NZ620809B2 - Removal of hydrogen sulfide as ammonium sulfate from hydropyrolysis product vapors - Google Patents

Abstract

Disclosed is a method for processing biomass into hydrocarbon fuels and removing hydrogen sulphide by reacting with ammonia to form ammonium sulfate, wherein the method comprises: (a) processing a biomass in a hydropyrolysis reactor resulting in hydrocarbon fuels, char, and a process vapour stream(110); (b) cooling the process vapour stream to a condensation temperature (120); (c) separating the process vapour stream into a primary cooled vapour product stream, a liquid hydrocarbon stream, and a primary aqueous stream (130); wherein the primary cooled vapour product stream comprises non-condensable process vapours, hydrogen, hydrogen sulfide; carbon monoxide, and carbon dioxide, the liquid hydrocarbon stream comprises condensable hydrocarbons, and the primary aqueous stream comprises water, ammonia, hydrogen sulfide and ammonium sulfide; (d) treating the primary aqueous stream with a sour water stripper; (e) concentrating the hydrogen sulfide and ammonia into a cooled process water stream, and a second purified water stream; (f) sending the cooled process water stream to a catalytic reactor (140); (g) injecting air into the catalytic reactor (141) to obtain a concentrated treated stream containing water, ammonia and ammonium sulfate.; and a second gaseous stream containing nitrogen and oxygen (142). 110); (b) cooling the process vapour stream to a condensation temperature (120); (c) separating the process vapour stream into a primary cooled vapour product stream, a liquid hydrocarbon stream, and a primary aqueous stream (130); wherein the primary cooled vapour product stream comprises non-condensable process vapours, hydrogen, hydrogen sulfide; carbon monoxide, and carbon dioxide, the liquid hydrocarbon stream comprises condensable hydrocarbons, and the primary aqueous stream comprises water, ammonia, hydrogen sulfide and ammonium sulfide; (d) treating the primary aqueous stream with a sour water stripper; (e) concentrating the hydrogen sulfide and ammonia into a cooled process water stream, and a second purified water stream; (f) sending the cooled process water stream to a catalytic reactor (140); (g) injecting air into the catalytic reactor (141) to obtain a concentrated treated stream containing water, ammonia and ammonium sulfate.; and a second gaseous stream containing nitrogen and oxygen (142).

Description

REMOVAL OF HYDROGEN SULFIDE AS AMMONIUM SULFATE FROM HYDROPYROLYSIS T VAPORS Field of the Invention This invention relates to a process that removes hydrogen sulfide (H2S) from product vapors exiting a yrolysis reactor via reaction with ammonia (NH3) to form ammonium sulfide. In addition, the process converts en sulfide to ammonium sulfate.

Description of Related Art The process of the present invention relates to removal of H28 from the effluent vapors exiting a hydropyrolysis reactor. Hydropyrolysis reactors are known in the art.

Commercially, HZS is commonly removed from vapor streams via the Claus process, in a Claus plant. In the Claus Process, H2S is ed to form sulfur e (802) and then the sulfur dioxide is reacted with more H2S to produce water (H20) and elemental sulfur. The overall reaction is: 2HZS+02—>Sz+2H20 This process is nown, and has been widely applied in the refining and reforming of petroleum products. However, the process is complex, and often es multiple reaction ' steps. Moreover, the process can be most efficiently applied to s containing 25% or more of H28, on a molecular basis. If streams containing ammonia, as well as HZS are processed in a Claus plant, the ammonia is oxidized along with the H28. This is not ble, e a is a potentially-valuable reaction product of the hydropyrolysis process.

A significant portion of the product vapor stream from the yrolysis r comprises water vapor and hydrocarbons with boiling points below 70 degrees Fahrenheit, at atmospheric pressure. The product vapor from the hydropyrolysis reactor must be cooled to ambient temperatures in order for liquid hydrocarbons to be recovered as a separate product stream. When the product vapor stream is cooled, water vapor in the product vapor stream condenses to form liquid water, and a significant fraction of any H28 and any NH3 in the product vapor stream go into solution in the liquid water. The resulting aqueous solution then contains ammonia and e compounds.

