Catalytic adsorbents obtained from municipal sludges, industrial sludges, compost and tobacco waste and process for their production

Abstract

Industrial waste derived adsorbents were obtained by pyrolysis of sewage sludge, metal sludge, waste oil sludge and tobacco waste in some combination. The materials were used as media to remove hydrogen sulfide at room temperature in the presence of moisture. The initial and exhausted adsorbents after the breakthrough tests were characterized using sorption of nitrogen, thermal analysis, XRD, ICP, and surface pH measurements. Mixing tobacco and sludges result in a strong synergy enhancing the catalytic properties of adsorbents. During pyrolysis new mineral phases are formed as a result of solid state reaction between the components of the sludges. High temperature of pyrolysis is beneficial for the adsorbents due to the enhanced activation of carbonaceous phase and chemical stabilization of inorganic phase. Samples obtained at low temperature are sensitive to water, which deactivates their catalytic centers.

Claims

1. A method of removing acidic gases from wet air streams comprising putting an adsorbent comprising a) a waste material composition, comprising: one of compost or compost materials and sludge; (1) wherein the compost is one of tobacco waste, waste paper, wood char or a combination thereof; (2) wherein the sludge is at least one of waste oil, metal, or municipal sludge; (ii) 20-30% porous organic carbon with incorporated organic nitrogen species; and (iii) 70-80% inorganic matter; b) adsorbent characteristics, wherein; (i) the adsorbent is capable of adsorbing up to about 30% of the adsorbent's weight in hydrogen sulfide; (ii) a surface area of the adsorbent is 10-200 m.sup.2/g; and (iii) the pH of the adsorbent is between 7-12; in contact with the wet air stream and allowing the adsorbent to adsorb the acidic gases.

2. The process of claim 1, wherein the acidic gases are one or more of hydrogen sulfide, sulfur dioxide, hydrogen cyanide, and nitrogen dioxide.

3. The process of claim 1, wherein the acidic gas is hydrogen sulfide which reacts within organic matter to be oxidized to sulfur dioxide or elemental sulfur and salt forms thereof.

4. The process of claim 1, wherein the wet air stream is effluent from a sewage treatment plant, gaseous fuel, or gases from hydrothermal vents.

5. A method of removing acidic gases from wet air streams comprising the steps of: a) composting tobacco waste, waste paper, wood char or a combination thereof; b) thermally drying at least one of dewatered waste oil or metal sludge; c) mixing the dried sludge and the compost; d) pyrolyzing the mixture at temperatures between 600° C. and 1100° C., comprising the steps of: (i) heating the mixture between 5 and 10° C./minute; (ii) holding the heated mixture between 60 and 90 minutes; and (e) forming an adsorbent, wherein: (i) the adsorbent is capable of adsorbing up to about 30% of the adsorbent's weight in hydrogen sulfide; (ii) a surface area of the adsorbent is 10-200 m.sup.2/g; and (iii) the pH of the adsorbent is between 7-12; (f) putting said adsorbent in contact with the wet air stream; and (g) allowing the adsorbent to adsorb the acidic gases.

6. The process of claim 5, wherein the acidic gases are one or more of hydrogen sulfide, sulfur dioxide, hydrogen cyanide, and nitrogen dioxide.

7. The process of claim 5, wherein the temperature of pyrolysis is between 800 and 1000° C.

8. The process of claim 7, wherein the temperature of pyrolysis is between 900 and 1000° C.

9. The process of claim 5, wherein the temperature of pyrolysis is between 600 and 900° C. and the adsorbent is further treated with 15-20% HCl.

10. The process of claim 9, wherein the temperature of pyrolysis is between 800 and 900° C.

11. The process of claim 5, wherein the adsorbent may be regenerated by heating to 300-500° C. to remove elemental sulfur and sulfur dioxide.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) The above and still further objects, features and advantages of the present invention will become apparent upon consideration of the following detailed description of a specific embodiment thereof, especially when taken in conjunction with the accompanying drawings wherein like reference numerals in the various figures are utilized to designate like components, and wherein:

(2) FIG. 1 is a SEM image of the carbon nanotubes on the surface of sewage sludge-derived adsorbent of the prior art;

(3) FIGS. 2A and 2B are graphs depicting the predicted and measured volume of meso- and micro-pores, respectively, for the adsorbents derived from mixtures of industrial and municipal sludges;

(4) FIG. 3 is a graph depicting dependence of H2S removal capacity on the volume of mesopores in industrial and municipal sludge-derived adsorbents;

(5) FIG. 4 is a graph depicting a comparison of the predicted and measured H2S breakthrough capacity for sewage and industrial sludge-based adsorbents;

(6) FIG. 5 is a graph depicting DTG curves in nitrogen for selected adsorbants for initial and H2S exposed samples (E);

(7) FIG. 6 is a graph depicting DTG curves in nitrogen for selected adsorbants for initial and H2S exposed samples (E);

(8) FIGS. 7A and 7B illustrate X-ray diffraction patterns at 650° C. and 950° C., respectively;

(9) FIG. 8 illustrates changes in pore size distribution after H2S adsorption;

(10) FIG. 9 illustrates DTG curves in nitrogen for initial and exhausted samples;

(11) FIG. 10 shows X-ray diffraction patterns for samples obtained at 650° C.;

(12) FIG. 11 illustrates a comparison of the measured and predicted mesopores volume for WOSS samples obtained at various conditions;

(13) FIG. 12 illustrates a comparison of the measured and predicted H2S breakthrough capacities for samples obtained at various conditions;

(14) FIG. 13 illustrates the H2S breakthrough capacity curves for adsorbents obtained at 650° C.;

(15) FIG. 14 illustrates the H2S breakthrough curves for adsorbents obtained at 950° C.;

(16) FIG. 15 illustrates the dependence of the H2S breakthrough capacity on the amount of preadsorbed water;

(17) FIG. 16 illustrates a comparison of measured and calculated (assuming the physical mixture of components) H2S breakthrough capacities;

(18) FIG. 17 illustrates XRD patterns for tobacco derived samples;

(19) FIG. 18 illustrates XRD patterns for metal and waste oil sludge derived adsorbents;

(20) FIG. 19 illustrates a XRD diffraction pattern for composite tobacco/metal sludge based adsorbents;

(21) FIG. 20 illustrates nitrogen adsorption isotherms for samples pyrolyzed at 650° C.;

(22) FIG. 21 illustrates nitrogen adsorption isotherms for samples pyrolyzed at 950° C.;

(23) FIG. 22 illustrates pore size distributions for single component samples;

(24) FIGS. 23A and 23B illustrate pore size distributions for samples pyrolyzed at 650° C.;

(25) FIGS. 24A and 24B illustrate pore size distributions for samples pyrolyzed at 950° C.;

(26) FIG. 25 shows a comparison of the volume of micropores measured and calculated assuming physical mixture of the components;

(27) FIG. 26 shows a comparison of the volume of mesopores measured and calculated assuming physical mixture of the components;

(28) FIG. 27 illustrates the dependence of H2S breakthrough capacity on the volume of pores (micropores and mesopores for samples pyrolyzed at two temperatures);

(29) FIG. 28 illustrates DTG curves in nitrogen for single component samples;

(30) FIGS. 29A and 29B illustrate DTG curves in nitrogen for samples pyrolyzed at 650° C.; and

(31) FIGS. 30A and 30B illustrate DTG curves in nitrogen for samples pyrolyzed at 950° C.

DETAILED DESCRIPTION OF THE INVENTION

(32) Industrial sludges such as waste oil sludge and metal sludge can be utilized using pyrolysis to produce new catalytic adsorbents. An important result of mixing is an enhancement in the properties of the above-mentioned sewage sludge-based adsorbents. Although only waste oil sludge can lead to adsorbents with an exceptional ability for desulfurization with 30 wt % removal capacity, the presence of sewage sludge is an economically feasible method of utilizing this abundant material.

(33) Mixing the sludge and their pyrolysis resulted in the enhanced properties compared to the physical mixture of pyrolized single components. FIGS. 2A and 2B show the comparison of the volumes of pores measured and predicted for the physical mixture of waste oil sludge (WO), sewage sludge (SS) and metal sludge (MS). The generally observed trend indicates that mixing sludges results in the development of an additional pore volume. That pore volume, especially mesopores, was identified as one of the factors governing the adsorption capacity. FIG. 3 shows the dependence of the H2S removal capacity on the volume of mesopores. Since the analysis of materials pH and thermodesorption indicated elemental sulfur as an oxidation product, only mesopores can store such amount of sulfur as found from H2S breakthrough capacity tests (up to 30 wt %).

