of water to the reactants with the result that the capacity of Compound C was increased to 0.34. These experiments indicate that Compound C has considerably less capacity than Compounds A and D under substantially dry conditions (compare with Tables 1 and 3) whereas the capacity of magnetite was substantially reduced when the kerosene con¬ tained more water. Table 6, which follows, shows the analytical results obtained with regard to unreacted iron oxide and x-ray diffraction analyses of the reaction products obtained in the experimental runs of Table 5. TABLE 6 Exp. Remai i m ng FeS 2 Rati o Total Capaci ty Fe 3 S 4 No. Iron Ox ide Sulfur (%) (%) ( %) ή F ϊ - (S ) g i ron oxi 13. 95 5±1 — — 2. 7 0.15 14. 85 14-4 — — 7.5 0.38 15. 85 5±1 2.7 0.05 As to the kinetic "K" value in the above description in the pH range 8-10, the derived rate law for Compound A is as follows: [S l = K x [SJ 2 x [H + ] } - 06 x [A] " dt^ τ wherein [S.] is sulfide concentration in ppm, t is time in minutes, d[S t ] dt is the instantaneous rate of change of dissolved sulfide concen trations, [H ] is hydrogen iron concentration and [A] is iron oxide -1 -1 2 concentration (lb./bbl). K is the rate constant in min. ppm cm x 1/mole and equal to approximately 2000. At Ph 8-10, the derived rate law agrees closely with Rickard's analysis of the reaction of hydrated iron oxide (ferric hydroxide) and hydrogen sulfide [Am. J. Sci. , 274:941 (1974)]. When [S ] and [H + ] are measured intermittently during the course of continuous acid reaction the substitution of observed [S^] and [H + ] values into the rate law equation above yields apparent K values which define relative differences in reaction rates among differe iron oxides. For purpose of this application, the rate constant K, measured as min ppm " cm x liters/mole, is calculated for iron oxide concentra- o tions measured in kg/ , and is as appears in the following derived rate law: d[S.] = -K x [H+] 1 '06 x [A] dt τ where: [S. ] i s sul fide concentration i n ppm. t i s time in minutes . d[S . ]/dt i s the i nstantaneous rate of change of di ssol ved sul fi de concentrations. [H ] is hydrogen ion concentration. [A] is iron oxide concentration kg/m . Industrial Applicability: . Benefits of the present invention include the following: as applie to hydrocarbon liquids, for example kerosene, the liquid is rendered sub stantially free of hydrogen sulfide; thus previously contaminated liquid products, theretofore incapable of meeting commercial specifications and which may be corrosive in use, are by the present process rendered fully acceptable. OMFI

Claims: Claims The embodiments of the invention in which an exclusive property o privilege is claimed are defined as follows: 1. The process for scavenging hydrogen sulfide from a hydrocarbo 5 liquid containing said sulfide which comprises contacting the hydrogen sulfide in said liquid with dry or substantially dry iron oxide particl 2 having a surface area of at least 0.5m / and composed of a crystalline phase of Fe 2 0 3 , Fe 3 0. and combinations together with an amorphous e 2 0 3 moiety, said particles being used in an amount sufficient to reduce the 10 hydrogen sulfide concentration in said liquid to a predetermined level. 2. The process according to Claim 1, wherein the contacting is carried out for a period of time sufficient to form stable reaction products including FeS_ and Fe 3 S.. 3. The process for scavenging hydrogen sulfide from a substan- 15 tially anhydrous hydrocarbon liquid containing said sulfide in amounts in excess of 20 ppm which comprises contacting the hydrogen sulfide in said liquid with iron oxide particles having a surface area of at least 2 3.5 m / , a kinetic "K" value of at least 1000 and composed of a crysta line phase of Fe 0., substantially free of a crystalline e 2 0 3 phase, 20 and an amorphous Fe 2 0~ moiety and containing from about 0.001 to about 0.5% by weight of water, said particles being used in an amount suffici to reduce said hydrogen sulfide content to less than 10 ppm and said contacting being carried out for a period of time sufficient to form stable reaction products including FeS and Fe~S.. 25 4. The process for scavenging hydrogen sulfide from a substantial anhydrous hydrocarbon liquid containing said sulfide in amount in excess of 20 ppm which comprises contacting the hydrogen sulfide in said liquid 2 with iron oxide particles having a surface area of at least 3.5 m / , a kinetic "K" value of at least 1000, a water content of from about 0.001 30 to about 0.5% by weight and composed of a crystalline phase of Fe ^ O.,, substantially free of an Fe-,0. crystalline phase, and an amorphous Fe 2 0 3 moiety, said particles being used in an amount sufficient to reduce said hydrogen sulfide content to less than 10 ppm and said contac ing being carried out for a period of time sufficient to form stable 35 reaction products including FeS 2 and F.,S..

Inventors: FOX IRWIN
Applicants: GAS SWEETENER INC
Application year: 1981
Main classification: B01D53
IPC codes: C07C7, C10G25