Processes by which water-soluble sulfide compounds can be catalytically reacted with oxygen to form stable sulfate compounds are disclosed in Marinangeli et al., U.S. Patent 5,207,927 Gillespie, U.S. Patent 5,470,486. The approach taught by Marinangeli WO 19558 PCT/U82012/048345 et al., involves passing an s stream containing both the sulfide compound and oxygen over an appropriate oxidizing catalyst, under conditions wherein the pH of the solution is 9— 12, and an oxygen-to—sulfur ratio greater than about 5 is maintained. The approach taught by Gillespie requires a pH greater than 12 and an -to-sulfur ratio greater than about 4 be maintained. Both approaches prefer metal phthalocynanines with Gillespie preferring the use of carbon supports. A product stream that is substantially free of sulfide compounds is thus obtained, since all sulfide nds have been converted to sulfate compounds.

SUMMARY OF THE INVENTION In the hydropyrolysis r ofthe s of the present invention, a biomass feedstock is ted into a stream containing the following: 1. Deoxygenated condensable hydrocarbons (with properties corresponding to those of gasoline, diesel and kerosene) 2. ndensable hydrocarbon vapors (such as methane, ethane, e and ), 3. Other non—condensable vapors (C02, CO, and hydrogen), 4. Water and species which are soluble in liquid water, such as ammonia (NHg), and hydrogen sulfide (H28).

The NH3 is present in the hydropyrolysis product stream due to the presence of nitrogen in the biomass feedstock. The H28 is present in the hydropyrolysis stream due to the presence of sulfur in the s feedstock. The nitrogen and the sulfur in the feedstock react with hydrogen in the hydropyrolysis reactor to form NH3 and H28, respectively.

It is one object of this invention to provide a method by which hydrogen sulfide can be removed from a product vapor stream, produced by the hydropyrolysis of biomass. Hydropyrolysis experiments, in the course of which biomass was deoxygenated and converted to products including hydrocarbons, have shown that the stream of vapor leaving the hydropyrolizer contains water vapor, NH3, and H28, in proportions that make this product uniquely suited to a process in which the H28 is combined with the NH3 in an aqueous solution, and then oxidized to form ammonium sulfate. These experiments are original, and the concentrations of nitrogen and sulfur compounds in the vapor stream are unexpected and surprising. The experiments are described in detail in the examples presented below.

In order to carry out yrolysis in the hydropyrolysis reactor associated with the present invention, some portion of the hydropyrolysis t stream from the reactor may be sent to a steam reformer, and there d with steam to produce hydrogen.

Generally, it will be desirable to send some or all of the ndensable hydrocarbon vapors, such as methane, ethane, butane, etc., to the reformer. The hydrogen thus obtained may then be introduced back into the hydropyrolysis reactor, so that hydropyrolysis can continue to be carried out. The need for a source of hydrogen, external to the yrolysis process associated with the present ion, may thus be reduced or eliminated. Note that H28 will be present in the t vapor stream from the hydropyrolysis process whenever sulfiir is present in the feedstock, and the presence of the H28 creates several ms.

The H28 in the product vapor stream is highly toxic to humans. In addition, the H2S can poison the catalysts ed in steam reforming of product vapors from the hydropyrolysis reactor. er, the H28 can be reacted with NH3 to e ammonium sulfide ((NH4)2S), and then oxidized to produce ammonium sulfate ((NH4)2SO4), a product with considerable commercial value as a fertilizer.

The present invention describes a process which allows the H23 and NH3 contained in product vapor from hydropyrolysis of biomass to be captured in an aqueous stream. Biomass hydropyrolysis experiments have demonstrated that the hydropyrolysis process ated with the present invention produces a product stream that ns water vapor, H28, and NH3 in particular quantities that make it possible to obtain the requisite conditions for H2S removal via conversion to (NH4)2SO4. Substantially all the H28 captured in the aqueous stream is reacted with NH3 to form (NH4)2S. In addition, a surplus of unreacted NH3 is provided and dissolved in the aqueous stream, in order to increase the pH of the aqueous stream to approximately 12 or greater or lesser as required for subsequent conversion of (NH4)2S to (NH4)2SO4. The stream can then be reacted with oxygen in a thermal, non-catalytic conversion zone to substantially convert the dissolved (NH4)2S to (NH4)2SO4 and thiosulfate. The stream can be further contacted with oxygen and an oxidizing catalyst in ance with the method disclosed in Gillespie, US. Patent ,470,486 or, alternatively, the incoming aqueous stream can be reacted with oxygen, in the presence of an appropriate catalyst, in accordance with the method disclosed in the US.