(34) Besides porosity, surface chemistry is also altered during pyrolysis of the sludge mixture as compared to the single components. FIG. 4 shows the comparison of the measured and predicted capacity based on the performance of the individual components assuming the physical mixture. The huge enhancement found, reaching 100%, is the result of changes in the composition and the surface distribution of an inorganic phase. The sludges studied contain iron, copper, nickel, zinc, calcium, chromium and other metals in significant quantities. Their high temperature reaction in the presence of carbon phase can lead to unique spinel/mineral-like components active in the oxidation reactions.

(35) FIG. 5 illustrates an increase in the mass of the sample obtained by high temperature pyrolysis. FIG. 5 shows DTG curves in nitrogen for selected adsorbants for initial and H2S exposed samples (E). The phenomenon was not observed for the samples pyrolized at low temperature. While not intending to be bound by theory, the increase may be a result of nitride formation. It was found the certain ceramic materials, when exposed to nitrogen in the presence of char, are able to form nitrides. Formation of these ceramics can be crucial for catalytic performance.

(36) Although the best adsorbents are obtained at about 650° C., the synergy is the most predominant at about 950° C. when a mineral like/ceramic phase is formed. Moreover, an increase in the mass of samples under nitrogen at about 600° C. indicates that ceramic components of adsorbents form nitrides in the presence of carbon. FIG. 6 illustrates DTG curves in nitrogen for selected adsorbants for initial and H2S exposed samples (E). Those ceramics must be active in the process of H2S adsorbents since an increase in mass significantly decreased after exposure to hydrogen sulfide and water. The surface of adsorbents treated at about 950° C. has very low affinity to retain water (hydrophobic). Temperature has also an effect on the density of the final products, which varies from about 0.25 at 650° C. to about 0.50 at 950° C.

(37) As mentioned above, unique compounds exist as crystallographic phases and they consist of metals such as calcium, magnesium, alumina, copper, iron, zinc and nonmetals such as oxygen sulfur, carbon and silica. The level of mineralization increases with an increase in the pyrolysis temperature and time. Higher temperature results in formation of two component metal-nonmetal crystallographic compounds with metals at low oxidation states. FIGS. 7A and 7B show the changes in the X-ray diffraction pattern for samples obtained at different temperatures. FIG. 7A illustrates the X-ray diffraction pattern at 650° C. and FIG. 7B is at 950° C.

(38) Advantage of the present invention include the fact that the sorbents obtained from industrial sludge have five times higher capacity for hydrogen sulfide removal than unmodified carbons. Their capacity is comparable to that of caustics impregnated carbon used worldwide as hydrogen sulfide adsorbents in sewage treatment plants. Furthermore, the kinetics of the removal process are very fast and no heat is released. Moreover, during adsorption, H.sub.2S reacts with inorganic matter and is oxidized to elemental sulfur. The product is environmentally inert. Importantly, the pH of the spent material is basic, so it can be safely discarded. Only small amounts of SO.sub.2 are released. Another advantage of the invention is that, since the sorbents are obtained from waste sludge, the significant amount of industrial and municipal waste can be recycled and reused in sewage treatment plants. The sorbents can be also used in desulfurization of gaseous fuels (for fuel cell applications) and in hydrothermal vents. The sorbents find another environmental application in removal of mercury from waste water. Furthermore, there is the possibility of regeneration of spent materials using heating to about 300° C. to remove elemental sulfur.

Example 1

(39) The homogeneous mixtures of waste sludges were prepared as listed in Table 3 and dried at 120° C. The dried samples were then crushed and pyrolized in a horizontal furnace at 950° C. for 30 min. The temperature ramp was 10 degrees/minute. An inert atmosphere was provided by 10 ml/min. flow of nitrogen. The yields, ash content and densities of materials are listed in Table 3.

(40) TABLE-US-00003 TABLE 3 Adsorbents' composition, yields, ash content and densities. Solid Yield γ Wet con- Dry (dry Ash [g/ Sample composition tent composition mass) content* cm.sup.3] WO WO: 100% 23.6 WO: 100% 29 92 0.48 SS SS: 100% 24.6 SS: 100% 45 80 0.46 MS MS: 100% 23.4 MS: 100% 47 @ 0.85 WOSS WO: 50% — WO: 49% 34 @ 0.46 SS: 50% SS: 51% WOMS WO: 50% — WO: 50% 50 @ 0.47 MS: 50% MS: 50% WOSSMS WO: 40% — WO: 46% 41 @ 0.46 SS: 40% SS: 31% MS 10% MS 23% *Determined as mass left at 950° C. after in TA run in air. @ - not determined due to reaction with air during burning

(41) The performance of materials as sorbents for hydrogen sulfide was evaluated using lab developed breakthrough tests. Adsorbent samples were packed into a column (length 60 mm, diameter 9 mm, bed volume 6 cm3) and pre-humidified with moist air (relative humidity 80% at 25° C.) for an hour. The amount of adsorbed water was estimated from the increase in the sample weight after pre-humidification (the sorbents were removed from the column and weighted). Moist air containing 0.3% (3,000 ppm) H2S was then passed through the column of adsorbent at 1.4 L/min. The breakthrough of H2S was monitored using an Interscan LD-17 H2S continuous monitor system interfaced with a computer data acquisition program. The test was stopped at the breakthrough concentration of 350 ppm. The adsorption capacities of each sorbent in terms of grams of H2S per gram of material were calculated by integration of the area above the breakthrough curves, and from the H2S concentration in the inlet gas, flow rate, breakthrough time, and mass of sorbent. The obtained results are collected in Table 4.

(42) TABLE-US-00004 TABLE 4 H.sub.2S breakthrough capacities, adsorption of water and surface pH before and after H2S adsorption (E—after exposure to H.sub.2S). Brth capacity Bth Water capacity capacity adsorbed Sample [mg/g] [mg/cm.sup.3] [mg/g] pH pHE WO 109 52 0 9.9 9.4 SS 45 21 26 10.9 10.0 MS 2.8 2.4 0 10.67 10.04 WOSS 108 50 11 10.8 9.1 WOMS 86 40 3 9.9 8.8 WOSSMS 121 56 4 10.5 9.4

(43) Characterization of pore sizes and adsorption capacity of materials prepared was accomplished using physical sorption measurement. The equilibrium adsorption isotherms of N2 were measured by volumetric techniques. From the isotherms, the pore size distribution (PSD) was evaluated using the Density Functional Theory (DFT). The surface area was calculated using BET approach and micropore volumes using Dubinin-Radushkevich equation (DR). The results are presented in Table 5. The symbol “Δ” represents the difference in the specific pore volume before and after deposition of sulfur. For all samples but MS an increase in the volume of mesopores was found as a result of deposition of elemental sulfur and formation of new pores within that deposit. The examples of PSDs are presented in FIG. 8.

(44) TABLE-US-00005 TABLE 5 Parameters of porous structure (WO—waste oil origin; SS—sewage sludge origin; MS—metal sludge origin; E—after exposure to H2S). V.sup.mes V.sup.t S.sup.BET V.sup.mic AV.sup.mic [cm.sup.3/ AV.sup.mes [cm.sup.3/ V.sup.mic Sample [m.sup.2/g] [cm.sup.3/g] [cm.sup.3/g] g] [cm.sup.3/g] g] V.sup.t WO 132 0.050 0.314 0.364 14 WO-E 96 0.034 −0.16 0.355 0.041 0.389 8 SS 141 0.058 0.151 0.209 28 SS-E 121 0.032 −0.26 0.190 0.039 0.222 17 MS 10 0.002 0.015 0.017 12 MS-E 4 0.001 −0.01 0.005 −0.010 0.006 17 WOSS 150 0.061 0.163 0.224 41 WOSS-E 89 0.030 −0.31 0.258 0.096 0.288 31 WOMS 70 0.022 0.144 0.166 13 WOMS-E 60 0.017 −0.05 0.154 0.010 0.171 11 WOSSMS 144 0.053 0.267 0.320 20 WOSSMS-E 59 0.022 −0.21 0.183 −0.085 0.205 11

(45) Thermal analysis was carried out to identify the oxidation products and to balance the amount of sulfur deposited on the surface and the results are below in Table 6. The peaks between 200-450° C., illustrated in FIG. 9, represent the removal of elemental sulfur.

(46) TABLE-US-00006 TABLE 6 Weight losses in various temperature ranges and amount of sulfur adsorbed from H2S breakthrough capacity test. Weight loss is corrected for amount adsorbed in H2S breakthrough test (Bth. Cap.) (E - after exposure to H.sub.2S). S Bth Sample 20-150° C. Δ 150-450° C. Δ 450-700° C. Δ 800-1000° C. Δ Total Δ Capacity WO 3.02 0.84 0.05 2.3 WO-E 2.31 0 9.20 8.36 1.0 0.95 1.9 0.0 9.31 10.2 SS 2.40 1.15 0.12 4.96 6.22 SS-E 3.45 1.0 1.15 0 0.03 0 2.7 6.8 4.23 WOSS 3.48 0.21 0.43 2.67 WOSS-E 3.15 0 5.85 5.64 0.53 0.1 2.67 0 5.64 10.1 WOMS 0.58 +1.88 +0.80 2.64 WOMS-E 0.81 0.23 2.56 4.44 +0.59 0.21 2.12 0 4.88 8.08 WOSSMS 1.77 0.06 0.55 2.83 WOSSMS-E 3.30 1.53 2.34 2.28 0.58 0.03 4.11 1.28 5.12 11.4

(47) X-Ray fluorescence was used to evaluate the content of iron, and sulfur after exhaustion. The results are presented in Table 7. Although the total amount is not given the intensities of the peaks in arbitrary units are related to the amount of specific species.

(48) TABLE-US-00007 TABLE 7 XRF results. Sample Fe S(E) WO 139.6 2496.86 SS 8584.02 ND MS 12844.08 ND WOSS 7321.80 ND WOMS 12574.54 732.85 WOSSMS 12173.98 1352.93

Example 2

(49) The homogeneous mixtures of waste sludges were prepared as listed in Table 8 and dried at 120° C. The dried samples were then crushed and pyrolized in a horizontal furnace at 650° C. for 30 min. The temperature ramp was 10 degrees/minute. An inert atmosphere was provided by 10 ml/min flow of nitrogen. The yields, ash content and densities of materials are listed in Table 8.

(50) TABLE-US-00008 TABLE 8 Adsorbents' composition, yield, and densities (LT—low temperature, 650° C.). Wet Solid Dry Yield γ Sample composition content composition (dry mass) [g/cm.sup.3] WOLT WO: 100% 23.6 WO: 100% 32 0.26 SSLT SS: 100% 24.6 SS: 100% 47 0.52 MSLT MS: 100% 23.4 MS: 100% 0.47 WOSSLT WO: 50%  — WO: 49%  0.36 SS: 50%  SS: 51%  WOMSLT WO: 50%  — WO: 50%  58 0.38 MS: 50%  MS: 50%  WOSSMSLT WO: 40%  — WO: 46%  46 0.38 SS: 40%  SS: 31%  MS 10%  MS 23%  *Determined as mass left at 950° C. after thermol analyses run in air.

(51) The performance of materials as sorbents for hydrogen sulfide was evaluated using lab developed breakthrough tests. Adsorbent samples were packed into a column (length 60 mm, diameter 9 mm, bed volume 6 cm.sup.3) and pre-humidified with moist air (relative humidity 80% at 25° C.) for an hour. The amount of adsorbed water was estimated from the increase in the sample weight after pre-humidification (the sorbents were removed from the column and weighted). Moist air containing 0.3% (3,000 ppm) H.sub.2S was then passed through the column of adsorbent at 1.4 L/min. The breakthrough of H.sub.2S was monitored using an Interscan LD-17 H.sub.2S continuous monitor system interfaced with a computer data acquisition program. The test was stopped at the breakthrough concentration of 350 ppm. The adsorption capacities of each sorbent in terms of grams of H.sub.2S per gram of material were calculated by integration of the area above the breakthrough curves, and from the H.sub.2S concentration in the inlet gas, flow rate, breakthrough time, and mass of sorbent. The obtained results are collected in Table 9.

(52) TABLE-US-00009 TABLE 9 H2S breakthrough capacities, adsorption of water and surface pH before and after H.sub.2S adsorption (LT—low temperature, 650° C.; E—after exposure to H.sub.2S). Brth capacity Bth capacity Water adsorbed Sample [mg/g] [mg/cm.sup.3] [mg/g] pH pH-E WOLT 315 82 48 9.3 9.3 SSLT 9 5 18 10.9  11.1  MSLT 79 37 0 7.8 7.1 WOSSLT 146 53 21 9.2 9.1 WOMSLT 130 49 14 9.8 9.4 WOSSMSLT 73 33 20 9.7 9.2

(53) Characterization of pore sizes and adsorption capacity of materials prepared was accomplished using physical sorption measurement. Equilibrium adsorption isotherms of N2 will be measured by volumetric techniques. From the isotherms the pore size distribution was evaluated using the Density Functional Theory (DFT). The surface area was calculated using BET approach and micropore volumes using Dubinin-Radushkevich equation (DR). The results are presented in Table 10. The symbol “Δ” represents the difference in the specific pore volume before and after deposition of sulfur.

(54) TABLE-US-00010 TABLE 10 Parameters of porous structure (LT—low temperature, 650° C.; E - after exposure to H.sub.2S) V.sub.mic V.sub.mes V.sub.t S.sub.BET [cm.sup.3/ ΔV.sub.mic [cm.sup.3/ ΔV.sub.mes [cm.sup.3/ V.sub.mic/ Sample [m.sup.2/g] g] [cm.sup.3/g] g] [cm.sup.3/g] g] V.sub.t WOLT 202 0.074 0.765 0.839 10 WOLT-E 83 0.032 −0.42 0.434 −0.321 0.517 6 SSLT 92 0.037 0.113 0.150 25 SSLT-E 79 0.029 −0.008 0.106 −0.007 0.135 27 MSLT 34 0.014 0.122 0.136 11 MSLT-E 25 0.011 −0.003 0.160 0.038 0.171 6 WOSSLT 154 0.058 0.459 0.517 12 WOSSLT-E 72 0.027 −0.031 0.281 −0.178 0.308 10 WOMSLT 92 0.036 0.270 0.306 12 WOMSLT-E 65 0.026 −0.010 0.265 −0.005 0.291 9 WOSSMSLT 110 0.042 0.372 0.415 10 WOSSMSLT-E 59 0.023 −0.011 0.250 −0.122 0.273 8
Thermal analysis was carried out to identify the oxidation products and to balance the amount of sulfur deposited on the surface is listed in Tables 11A and 11B, noting two different temperature ranges.
Tables 11A and 11B—Weight losses [in %] in various temperature ranges and amount of sulfur adsorbed from H2S breakthrough capacity test [in %]. Weight loss is corrected for amount adsorbed in H2S breakthrough test (Bth. Cap.); (LT—low temperature, 650° C.; E—after exposure to H.sub.2S).

(55) TABLE-US-00011 TABLE 11A S brth Sample 20-150° C. Δ 150-450° C. Δ 450-700° C. Δ 800-1000° C. Δ Total Δ capacity WOLT 4.70 1.85 1.00 6.69 WOLT-E 7.21 2.51 34.6 32.75 4.88 3.88 7.28 0.59 39.7 29.6 SSLT 1.86 0.59 0.97 9.18 SSLT-E 3.34 1.48 1.40 0.81 1.93 0.96 9.53 0.35 3.6 8.4 WOSSLT 3.56 1.49 1.04 10.46 WOSSLT-E 5.20 1.64 15.9 14.41 2.87 1.83 12.17 1.71 19.59 13.7

(56) TABLE-US-00012 TABLE 11B S brth Sample 20-150° C. Δ 150-400° C. Δ 400-650° C. Δ 150-650° C. Total Δ capacity WOLT 4.70 1.71 0.77 WOLT-E 5.42 0.72 23.35 21.64 3.41 2.64 31.6 31 SSLT 1.86 0.46 0.68 SSLT-E 3.08 1.22 1.03 0.57 1.48 0.80 1.38 0.9 MSLT 3.66 1.37 0.78 MSLT-E 4.48 0.82 13.3 11.93 2.28 1.5 15.2 14.3 WOSSLT 1.01 0 2.49 WOSSLT-E 1.16 0.15 6.62 6.62 2.13 0 7.14 7.7 WOMSLT 3.31 0 0.93 WOMSLT-E 2.86 0 6.13 6.13 2.78 1.85 9.00 12.7 WOSSMSLT 1.52 0 3.23 WOSSMSLT-E 4.65 3.13 8.2 8.2 3.16 0 9.20 12.0

Example 3

(57) The homogeneous mixtures of waste sludges were prepared as listed in Table 12 and dried at 120° C. The dried samples were then crushed and pyrolyzed in a horizontal furnace at 950° C. for 60 min. The temperature ramp was 10 deg/min An inert atmosphere was provided by 10 ml/min flow of nitrogen. The yields and densities of the materials are listed in Table 12.