Patent 927 (Marinangeli, et al.). By employing either technology, within the ranges of pH, oxygen to sulfur mole ratio, pressure, temperature, and liquid hourly space velocities In one aspect there is provided a method for processing biomass into hydrocarbon fuels comprising: processing a biomass in a hydropyrolysis reactor resulting in hydrocarbon fuels, char, and a process vapor stream; cooling the process vapor stream to a condensation temperature resulting in an aqueous stream; sending the aqueous stream to a catalytic reactor; injecting air into the catalytic reactor to obtain an aqueous product stream containing ammonia and ammonium sulfate; and ing a cooled product vapor , containing non-condensable process vapors comprising H2, CH4, CO, CO2, ammonia and hydrogen e.

In another aspect there is ed a method for removal of sulfur from biomass conversion products comprising: processing the biomass in a hydropyrolysis reactor, resulting in char and a heated process vapor stream containing hydrogen, water vapor, condensable hydrocarbon vapors, noncondensable hydrocarbon vapors, carbon monoxide and carbon dioxide; g the process vapor stream to a condensation temperature to a cooled and condensed product ; AH26(10987121_1):RTK separating the cooled and condensed product stream into a gaseous and liquid component; obtaining a liquid hydrocarbon stream; obtaining an aqueous , containing water, ammonia, and ammonium sulfide; obtaining a cooled product vapor stream, containing non-condensable process vapors comprising H2, CH4, CO, CO2, ammonia and hydrogen sulfide; sending the aqueous stream to a tic reactor; injecting air into the catalytic reactor thereby oxidizing ammonium sulfide over a catalyst resulting in ammonium sulfate; obtaining an aqueous product stream ning water, ammonia and ammonium e; ating excess water from the aqueous t stream containing ammonium sulfate resulting in steam and a concentrate of ammonium sulfate; cooling the concentrate of ammonium sulfate to precipitate out the ammonium sulfate as crystallized um sulfate; and filtering out the crystallized ammonium sulfate.

AH26(10987121_1):RTK WO 19558 shows a process flow diagram according to one preferred embodiment of this invention, in which the treated s product stream, containing water, NH3, and (NH4)2SO4, is treated in a sour-gas stripper. shows a process flow diagram according to one preferred embodiment of this invention, in which a sour-water stripper removes NH3 and H28 from the primary s stream prior to the introduction of the s stream to the oxidation reactor. shows a process flow diagram according to one preferred embodiment of this invention, which incorporates both an H2S removal unit, associated with the cooled vapor product stream, and a sour-water stripper upstream of the oxidation reactor.

DETAILED PTION OF THE PRESENTLY PREFERRED EMBODIMENTS FIGS. 1-6 show various preferred embodiments of the t invention. shows a process flow diagram, illustrating the simplest embodiment of the s of the present invention, in which H2S is captured in a primary aqueous stream containing NH3, and oxidized in a reactor to form (NH4)2SOA. Product streams in this embodiment include a cooled vapor stream comprising primarily process vapors, and ning some H2S, a liquid stream comprising primarily condensed hydrocarbons, a second vapor stream comprising primarily nitrogen and oxygen, and a treated aqueous stream comprising primarily water, NH3, and (NH4)2SO4. shows the first and most elementary embodiment of the process of the present invention. Biomass 111 and hydrogen 112 are'introduced into a yrolizer 110, which produces a solid, carbonaceous product 113 red to as char) and a product vapor stream 114. The solid product 113 comprises primarily aceous residue, remaining after the hydropyrolysis of the biomass feedstock 111. The product vapor stream 114 leaves the hydropyrolizer 110 (which may comprise a single r, or multiple reactors in series) at a temperature that is teristic of such hydropyrolytic processes, at a minimum, high enough that all constituents are maintained in a gaseous state. However, as is characteristic of such hydropyrolytic conversion processes, the temperature may also be cantly higher than this minimum. The product vapor stream 114 primarily comprises: 1. Deoxygenated sable hydrocarbons (with properties corresponding to those of gasoline, diesel and kerosene) 2. Non-condensable hydrocarbon vapors (such as methane, ethane, e and butane), 3. Other ndensable vapors (CO2, CO, and H2), 4. Water and species which are soluble in liquid water, such as ammonia (NH3), and hydrogen sulfide (H2S).