(58) TABLE-US-00013 TABLE 12 Adsorbents' composition and their densities Wet Solid Dry γ Sample composition content composition [g/cm.sup.3] WO60 WO: 100% 23.6 WO: 100% 0.47 SS60 SS: 100% 24.6 SS: 100% 0.46 MS60 MS: 100% 23.4 MS: 100% 0.84 WOSS60 WO: 50%  — WO: 49%  0.41 SS: 50%  SS: 51%  WOMS 60 WO: 50%  — WO: 50%  0.46 MS: 50%  MS: 50%  WOS S MS 60 WO: 40%  — WO: 46%  0.45 SS: 40%  SS: 31%  MS 10% MS 23%

(59) The performance of materials as sorbents for hydrogen sulfide was evaluated using tab developed breakthrough tests. Adsorbent samples were packed into a column (length 60 mm, diameter 9 mm, bed volume 6 cm.sup.3) and prehumidified with moist air (relative humidity 80% at 25° C.) for an hour. The amount of adsorbed water was estimated from the’ increase in the sample weight after pre-humidification (the sorbents were removed from the column and weighted). Moist air containing 0.3% (3,000 ppm) H.sub.2S was then passed through the column of adsorbent at 1.4 L/min. The breakthrough of H.sub.2S was monitored using an Interscan LD-17 H.sub.2S continuous monitor system interfaced with a computer data acquisition program. The test was stopped at the breakthrough concentration of 350 ppm. The adsorption capacities of each sorbent in terms of grams of H.sub.2S per gram of material were calculated by integration of the area above the breakthrough curves, and from the H.sub.2S concentration in the inlet gas, flow rate, breakthrough time, and mass of sorbent. The obtained results are collected in Table 13.

(60) TABLE-US-00014 TABLE 13 H2S breakthrough capacities, adsorption of water and surface pH before and after H.sub.2S adsorption (E—after exposure to H.sub.2S) Brth Bth Water capacity capacity adsorbed Sample [mg/g] [mg/cm.sup.3] [mg/g] pH pH-E WO60 61 29 11 10.7 10.2 SS60 78 36 26 10.5 9.3 MS60 2 1.7 0 9.8 9.6 WOSS60 78 32 36 11.8 9.8 WOMS60 9.4 WOSSMS60 73 33 20 10.7 10.2

Example 4

(61) X-ray diffraction measurements were conducted on WO, SS, MS, WOSS and WOSSMS adsorbent samples using standard powder diffraction procedure. Adsorbents were ground with methanol in a small agate mortar. Grinding of the adsorbents by hand ensures particle sizes between 5-10 μm, which prevents line broadening in diffraction peaks. The mixture was smear-mounted onto the zero-background quartz window of a Philips specimen holder and allow to air dry. Samples were analyzed by Cu KO radiation generated in a Phillips XRG 300 X-ray diffractometer. A quartz standard slide was run to check for instrument wander and to obtain accurate location of 2Θ peaks.

(62) In the waste oil based sludge sample heated at 650° C. (WO650) only metallic copper was detected as a separate crystallographic phase. See, FIG. 10. In the case of SS650, quartz (SiO.sub.2), cristobalite (SiO.sub.2), truscottite Si.sub.24)O.sub.58(OH).sub.8 2H.sub.2O), and metallic iron are present. After mixing two components and heating at 650° C., besides quartz, cristobalite and metallic iron and copper, anorthite (CaAl.sub.2Si.sub.2O.sub.8) and diaspore (AlO(OH)) are detected.

(63) Comparison of the diffraction patterns presented in FIG. 10 clearly shows the synergetic effect in the chemical composition of materials. New components formed having their origin on addition of silica (coming from sewage sludge), and iron and zinc from waste oil sludge. These results indicated formation of new phases with an increase in the pyrolysis temperature and time. FIG. 10 shows the changes in chemistry after pyrolysis for half an hour at 650° C. while FIGS. 7A and 7B compare the sample pyrolyzed at 950° C.

(64) The examples of crystallographic phases found for samples pyrolyzed at various conditions are presented in Tables 14 and 15. The headings indicate the composition of the sample, the temperature it was pyrolyzed at and the duration of the pyrolysis. For example, SS650-0.5 is sewage sludge pyrolyzed at 650° C. for 30 minutes.

(65) TABLE-US-00015 TABLE 14 Crystallographic phases identified based on XRD analysis WOSS650- WOSS950- SS650-0.5 W0650-0.5 0.5 SS950-0.5 W0950-0.5 0.5 Aluminum Aluminum Anorthite Iron, Fe Al Al CaAl.sub.2Si.sub.2O.sub.8 Iron, Fe Iron, Fe Bayerite Al(OH).sup.3 Bornite Bornite Bornite Cu.sub.5FeS.sub.4 Cu.sub.5FeS.sub.4 Cu.sub.5FeS.sub.4 Maghemite Fe.sub.2O.sub.3 Cohenite Fe.sub.3C Lawsonite CaAl.sub.2Si.sub.20.sub.7(O H).sub.2 H.sub.2O Hibonite CaAl.sub.12O.sub.19 Diaspore Ankerite A1O(OH) Ca(Fe, Mg)CO.sub.3).sub.2 Calcite Huntite Vaterite Vaterite Magnesium Mg3C(CO3)4 CaCO.sub.3 CaCO3 Sapphirine Sapphirine Sapphirine (Mg.sub.4A1.sub.4)A1.sub.4Si.sub.2O.sub.20 (Mg.sub.4A1.sub.4)A1.sub.4Si.sub.2O.sub.20 (mg.sub.4A1.sub.4)A1.sub.4Si.sub.2O.sub.20 Spinel Spinel MgA12O4 MgA1.sub.2O.sub.4 Barringerite Zincite Zincite Fe.sub.2P ZnO ZnO Wurtzite Wurtzite ZnS ZnS Goethite Ferroxyhite, Lepidicroc FeO(OH) goethite Ite, FeO(OH) FeO(OH) Almandine Smithsonite Fe3A12(SiO4)3 ZnCO.sub.3 Quartz Quartz Quartz Cristobalite SiO.sub.2 SiO.sub.2 SiO.sub.2

(66) TABLE-US-00016 TABLE 15 Crystallographic phases identified based on XRD analysis MS650 MS950 WOSSMS650 WOSSMS950 Aluminum Aluminum Al Iron, Fe Iron, Fe Iron, Fe Copper, Cu Copper, Cu Zinc, Zn Huntite Mg.sub.5Ca(CO.sub.3) Hernatite, Fe.sub.2O.sub.3 Fersilicite, FeSi Moisanite, SiC Margarite, CaAl(Si.sub.2Al.sub.2)O.sub.10(OH).sub.2 Almandine Sphalerite, ZnS Fe.sub.3Al.sub.2(SiO.sub.4).sub.3 Pyrrhotite, Pyrrhotite, Pyrrhotite, Fe.sub.1−xS Fe.sub.1−xS Fe.sub.1−xS Trioilite, FeS Trioilite, FeS Trioilite, FeS Pyrope, Spinel Mg.sub.3Al.sub.2(SiO.sub.4).sub.3 MgA1.sub.2O.sub.4 Chalocopyrite CuFeS.sub.2 Pyrrohotite Sphalerite Fe.sub.7S.sub.8 ZnS Zhanghengite, CuZn Quartz, SiO.sub.2 Quartz, Cristobalite Moganite, SiO.sub.2 SiO.sub.2

(67) Thus, in sewage sludge origin materials obtained at 950° C. such spinel-like compounds as wurtzite (ZnS), ferroan (Ca.sub.2(Mg,Fe).sub.5(SiAl).sub.8O.sub.22(OH).sub.2), chalcocite (Cu.sub.1.96S), spinel (MgAl.sub.2O.sub.4), and feroxyhite (FeO(OH)) were found. In waste oil-based materials besides metallic iron, bornite (Cu.sub.5FeS.sub.4), hibonite (CaAl.sub.12O.sub.19), zincite (ZnO), ankerite (Ca(Fe, Mg)(CO.sub.3).sub.2) are present. In metal sludge based adsorbent aluminum, metallic iron, copper, zinc, pyrope (Mg.sub.3Al.sub.2(SiO.sub.4).sub.3), perrohotite (Fe.sub.7S.sub.8), Chalocopyrite (CuFeS.sub.2), Triolite (FeS) and Fersilicite, (FeSi) exist. Mixing sludges results in synergy enhancing the catalytic properties which is linked to formation of new entities such as sapphirine (Mg.sub.3,5Al.sub.9Si.sub.1.5O.sub.20), maghemite (Fe.sub.2O.sub.3), cohenite (Fe.sub.3C), lawsonite (CaAl.sub.2Si.sub.2O.sub.7(OH)2H.sub.2O), smithsonite (ZnCO.sub.3), sphalerite (ZnS), and hematite (Fe.sub.2O.sub.3).

(68) The materials obtained at 650° C. differ significantly from those obtained at 950° C. In the latter, more double-component crystallographic phases (metal-nonmetal) are present with metals at lower oxidation states. The samples pyrolyzed at 650° C. contain more aluminosilicates with calcium, magnesium and iron cations.

Example 5

(69) The performance of adsorbents obtained at 650° C. and 950° C. for 0.5 hour or 1 hour as H2S removal media was compared. The results are presented in Tables 16-18.

(70) TABLE-US-00017 TABLE 16 H2S breakthrough capacities, amount of water pre-adsorbed, and pH values for the initial and exhausted adsorbents. H25 Brth. H2S Brth. Water Cap. Cap. adsorbed Sample [mg/g] rmg/cm.sub.3] [mg/g] pH pH-E W0650-0.5 315 82 48 9.3 9.3 W0950-0.5 109 52 0 9.9 9.4 W0950-1 62 29 11 10.7 10.2 SS650-0.5 9 5 18 10.9 11.1 SS950-0.5 42 21 26 10.9 10.0 SS950-1 78 36 26 10.5 9.3 W0SS950-0.5 146 53 21 9.2 9.1 WOSS950-0.5 108 50 11 10.8 9.1 W0SS950-1 78 32 36 11.8 9.4

(71) TABLE-US-00018 TABLE 17 Shift in the pH-ΔpH between initial and exhausted samples, amount of sulfur expected based on the H.sub.2S breakthrough capacity-SBT, weight loss between 150-400° C., [ ]W, and selectivity for oxidation to elemental sulfur, S.sub.el SBT ΔW S.sub.el Sample ΔpH [%] [%] [%] W0650-0.5 0 30.8 22.52 73 W0950-0.5 0.5 10.7 6.04 56 W0950-1 0.5 6.1 4.39 72 SS650-0.5 0 0.8 0.15 19 SS950-0.5 0.9 4.1 2.02 47 SS950-1 0.8 7.7 4.32 56 WOSS650-0.5 0.1 14.2 11.91 83 WOSS950-0.5 1.7 10.6 4.58 42 WOSS950-1 2.4 7.7 6.32 82

(72) TABLE-US-00019 TABLE 18 Structural parameters calculated from nitrogen adsorption isotherms S.sub.BET V.sub.mic V.sub.mes V.sub.t Sample [m.sup.2/g] [cm.sup.3/g] [cm.sup.3/g] [cm.sup.3/g] V.sub.mes/V.sub.t W0650-0.5 202 0.074 0.765 0.839 0.92 W0650-0.5E 83 0.032 0.434 0.517 0.84 W0950-0.5 132 0.050 0.314 0.364 0.86 W0950-0.5E 96 0.054 0.355 0.389 0.91 W0950-1 92 0.037 0.303 0.340 0.89 W0950-1E 64 0.024 0.275 0.299 0.92 SS650-0.5 92 0.037 0.113 0.150 0.75 S5650-0.5E 79 0.029 0.106 0.135 0.78 SS950-0.5 141 0.058 0.151 0.209 0.72 SS950-0.5E 121 0.032 0.190 0.222 0.85 SS950-1 125 0.049 0.138 0.187 0.74 S5950-1E 47 0.018 0.124 0.132 0.94 WOSS650-0.5 154 0.058 0.459 0.517 0.89 WOSS650-0.5E 72 0.027 0.281 0.308 0.91 WOSS950-0.5 150 0.061 0.163 0.224 0.73 WOSS950-0.5E 89 0.030 0.258 0.288 0.89 WOSS950-1 199 0.075 0.377 0.447 0.84 WOSS950-1E 79 0.031 0.269 0.300 0.90

(73) The results demonstrate the possibility of obtaining the valuable desulfurization catalysts from mixture of waste oil sludge and sewage sludge. Up to 30 wt % hydrogen sulfide can be retained on their surface. The surface properties, such as porosity, selectivity, or catalytic activity can be modified by changing the pyrolysis conditions. The catalytic activity and hydrogen sulfide removal capacity are directly related to the new surface chemistry formed by solid-state reactions during pyrolysis. This chemistry can also be controlled to certain degree by varying the composition of the precursor mixture. As a result of the synergy between the sludge components new chemistry and porosity is formed which enhances both the physicochemical properties of the materials and their performance. FIG. 11 shows the comparison of the predicted (based on the composition and yield of the individual components) and measured volume of mesopores while FIG. 12 compares the predicted and measured H2S breakthrough capacities.

Example 6

(74) Equilibrium studies for adsorption of acid red and basic fuchsin were conducted in a series of 100 ml Erlenmeyer flasks at 293 K. Each flask was filled with 10 ml of dye solution—with concentrations between 10-1000 mg/l. After equilibration, the samples were filtrated, analyzed for their dyes content and the equilibrium adsorption capacity was calculated. The equilibrium data was fitted to the so-called Langmuir-Freundlich single solute isotherm. The results are presented in Table 19. The variable q.sub.m is the adsorption capacity per unit gram of adsorbent, K is the Langmuir-type equilibrium constant, and the exponential term n is the heterogeneity parameter of the site energy.

(75) TABLE-US-00020 TABLE 19 Fitting parameters to Langmuir-Freundlich isotherm q.sub.m K ample [mg dye/g] [1/mg] n R.sup.2 Acid Red1 SS 45.00 0.10 0.44 0.9706 WO 46.35 0.14 0.23 0.9757 WOSSO 71.19 0.17 0.75 0.9610 WOSS650 68.40 0.15 0.74 0.9325 WVA 71.42 0.029 0.76 0.9919 Basic Fuchsin SS 70.36 0.03 0.36 0.9969 WO 94.21 0.18 0.65 0.9851 WOSS 126.89 0.29 0.59 0.9929 WOSS650 105.94 0.15 0.57 0.9804

(76) The adsorption capacity is much higher than that for commercial activated carbon and it is attributed to the high volume of mesopores and the presence of mineral-like structures, which can participate in ion exchange reactions and precipitation reactions.

Example 7

(77) To check the effect of water exposure on the porosity of samples, the materials were dispersed in water and shake in room temperature for 24 hours. After drying the surface area, pore volumes and the average pore sizes were determined. The results indicted an increase in the volume of mesopores are as a result of the reaction of inorganic oxides/salts with water. The results are presented in Table 20. Δ is the average pore size.

(78) TABLE-US-00021 TABLE 20 Structural parameters S.sub.BET V.sub.mic V.sub.mes V.sub.t Δ Sample (m.sup.2/g) (cm.sup.3/g) (cm.sup.3/g) (cm.sup.3/g) V.sub.mic/V.sub.t (Å) SS 950 103 0.043 0.100 0.143 0.301 56 SS950-H.sub.20 100 0.041 0.095 0.136 0.302 55 W950 128 0.047 0.363 0.414 0.114 130 W0950-H.sub.20 109 0.040 0.390 0.431 0.093 158 WOSS950 192 0.077 0.279 0.356 0.216 74 WOSS950-H.sub.20 174 0.068 0.301 0.369 0.184 85 WOSS650 108 0.043 0.317 0.356 0.121 132 WOSS0650-H.sub.20 199 0.077 0.253 0.332 0.232 67

Example 8

(79) Equilibrium studies for adsorption of copper were conducted in a series of 100 ml Erlenmeyer flasks at 20° C. Each flask was filled with 10 ml of copper chloride solution with concentrations between 10-1000 mg/l. After equilibration, the samples were filtrated, analyzed for their coppers content and the equilibrium adsorption capacity was calculated. The equilibrium data was fitted to the so-called Langmuir-Freundlich single solute isotherm. The results are presented in Table 21. The variable q.sub.m is the adsorption capacity per unit gram of adsorbent, K is the Langmuir-type equilibrium constant, and the exponential term n is the heterogeneity parameter of the site energy. The adsorption capacity, especially for samples obtained at 650° C. is much higher than that on activated carbon.

(80) TABLE-US-00022 TABLE 21 Fitting parameters of copper (Cu.sup.2+) adsorption isotherms to Langmuir-Freundlich Equation q.sub.m K Sample [mg Cu.sup.2+/g] [1/mg] n R.sup.2 SS650 63.48 0.009 0.65 0.9985 W0650 74.28 0.025 0.72 0.9964 WOSS650 69.72 0.018 0.78 0.9978 SS950 34.01 0.001 0.51 0.9970 W0950 15.88 0.006 0.92 0.9834 WOSS950 47.08 0.001 0.43 0.9957

Example 9

(81) The content of Fe, Ca, Cu, Zn, and Mg was determined in the single component samples, and based on the composition of the mixed samples, the content of these elements was evaluated. The results are presented in Table 22.

(82) TABLE-US-00023 TABLE 22 Cr Sample Fe [%] Ca [%] Mg [%] Cu [%] Zn[%] [ppm] SS650 4.9 4.8 1.3 0.13 0.19 58 SS950 6.1 5.1 1.1 0.17 0.09 90 W0650 3.2 4.0 11.0 0.20 0.54 140 W0950 3.7 5.1 8.4 0.25 0.51 280 MS950 2.2 14 0.46 0.77 0.16 6700 WOSS650* 4.0 4.4 6.15 0.16 0.36 99 WOSS950* 4.9 5.1 4.75 0.21 0.3 185 WOSSMS950* 4.4 6.9 3.89 0.32 0.27 1488 *evaluated assuming the same yield of each component (50%).