The vapor stream is passed through a condenser 120, or other device, or other set of devices, wherein the temperature of the vapor stream is reduced to a point where substantially all the condensable hydrocarbons can be recovered as a liquid stream. At this point, three phases develop: A cooled vapor phase, a hydrocarbon phase, and an aqueous phase. The cooled product stream, containing all three phases, is sent to a separator 130, where the three phases can be split up into three separate streams.

The sable hydrocarbon product stream 132 is preferably recovered at this point. The H2S that was initially in the hot product vapor stream 114 is now divided, with some exiting the separator in the cooled vapor stream 131, and some in the primary aqueous stream 133. A trace of H28 may also-be present in the liquid hydrocarbon stream 132, but the solubility of the polar H2S molecule in the liquid hydrocarbon stream is minimal.

The cooled vapor product stream 131 leaving the separator comprises ily H2, ndensable hydrocarbons, CO2, CO, and H28.

The primary aqueous stream 133 leaving the separator comprises primarily water, NH3, and ammonium sulfide ((NH4)2S). The (NH4)2S in this stream is ed when the H28 from the vapor stream enters the aqueous stream and reacts with NH3, which is also in solution in the aqueous stream. It is an object of this invention to control the process of the invention in such a manner that the pH of the primary aqueous stream 133 is approximately 12, meaning that the concentration of NH3 (as NH4OH) in the stream is great enough to produce a strongly—basic solution. This is helpful, in part, to help stabilize the H28 and increase its solubility in the s stream. It is also a preferred condition for the operation of the ion reactor 140, wherein the (NH4)2S is oxidized to produce (NH4)2SO4.

The primary aqueous stream 133 from the separator 130 is then introduced to an oxidation reactor 140, also referred to as a catalytic reactor herein. A stream of air 141 is also introduced to the ion r, in an amount sufficient to supply approximately 5 moles of oxygen for each mole of sulfur. After reaction at an appropriate temperature and pressure, in the presence of an appropriate catalyst, and for a sufficient residence time, the (NH4)2S in the primary aqueous stream 133 is substantially completely oxidized.

In accordance with this first embodiment of the process of the present invention, a treated aqueous product stream 142 is preferably obtained from the oxidation r, including NH3, liquid water, and (NH4)2SO4. In addition, a reactor gas product stream 143 is obtained from the oxidation reactor, primarily comprising nitrogen and unused oxygen, and containing traces of NH3 and water vapor. It will be noted that, in this first embodiment, a significant concentration of H28 is still present in the cooled product vapor stream 131 g the separator unit 130. is a process flow diagram, illustrating an embodiment of the s of the present ion, in which H2S that still remains in the cooled vapor product stream is captured in a sorbent bed. In this case, removal of the H28 remaining in the cooled product vapor stream is ntially te. illustrates a second embodiment of the process of the present invention.

In this second embodiment an H28 removal unit 250 has been added, ream of the separator 230. The y cooled vapor product stream 231 passes h the H28 removal unit 250 (which may comprise a sorbent bed, liquid wash, or other similar apparatus). The H28 in the y cooled vapor product stream 231 is substantially completely removed from the primary cooled vapor product stream 231, and a secondary cooled vapor product stream 251 comprising primarily H2, C0, C02, and non-condensable hydrocarbon vapors is obtained. In this embodiment, the H28 is not recovered, and would, for example, be disposed of when the H28 removal unit 250 is regenerated with H2S-containing waste being appropriately discarded. illustrates a third embodiment of the process of the present invention.