Example 10

(83) Materials

(84) Two industrial sludges, waste oil sludge (WO) and metal sludge (M) from Newport News Shipyard were mixed with dry tobacco compost, homogenized, dried at 120° C. for 48 hours and then carbonized at 650° C. and 950° C. in nitrogen in a horizontal furnace. The heating rate was 10 deg/min with a one hour holding time. The weight of the wet industrial sludges (they contain 75% water) was adjusted to have 10% and 50% industrial sludge component based on the dry mass. The names of the adsorbents obtained, their compositions along with the yield, ash content and bulk density are collected in Table 23. Tobacco waste is referred to as TC.

(85) The waste oil sludge was treated with CaCl.sub.2, Na.sub.3PO.sub.4, NaOH and alum. Metal sludge treatment history includes addition of sulfuric acid and sodium hydroxide for pH adjustments, Al.sub.2SO.sub.4 for coagulation, anionic and cationic polymers, sodium bisulfide for chromium reduction, lime and CaCl.sub.2. Thus, besides alkaline or alkaline earth element-containing compounds and iron, the waste oil sludge also contains 0.4% Cu, 2% Zn and between 200 and 1000 ppm of chromium, lead and nickel. In metal sludge there are less than 1% each of cadmium, chromium, copper, lead, manganese, selenium, vanadium and zinc. The content of volatile compounds in both waste oil sludge and metal sludge reaches 40% their dry mass, while the content of water in as-received materials is about 75%.

(86) TABLE-US-00024 TABLE 23 Names of the adsorbents, their compositions, pyrolysis temperature, yield, bulk density an ash content Pyrolysis Bulk Dry waste Temperature Yield Density Ash Sample composition [° C.] [%] [g/cm.sup.3] [%] CTCA TC: 100% 650 52 0.63 67 CTCB TC: 100% 950 51 0.52 76 CWOB WO: 100% 950 30 0.48 92 CMB M: 100% 950 47 0.58 ND CTCWO-1A TC 90%; WO 10% 650 52 0.42 72 CTCWO-2A TC 50%; WO 50% 650 53 0.41 67 CTCWO-1B TC 90%; W010% 950 45 0.40 78 CTCWO-2B TC: 50%; WO 50% 950 38 0.40 86 CTCM-1A TC 90%; M 10(7o 650 0.55 63 CTCM-2A TC 50%; M 50% 650 65 0.52 86 CTCM-1B TC 90%; M 10% 950 0.58 95 CTCM-2B TC 50%; M 50% 950 57 0.30 96
Evaluation of H2S Sorption Capacity

(87) A custom-designed dynamic test was used to evaluate the performance of adsorbents for H2S adsorption from gas streams as described above. Adsorbent samples were ground (1-2 mm particle size) and packed into a glass column (length 370 mm, internal diameter 9 mm, bed volume 6 cm.sup.3), and pre-humidified with moist air (relative humidity 80% at 25° C.) for one hour. The amount of water adsorbed was estimated from an increase in the sample weight. Moist air (relative humidity 80% at 25° C.) containing 0.3% (3,000 ppm) of H.sub.2S was passed through the column of adsorbent at 0.5 L/min. The flow rate was controlled using Cole Parmer flow meters. The breakthrough of H.sub.2S was monitored using MultiRae photoionization sensor. The test was stopped at the breakthrough concentration of 100 ppm. The adsorption capacities of each adsorbent in terms of mg of hydrogen sulfide per g of adsorbent were calculated by integration of the area above the breakthrough curves, and from the H.sub.2S concentration in the inlet gas, flow rate, breakthrough time, and mass of sorbent. For each sample the test was repeated at least twice. Besides H.sub.2S the content of SO.sub.2 in the outlet gas was also monitored using MultiRae photoionization sensor. The adsorbents exhausted after H.sub.2S adsorption are designated by adding an additional letter E to their names.

(88) Characterization of Pore Structure of Adsorbents

(89) On the materials obtained sorption of nitrogen at its boiling point was carried out using ASAP 2010 (Micromeritics). Before the experiments, the samples were outgassed at 120° C. to constant vacuum (10-4 ton). From the isotherms, the surface areas (BET method), total pore volumes, Vt, (from the last point of isotherm at relative pressure equal to 0.99), volumes of micropores, V.sub.mic (DR), mesopore volume V.sub.mes, total pore volume, V.sub.t, along with pore size distributions were calculated (DFT).

(90) pH

(91) The pH of a carbonaceous sample suspension provides information about the acidity and basicity of the surface. A sample of 0.4 g of dry carbon powder was added to 20 mL of distilled water and the suspension was stirred overnight to reach equilibrium. Then the pH of suspension was measured.

(92) Thermal Analysis

(93) Thermal analysis was carried out using TA Instrument Thermal Analyzer. The instrument settings were: heating rate 10° C./min and a nitrogen atmosphere with 100 mL/min flow rate. For each measurement about 25 mg of a ground adsorbent sample were used. For analysis of the results the derivative thermogravimetric curves (DTG curves) are used. Ash content was determined from the residue left at 800° C. after heating the samples in air.

(94) Elemental Analysis

(95) Metal content in the adsorbents was determined using ICP in LSL labs, Syracuse, N.Y.

(96) XRD

(97) X-ray diffraction measurements were conducted using standard powder diffraction procedure. Adsorbents were ground with methanol in a small agate mortar. Grinding of the adsorbents by hand ensures particle sizes between 5-10 which prevents line broadening in diffraction peaks. The mixture was smear-mounted onto the zero-background quartz window of a Phillips specimen holder and allow to air dry. Samples were analyzed by Cu K.sub.a radiation generated in a Phillips XRG 300 X-ray diffractometer. A quartz standard slide was run to check for instrument wander and to obtain accurate location of 20 peaks.

(98) The H.sub.2S breakthrough curves are presented in FIGS. 13 and 14. As seen based on the steep rise in the breakthrough curves all tobacco based materials have short diffusion zone and almost immediately after H.sub.2S is detected in the outlet gas, the adsorbents stop to work allowing the challenge gas to pass chemically undisturbed through the bed. No SO.sub.2 concentration was detected which indicates that all H.sub.2S is converted to sulfur. In the case of metal and oil sludge derived materials small concentrations of sulfur dioxide, up to few ppm were measured at the same time when hydrogen sulfide appeared in the outlet gas. Even after mixing 50% tobacco waste and 50% waste oil, the kinetics of hydrogen sulfide retention characteristic to tobacco were still predominant since the shape of the slope of the curve does not resemble the one obtained for waste oil derived adsorbent.

(99) The results of the H.sub.2S breakthrough capacity measurements are summarized in Table 24 where besides the capacity expressed unit mass per gram of the adsorbents and per unit volume of the bed, the amount of water adsorbed during the prehumidification and the pH of the surface before and after adsorption process are reported.

(100) As seen from Table 24, the highest capacity is found for tobacco waste oil sludge compositions pyrolyzed at 950° C. Although higher content of oil sludge is beneficial for the performance, even only 10% waste oil sludge increases the performance about 100% compared to pure tobacco waste based material. For CTC material the high temperature of pyrolysis also significantly enhances the capacity. The results suggest the predominant influence of the tobacco waste on the performance since the waste oil sludge derived materials were reported to have best capacity at low temperature. In fact comparison of the capacity obtained for both tobacco and waste oils sludge based materials obtained at 950° C. clearly shows the synergetic effect; the capacity obtained for the mixture is much higher than for either one of its components.

(101) TABLE-US-00025 TABLE 24 H.sub.2S breakthrough capacity, amount of water absorbed and the PH values of adsorbent surfaces. H2S breakthrough water capacity adsorbed pH Sample [mg/g] [mg/cm.sup.3] [mg/g] initial exhausted CWOB 40.2 21.1 11 10.7 10.2 CMB 5.0 2.9 0 11.2 11.2 CTC-A 6.6 4.2 51.8 11.2 10.7 CTC-B 23.1 12.1 38.2 11.3 11.3 CTCWO-1A 16.1 6.7 45.4 10.6 9.6 CTCWO-2A 0.9 0.4 82.0 9.2 9.2 CTCWO-1B 42.6 17.8 35.4 10.0 9.8 CTCWO-2B 90.2 36.4 43.3 10.3 9.3 CTCM-1A 13.0 7.2 29.6 10.6 10.5 CTCM-2A 22.5 11.7 11.2 9.4 9.3 CTCM-1B 23.1 13.5 21.5 11.2 11.1 CTCM-2B 18.9 5.7 10.8 10.8 10.6

(102) As seen from Table 24, the highest capacity is found for tobacco waste oil sludge mixtures pyrolyzed at 950° C. Although higher content of oil sludge is beneficial for the performance, even only 10% waste oil sludge increases the performance about 100% compared to pure tobacco waste based material. For CTC material, the high temperature of pyrolysis also significantly enhances the capacity. These results suggest the predominant influence of the tobacco waste on the performance since the waste oil sludge derived materials were reported to have best capacity at low temperature. In fact comparison of the capacity obtained for both tobacco and waste oils sludge-based materials obtained at 950° C. clearly shows the synergetic effect; the capacity obtained for the mixture is much higher than for either one of its components.

(103) Pyrolysis of waste oil sludge/tobacco mixture at 650° C. with a high content of waste oil sludge component has a detrimental effect on the capacity. Although on the surface of this sample the high amount of water is adsorbed, the capacity is negligible. Since the materials from waste oil sludge pyrolized at 650° C. had a very high capacity (reaching 30% wt.), the tobacco component hinders the capacity when low temperature treatment is applied. On the other hand, when metal sludge is used and mixture is pyrolyzed at low temperature, the capacity is enhanced compared to pure tobacco or pure metal sludge. Pyrolyzing those two mixtures at high temperature enhances capacity for low sludge content indicating once again the importance of the tobacco phase for hydrogen sulfide removal on composite adsorbents.

(104) Taking into account variations in the behavior of the samples within their pyrolysis temperature, the relationship between the amount of water preadsorbed and the H.sub.2S breakthrough capacity was analyzed. As seen from FIG. 15, for the samples pyrolyzed at low temperature have a detrimental effect on the H.sub.2S breakthrough capacity. This may be linked to the low degree of mineralization and reactivity of the surface. It is likely that exposure to water causes its reaction with metal oxides and formation of hydroxides, which was observed previously. If the small pores are present, those hydroxides may block their entrances and thus decrease the available space for H.sub.2S adsorption and sulfur storage. This problem is readdressed below were the porosity is discussed.

(105) In the case of samples pyrolyzed at 950° C., water apparently enhances the capacity. This might be linked to its physical retention on the surface and formation of water film, in which the basic pH exists. This enables high concentration of HS ions and thus their oxidation to elemental sulfur.

(106) All samples have basic pH, which helps with in hydrogen sulfide removal. The lowest pH is found for the CTCWO-2A sample, which has also the very low H.sub.2S removal capacity. That pH is much lower than the pH of its components. The reason for this might be either in oxidation of the carbon phase or specific chemistry formed as a result of synergetic effect between the composite components.

(107) Checking the synergetic effect on the H.sub.2S breakthrough capacity, the measured values were compared to those calculated assuming the physical mixtures of the components, and taking into account their yields. The results presented in FIG. 16. While in the case of metal sludge only slight enhancement in the capacity is observed as a result of mixing, for the waste oil sludge/tobacco composites a significant synergetic effect is found with four fold increase in the capacity for CTCWO-2B.

(108) That synergetic effect might be the result of either new catalytic phases formed when the materials are mixed and exposed to high temperature, formation of new pores enhancing physical adsorption and storage of oxidation products, an increased dispersion of catalytic phase, or more likely, the combination of all of these factors.

(109) Using X-ray diffraction one may see both, the changes in the degree of crystallinity of the adsorbents and the formation of new phases as a result of solid state reaction. FIG. 17 shows the comparison of XRD patterns for CTC adsorbents obtained at 650 and 950° C. As seen from the analysis of the ash content (Table 23) all adsorbents, even those derived from only tobacco waste have the majority of the inorganic phase. In the case of CTCA only quartz, and magnesian of ferrosilite ((Fe,Mg)SiO.sub.3) are identified. Heating at 950° C. results in formation of more crystalline phases identified as bayerite (Al(OH).sub.3), ordered anorthite (CaAl.sub.2Si.sub.2O.sub.8), anthophyllite ((Mg, Fe).sub.7Si.sub.8O.sub.22(OH).sub.2), and barrigerite (Fe.sub.2P). Some of these minerals such as barrigerite, were also identified in sewage sludge derived materials in which enhanced H.sub.2S adsorption was found. Magnesium, calcium and iron from these minerals can contribute to catalytic oxidation of hydrogen sulfide to sulfur. In the case of CWOB metallic iron, bornite (Cu.sub.5FeS.sub.4), hibonite (CaAl.sub.12O.sub.19), zincite (ZnO) and ankerite (Ca(Fe Mg)(CO.sub.3).sub.2) are detected (FIG. 18). Heating metal sludge to 950° C. resulted in formation of numerous crystalline phases (multipeak pattern) from which pyrrohotite (Fe.sub.1-xS), troilite (FeS), pyrope (Mg.sub.3Al.sub.2(SiO.sub.4).sub.3), and metallic copper, zinc and iron have high probability to exist.

(110) A multipeak pattern is also observed for the mixtures of tobacco with metal sludge of various compositions and pyrolyzed at two different temperatures. Comparison of FIGS. 17, 18 and 19 clearly shows that new phases are detected. Examples of these new phases for CTCM-1A are spinel (MgAl.sub.2O.sub.4), margarite (CaAl.sub.2(Si.sub.2Al.sub.2)0.sub.10(OH).sub.2), malachite (Cu.sub.2CO.sub.3(OH).sub.2, calcite (CaCO.sub.3), cordierite (Mg.sub.2A.sub.14Si.sub.50.sub.18), pigeonite (Fe, Mg, Ca)SiO.sub.3), corundum (Al.sub.20.sub.3), tenorite (CuO), magnesioferrite (MgFe.sub.2O.sub.4), moissanite (SiC) and metallic iron. By pyrolyzing at 950° C., the mixture containing more metal sludge derived phase results in even more complex chemistry with predominant structures of mixed calcium iron and magnesium silicates and aluminosilicates. Some of them, as ferrocilite, anorthite were present in CTC-A. Examples are fosterite (Mg.sub.2SiO.sub.4), huntite (Mg.sub.3Ca(CO.sub.3).sub.4), aragonite (CaCO.sub.3), wollastonite (CaSiO.sub.3), dolomite (CaMg(CO.sub.3).sub.2, cohenite, (Fe.sub.3C) fersilicite (FeSi), covelite (CuS), bornite (CuSFeS.sub.4), grunerite (Fe.sub.7S.sub.18O.sub.22(OH).sub.2), hardystonite (Ca.sub.2ZnSi.sub.2O.sub.7) or akermanite (Ca.sub.2MgSi.sub.2O.sub.7). In this case, compared to the sample pyrolized at 650° C., more carbonates are present, likely the result of gasification of carbon, less aluminum is involved in crystalline phase, and more two element-compounds appear.

(111) Very complex and different form parent compound structure is obtained for CTCWO-2B (FIG. 19). In this case, besides significant amount of quartz, over 50 new compounds were detected. They are mainly aluminoslicate with magnesium, calcium, iron, sodium, copper and lead. Examples include: sodian of anorthite ((Ca, Na) (Al, Si).sub.2Si.sub.2O.sub.8), forsterite (Mg.sub.2SiO.sub.4), albite (CaAl.sub.2Si.sub.2O.sub.8), richterite (KNaCaMg.sub.5Si.sub.80.sub.22(OH).sub.2), renhahnite (Ca.sub.3(Si.sub.3O.sub.8(OH).sub.2), Dahlite (Ca.sub.9.35Na.sub.1.07(PO.sub.4).sub.5.46CO.sub.3), rockbridgeite (Fe.sub.5 (PO.sub.4).sub.3(OH).sub.5).

(112) Although surface chemistry can play a crucial role in the process of hydrogen sulfide oxidation on the surface of materials studied, its effects cannot be discussed in isolation from the description of porous structure. The nitrogen adsorption isotherms are collected in FIGS. 20 and 21. Their shapes and nitrogen uptakes indicate differences in the sizes and volume of pores. While tobacco derived adsorbents are both very microporous, addition of waste oil sludge and metals sludge component contributes to the development of mesoporosity. The structural parameters calculated from nitrogen adsorption isotherms are collected in Table 25. Either waste oil sludge or metal sludge addition increase the surface areas of samples obtained at 950° C. in spite of the fact that the surface areas of both components pysolyzed separately are much smaller This indicates the beneficial synergetic effect. That development of porosity can be caused by gasification of carbon phase by alkaline earth metals present in the sludges, which can be considered as self-activation. Adding more waste oil sludge increases surface area, volume of micropores and volume of mesopores. Although the latter are present in much higher volume in the CWOB adsorbent, the new volume of micropores is the result of activation during pyrolysis. On the other hand, addition of metal sludge, even in only small quantity seems to be most beneficial for tobacco/metal sludge mixtures. These materials have a new volume of mesopores formed, which do not exist in either tobacco or metal sludge only based materials. Gasification can be important here. Much more alkaline earth metals than in waste oil sludge results (Table 26) in formation of larger pores in the carbonaceous deposit. It is interesting that the smallest surface area and pore volume are obtained for metal sludge tobacco mixture with 50/50 ratio of composition pyrolyzed at 650° C. This is consistent with this sample low capacity for hydrogen sulfide removal. Since both tobacco derived samples have almost identical structural parameters the differences in their performance as hydrogen sulfide adsorbents must be attributed to differences in surface chemistry mentioned above.