In this third embodiment, an H2S removal unit 350 has been added, ream of the separator 330, as in the second embodiment, described above. The primary cooled vapor product stream 331 passes through the H28 removal unit 350 (which may comprise a reusable sorbent bed, amine scrubber, or some similar apparatus). The H28 in the primary cooled vapor product stream 331 is substantially tely removed, and a secondary cooled vapor t stream 351 comprising primarily H2, C0, C02, and non-condensable hydrocarbon vapors is obtained. However, in this third embodiment, the H28 is recovered from the H28 removal unit 350, in a stream 352 comprising primarily gaseous H28, and is sent to the oxidation reactor 340, along with the y aqueous stream 333. In the ion reactor, the gaseous H28 stream 352 is brought into contact with the primary aqueous stream 333 and an appropriate catalyst, and forms (NH4)2S, which is then oxidized to form (NH4)2SO4. In this way, a secondary cooled product vapor stream 351, containing only trace s of H28, and comprising ily H2, non-condensable hydrocarbons, CO2, and CO, is obtained. In on, the overall conversion of H28 is increased, and is higher than in the first embodiment of the process of the present invention, described above. illustrates a fourth embodiment of the process of the present invention.

Ammonia (NH3) is a potentially-valuable product, and is separated from the primary treated aqueous stream 442 leaving the oxidation reactor 440 in a ater stripper 460 in this fourth embodiment of the process of the present invention. This ch allows a gaseous stream 461 comprising primarily NH3 to be recovered, while the water and (NH4)2SO4 are recovered separately from the ater stripper in a secondary treated aqueous stream 462.

(NH4)2$O4 is highly water-soluble, and the aqueous solution of (NH4)2SO4 has potential value as an agricultural fertilizer. If desired, this solution can be concentrated by further heating of the secondary treated aqueous stream 462, which could drive off some or all of the water in the stream. illustrates a fifth embodiment of the process of the present invention.

This embodiment features a sour-water stripper 560 upstream of the oxidation r 540, 2O which accepts the primary aqueous stream 533 from the tor. Water, NH3 and H28, and any (NH4)2S formed by the reaction of NH3 and H28, are removed in the sour-water stripper 560, and leave the sour—water stripper as a gaseous stream 562. A stream of purified liquid water 561 is thereby produced. This purified water stream 561 is then available as a product stream. If desired, a portion of this purified water stream 561 can be brought back into contact with the gaseous stream 562 of NH3 and H28 from the sour-water stripper. In this case, the NH3 and H28 go back into solution in this portion of the liquid water stream 561, forming (NH4)2S, and this solution is then introduced into the oxidation reactor 540, for conversion to '(NH4)2SO4. However, preferably the purified water stream is not brought back into contact with the gaseous stream 562 and preferably, stream 562 is cooled as needed so that water in the stream is condensed and the NH3 and H28 in this stream go back into solution g S, and this solution is then introduced into the oxidation reactor 540, for conversion to (NH4)2SO4. This approach makes a stream of purified water 561 available, and creates a concentrated treated stream 542 of water, NH3 and (NH4)2SO4 at the outlet of the oxidation reactor 540. illustrates a‘sixth embodiment of the process of the present invention.

This embodiment features a sour-water stripper 660 upstream of the oxidation reactor 640, which accepts the primary aqueous stream 633 from the separator 630. It also features an H2S removal unit 650 ream of the separator 630, as in the third embodiment described herein above. The primary cooled vapor product stream 631 passes through the H28 removal unit 650 (which may comprise a sorbent bed, amine scrubber, or some similar apparatus).

The H28 in the y cooled vapor t stream 631 is ntially completely removed and a secondary cooled product vapor stream 651 comprising primarily H2, C0, C02, and non-condensable hydrocarbon vapors is obtained. As in the third embodiment, the H28 is recovered, in a stream 652 comprising primarily gaseous H2S, and is sent to the oxidation reactor 640.

As described herein above in the description of the fifth embodiment, dissolved NH3 and H28, and any (NH4)2S formed by the reaction ofNH3 and H28, are driven out of the primary aqueous stream 633 in the ater stripper 660. Water, NH; and H28, and any $ formed by the reaction of NH3 and H28, are removed in the sour-water stripper 660, and leave the sour-water er as a gaseous stream 662. A stream of purified water 661 is thereby produced. This purified water stream‘66l is then available as a t stream. If desired, a portion of this purified water stream 661 can be brought back into contact with the gaseous stream 662 of NH3 and H28 from the sour—water er. In this case, the NH3 and H28 go back into solution in this portion of the liquid water stream 661, forming S, and this solution is then introduced into the oxidation reactor 640, for conversion to (NH4)2SO4. However, preferably the purified water stream is not brought back into contact with the gaseous stream 662 and preferably, stream 662 is cooled as needed so that water in the stream is sed and the NH3 and H28 in this stream go back into solution forming (NH4)2S, and this solution is then introduced into the oxidation reactor 640, for sion to (NH4)2SO4. This approach makes a stream of purified water 661 available, and creates a concentrated treated stream 642 of water, NH3 and (NH4)2SO4 at the outlet of the oxidation reactor 540. The stream 652 of recovered H2S from the H28 l unit is also introduced to the oxidation reactor.