(113) TABLE-US-00026 TABLE 25 Structural parameters calculated from nitrogen adsorption SBET Vmic Vmeso Vt DBJH DDA E.sub.o Sample [m.sup.2/g] [cm.sup.3/g] [m.sup.2/g] [cm.sup.3/g] V.sub.mic/V.sub.t [Å] [Å] [kJ/mol] CTCA 73 0.037 0.016 0.053 0.698 69 15 25.06 CTCAE 0 0 0 0 0 0 0 0 CTCB 78 0.039 0.020 0.059 0.661 41 16 21.82 CTCB-E 42 0.017 0.039 0.056 0.304 44 17 19.28 CTCWO-1A 71 0.041 0.051 0.092 0.446 95 16 23.80 CTCWO-1AE 33 0.014 0.088 0.102 0.137 100 17 17.62 CTCWO-2A 35 0.015 0.165 0.180 0.083 123 21 10.09 CTCWO-2AE 13 0.009 0.127 0.136 0.066 144 21 9.61 CTCWO-1B 120 0.055 0.096 0.151 0.364 56 16 20.65 CTCWO-1BE 37 0.019 0.072 0.091 0.209 68 17 17.55 CTCWO-2B 162 0.069 0.180 0.249 0.277 61 17 20.01 CTCWO-2BE 59 0.026 0.163 0.189 0.138 85 18 15.45 CTCM-1A 77 0.035 0.071 0.106 0.330 63 15 23.94 CTCM-1AE 8 0.006 0.047 0.053 0.113 138 17 18.79 CTCM-2A 74 0.031 0.144 0.175 0.177 79 17 18.67 CTCM-2AE 24 0.013 0.115 0.128 0.102 124 18 16.36 CTCM-1B 96 0.043 0.113 0.156 0.276 62 16 20.53 CTCM-1BE 46 0.018 0.097 0.115 0.157 99 18 15.62 CTCM-2B 59 0.031 0.061 0.092 0.337 82 16 20.19 CTCM-2BE 49 0.022 0.109 0.131 0.168 107 18 16.67

(114) After H.sub.2S removal the surface area and volumes of micropores significantly decrease. For the majority of samples, but CTC-BE, CTCWO-1AE and CTCM-2BE the volume of mesopores increases. This phenomenon was observed before and was attributed to formation of new pores within either sulfur deposit in large pores, if capacity was high, or/and formation of hydroxides on the surface as a result of exposure to water during prehumidification. Although in the case of CTCM-2BE only small amount of water was adsorbed with relatively high amount of H2S, taking into account the small surface area of the samples, a significant, almost 100% increase in the volume of mesopores can be attributed to that sulfur deposit. The surface in large pores of the materials must be active since extensive gasification helped in high dispersion on the catalysts on the surface. For CTCWO-1AE, that increase can be attributed to the formation of hydroxides, since the surface is active and large amounts of water are adsorbed, and also to sulfur deposit. These hydroxides can totally block the porosity in the carbon deposit when more sludge derived phase is present and sample is exposed to moisture from the atmosphere. This likely happens in the case of CTCWO-2A, which was totally inactive in the process of H2S adsorption, contrary to only waste oil sludge based sample whose capacity was found significant previously and it was attributed to the high volume of mesopores, which, owing to their large sizes, cannot be blocked by hydroxides. As seen from Table 25 the average pore sizes calculated using Dubinin-Astakhov method are related to the values of the characteristic energy of adsorption, which is the highest for CTC-A, CTCWO-1A, and CTCM-1A. These materials are obtained at low temperature so they can be considered as chars or “underactivated” carbons.

(115) TABLE-US-00027 TABLE 26 Content of catalytic metals Cr Sample Fe [%] Ca [%] Mg [%] Cu [%] Zn [%] [ppm] CWOB 3.7 5.1 8.4 0.25 0.51 280 CMB 22 14 0.46 0.77 0.16 6700 CTCB 1.45 × 0.0115 0.00255 1.55 × 10.sup.−5 2 × ND 10−4 10.sup.−5

(116) Details about the differences in the porosity of our samples are presented in FIGS. 22, 23A & B and 24A & B as pore size distributions. For all samples on the distributions two regions can be seen. One consists of micropores which are much more heterogeneous in their sizes for CTC and CTWO series of samples than for CTCM. On the other hand, the heterogeneity of mesopores is much greater for the latter group of samples. After H.sub.2S adsorption the smallest pores are not seen anymore indicating that sulfur is deposited either there, or at their entrances, and the new pores appears, especially with the range of sizes between 50-200 Å. In same cases it happens with the expense of macropores. This shows importance of large porosity with catalytically active surface to the process of hydrogen sulfide oxidation. If only physical adsorption were predominant those pores would not play any role and would have a negative effect on the performance of materials based on the unit volume of the bed. Thus in the case of this groups of materials very light adsorbents can be used which may increase the cost effectiveness of the removal process.

(117) The synergetic effect of the porosity development in our materials is presented in FIGS. 25 and 26 where the measured volumes of micro and mesopores are compared to those calculated assuming the physical mixture of the components and taking into account the yield of materials. As dissussed above, the synergetic effects of the sludge components on activation of the final products is clearly seen with the most pronounced effects of waste oil sludge on the volume of micropores and metal sludge—on the volume of mesopores.

(118) To check the role of porosity for H.sub.2S adsorption, the dependence of the capacity on the volume of pores was analyzed. The results are presented in FIG. 27. As seen, a good relationship is found for the volume of micropores. They have they origin likely in the tobacco derived carbon phase thus this component of the H.sub.2S adsorption process has to have similar mechanism on all tobacco containing samples. Linear trend is also noticed for the volume of mesopores but only for materials obtained at 950° C. As it was shown above, water has a detrimental effect on the chemistry of low temperature pyrolyzed samples, thus the linear trend in his case is not expected. The linear relationship between the capacity and volume of mesopores indicates the activity of large pores in the process of hydrogen sulfide catalytic oxidation.

(119) The comparison of DTG curves before and after adsorption of hydrogen sulfide is presented in FIGS. 28, 29, and 30. The peaks on the curves represent weight loss due to the decomposition/desorption of surface species. For some initial samples as CTCB, CTCM-1A, CTCM-1B an increase in weight (negative peaks) is observed between 150 and 400° C. and between 600 and 800° C. The latter negative peak is also found for CTCWO-2B. This strange behavior was noticed previously for some metal sludge, waste oil sludge and even sewage sludge-based adsorbents. Since only nitrogen was present formation of nitrides was given as the only plausible explanation. After H.sub.2S adsorption a negative peak is present only at high temperature range for CTCM-2BE. For other samples it is compensated by weight loss caused by removal of deposited sulfur between 200-400° C. Although this weight loss/peak intensity should be proportional to the amount of hydrogen sulfide deposited on the surface in the case of material pyrolyzed at 650° C. addition to the weight loss occurs as a result of dehydroxylation of surface at temperature smaller than 600° C. The hydroxides were formed when samples were exposed to water during prehumidification and H2S adsorption.

(120) Pyrolysis of waste tobacco compost and industrial sludges from heavy industries leads to the development of effective catalyst for desulfurization of air. An important role of carbonaceous phase derived from waste tobacco is in its relatively high carbon content. That carbon contributes to the development of porosity in both, micro and mesopore ranges. This happens via self-activation of carbon material by alkaline earth metals and water released from the decomposition of inorganic matter during heat treatment. As a result of solid state reactions at high temperature new catalytic species are formed on the surface of adsorbent as a result of synergy between the components of sludges. Location of these species in mesopores is beneficial for the desulfurization process. The surface of those pores retain water film where hydrogen sulfide can dissociate in the basic environment, Sulfur formed in oxidation reaction can be stored there in large quantity without rapid deactivation of the catalytic centers by sterical hindrances. High temperature of pyrolysis is beneficial for the adsorbents due to the enhanced activation of carbonaceous phase and chemical stabilization of inorganic phase. Samples obtained at low temperature are sensitive to water, which deactivates their catalytic centers.

(121) The present invention is not to be limited in scope by the specific embodiments described herein. Indeed, various modifications of the invention in addition to those described herein will become apparent to those skilled in the art from the foregoing description and the accompanying figures. Such modifications are intended to fall within the scope of the appended claims.

(122) It is further to be understood that all values are approximate, and are provided for description.

(123) Patents, patent applications, publications, product descriptions, and protocols are cited throughout this application, the disclosures of which are expressly incorporated herein by reference in their entireties for all purposes.