This sixth embodiment of the process of the present invention makes a stream of purified water 661 available, and creates a concentrated treated stream 642 of water, NH3 and (NH4)ZSO4 at the outlet of the oxidation reactor 640. It also es a secondary stream of cooled vapor t 651 which may contain minute concentrations of H28, and promotes high overall sion of H28 to an (NH4)2SO4 product.

The char produced from the hydropyrolysis of biomass (land and water based biomass, wastes from processes utilizing these materials), as well as plastics derived from biomass or petroleum has been found to be an essentially inert carbonaceous material, free of hydrocarbon contaminants that are toxic to humans or plants. It is one intent of this invention to combine the char produced from the yrolysis of biomass or plastic with the ammonium sulfate recovered from this process to produce an agricultural fertilizer product, as a powder, granulated, or pelletized material that can both improve the y of a soil for use as an agricultural substrate and provide a fertilizing component for the sustenance of lignocellulosic biomass.

EXAMPLES A sample of wood with properties representative of those of most wood species was ted to hydropyrolysis. The tal composition of the wood is presented in Table A, below. The composition is presented on both an overall basis (which includes moisture and ash in the feedstock) and on a moisture- and ash-free (MAF) basis. As can be seen in Table A, small but significant quantities of nitrogen and sulfiir were t in the wood.

The yield of hydropyrolysis products, obtained in the vapor stream leaving the experimental hydropyrolizer, is given in Table B. Not all of the nitrogen and sulfur initially present in the wood is ultimately found in the vapor stream from the hydropyrolizer. Some of the sulfur and some of the nitrogen are chemically bound up in the stream of solid product (comprising char and ash) from the hydropyrolizer. However, the experiment demonstrated that the yield of NH3 in the primary product vapor stream tuted 0.18% of the mass of the ock, on an MAF basis. The yield of H28 constituted 0.05% of the mass of the feedstock, on an MAF basis. It will be noted that the total masses in Table B add up to 104.83%. This is due to the fact that a given quantity of moisture and ash-free wood reacts with hydrogen in the hydropyrolysis process, and the resulting ts have a r total mass than the wood that was reacted. 2012/048345 As an example, one might assume that one kilogram of moisture-free, ash-free wood is subjected to hydropyrolysis. In this case, the vapor stream contains 1.8 grams ofNH3 and 0.5 grams of H28. Due to the different molar masses of NH3 and H28, this equates to 0.106 moles of NH3 and 0.014 moles of H28. The molar ratio of NH3 to H2S is therefore 7.4 to 1. In order to form (NH4)2S in an aqueous solution, two moles ofNH3 are required for each mole of H28. The ve amounts of NH; and H28 in the vapor stream leaving the hydropyrolysis reactor are more than te to react all the H2S in the stream with NH3, and produce an aqueous solution of (NH4)28.

Further, the interaction with hydrogen in the hydropyrolysis process converts a significant on of the oxygen in the dry, ee wood into water vapor in the vapor stream leaving the hydropyrolysis s. Even if the feedstock is completely dry, there is still a significant formation of water during hydropyrolysis of the wood feedstock, and the amount of water produced is ent to substantially and completely dissolve all of the NH3 and H28 present in the hydropyrolysis product vapor stream.

While all or almost all of the NH; leaving the hydropyrolysis reactor ultimately goes into solution in the primary aqueous , the solubility of H28 in aqueous solutions s on a variety of factors, such as temperature, pressure, and pH of the solution. The NH3 in solution in the primary aqueous stream will render the solution alkaline, and this will significantly increase the solubility of H28 in the alkaline aqueous solution. H28 and NH3 react spontaneously in aqueous solution to form (NH4)2S, though the sulfide may be present in a dissociated form. r, not all the H28 in the product vapor stream is likely to enter the primary aqueous stream when the process vapors are cooled. A cooled vapor stream, containing a significant concentration of H28, is still likely to result in practice. The various embodiments of the process of the present invention, described above, provide means by which this ing tration of H28 can be removed from the cooled vapor stream, and, ultimately, reacted with NH3 and oxygen to form (NH4)2SO4.

In actual practice, the biomass feedstock conveyed into the hydropyrolizer will also contain some moisture, so the actual amount of water vapor in the heated vapor stream from the hydropyrolizer will contain significantly'more water that would be the case if the feedstock were bone dry. This phenomenon assists in removal of H28 from the cooled vapor stream, since the concentrations ofNH; and H28 in the primary aqueous stream will be even lower than they would be if the feedstock were completely dry, meaning that more H28 can WO 19558 be stripped from the cooled vapor stream in the ser and separator of the embodiments of the process of the present ion, described herein above. The solubility of (NH4)ZS in water is very high, and solutions of (NH4)ZS containing up to 52% by mass of (NH4)2S appear to be commercially ble.

Initial Composition _—_!_ % moisture Table A. Composition of Wood Feedstock Wood yrolysis Hot Vapor Product Yield (MAF Basis): Table B. Yield of hot vapor products from hydropyrolysis of wood, on a moisture- and ash—free (MAF) basis Not all biomass is equivalent, and a second ock, which differs significantly from wood in terms of mechanical properties, growth cycle, and composition, was also tested. This feedstock was com stover. Corn stover includes residues of corn stalks and husks, left over after the nutritious parts of the plant have been harvested. The sample examined was typical of most types of corn stover generated during harvesting of corn. The composition of the corn stover sample is presented on both an overall basis (which includes moisture and ash in the feedstock) and on a moisture- and ash—free (MAF) basis in Table C.

As can be seen in Table C, small but significant quantities of nitrogen and sulfur were present in the corn stover, as was the case with the wood feedstock. As can be seen from the table, the corn stover sample contained far more ash and far more moisture than did the sample of wood.

As with the wood feedstock, the ratio between hydrogen sulfide and ammonia in the hot product vapor leaving the corn stover hydropyrolysis process is very important.

The hydropyrolysis product vapor composition of corn stover was found to be very similar to that of wood, on an MAF basis. The relevant values are shown in Table D. One significant difference between Tables B and D relates to the trations of NH3 and H2S in the product vapor. The molar ratio ofNH3 to H28 in the product vapor, in the case of corn stover, is 15.2. Again, there is more than enough NH3 present to react with the H28 in the product there is more than vapor stream and form um sulfide. As was the case with wood, sufficient water formed, during hydropyrolysis of corn stover, to completely dissolve any um sulfide, and carry it in solution through the process of the present invention. It will be noted that the total masses in Table D add up to 106%. This is due to the fact that a given quantity of moisture and ash-free corn stover reacts with en in the hydropyrolysis s, and the resulting products have a greater total mass than the ock that was reacted.

Initial Composition Initial Composition, MAF Basis % c (MF) H( “— % O (MF) % N (MF) % S (MF) % ash (MF) % moisture Table C. Composition of corn typical stover sample Corn Stover Hydropyrolsyis Hot Vapor Product Yield (MAF Basis): Table D. Composition of t vapor, hydropyrolysis of typical corn stover, on MAF basis While in the foregoing specification this invention has been described in relation to certain preferred embodiments thereof, and many details have been set forth for purpose of illustration, it will be nt to those skilled in the art that the invention is susceptible to additional embodiments and that n of the details described herein can be varied considerably without departing from the basic principles of the invention.

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Claims (22)

CLAIM :

1. A method for processing biomass into hydrocarbon fuels sing: sing a biomass in a hydropyrolysis reactor resulting in hydrocarbon fuels, char, and a process vapor stream; cooling the process vapor stream to a condensation temperature resulting in an aqueous stream; sending the aqueous stream to a catalytic reactor; injecting air into the catalytic reactor to obtain an aqueous product stream containing ammonia and ammonium sulfate; and obtaining a cooled product vapor stream, containing non-condensable process vapors comprising H2, CH4, CO, CO2, ammonia and en sulfide.

2. The method of claim 1 r comprising: maintaining the aqueous stream at a pH of approximately 9-12 and a ratio of 5 atoms of oxygen for each atom of sulfur sent to the catalytic reactor in the aqueous stream.

3. The method of claim 1 or claim 2 further comprising: removing hydrogen e from the cooled product vapor stream.

4. The method of claim 3 further comprising: sending the hydrogen sulfide to the catalytic r, along with the aqueous stream, to react with ammonia present in the aqueous , to form ammonium sulfide and then ammonium sulfate; and recovering the cooled product vapor stream resulting in a high overall conversion of hydrogen sulfide to ammonium sulfate.

5. The method of any one of claims 1 to 4, further comprising: treating the aqueous stream leaving the tic reactor with a sour water stripper resulting in a gaseous stream comprising primarily ammonia and an aqueous stream comprising ily water and ammonium sulfate.

6. The method of claim 5 wherein the sour water stripper is positioned upstream of the catalytic r. AH26(10987121_1):RTK

7. The method of any one of claims 1 to 6 further comprising: treating the aqueous stream with a sour water stripper resulting in a stream of purified liquid water and a gaseous stream comprising primarily ammonia and hydrogen sulfide; recombining the purified liquid water with the ammonia and hydrogen sulfide, for subsequent treatment and sion in the catalytic r.

8. The method of any one of claims 1 to 7 further comprising: treating the aqueous stream with a sour water stripper positioned upstream of the catalytic reactor; removing the hydrogen sulfide from the aqueous stream resulting in a cooled process vapor stream, containing little to no hydrogen sulfide, and a purified water stream.

9. The method of any one of claims 1 to 8 further comprising: combining char produced from the hydropyrolysis of the s with red ammonium sulfate to create a nutrient for lignocellulosic s that also is a soil amendment.

10. The method of claim 9 further comprising: pelletizing the mixture of char and recovered ammonium sulfate to create a densified nutrient for lignocellulosic biomass that also is a soil ent.

11. The method of claim 9 further comprising: pelletizing the mixture of char, recovered ammonium sulfate, and agricultural fertilizers to create a densified nutrient for nourishing ellulosic biomass that also is a soil ent.

12. A method for removal of sulfur from biomass conversion products sing: sing the biomass in a hydropyrolysis reactor, resulting in char and a heated process vapor stream containing hydrogen, water vapor, condensable hydrocarbon vapors, densable hydrocarbon vapors, carbon monoxide and carbon dioxide; cooling the process vapor stream to a sation temperature to a cooled and condensed product stream; separating the cooled and condensed product stream into a gaseous and liquid component; obtaining a liquid hydrocarbon stream; obtaining an aqueous stream, containing water, ammonia, and ammonium sulfide; obtaining a cooled product vapor stream, containing non-condensable process vapors comprising H2, CH4, CO, CO2, ammonia and hydrogen sulfide; AH26(10987121_1):RTK sending the aqueous stream to a catalytic reactor; injecting air into the catalytic reactor y oxidizing ammonium sulfide over a catalyst resulting in ammonium e; obtaining an aqueous product stream containing water, ammonia and ammonium e; evaporating excess water from the aqueous product stream containing ammonium sulfate resulting in steam and a concentrate of ammonium sulfate; cooling the concentrate of ammonium sulfate to precipitate out the ammonium sulfate as crystallized ammonium sulfate; and ing out the crystallized um sulfate.

13. The method of claim 12 further comprising the step of: stripping ammonia from the aqueous stream containing water, ammonia and ammonium sulfate to create a te purified stream of gaseous ammonia.

14. The method of claim 13 further comprising the step of: introducing the aqueous stream containing ammonium sulfate a boiler to convert ammonium e to crystallized ammonium sulfate and steam.

15. The method of any one of claims 12 to 14 further comprising the step of: sending the steam from the evaporation step through a guard bed to remove trace H2S from the steam.

16. The method of claim 15 r comprising the step of: g the steam passing from the guard bed to a steam reformer.

17. The method of claim 14 further comprising the step of: sending the steam created by the boiler through a guard bed to remove trace H2S from the steam.

18. The method of claim 17 further comprising the step of: sending the steam passing from the guard bed to a steam reformer.

19. The method of any one of claims 12 to 18 wherein the catalyst is monosulfonated cobalt phthalocynanine. AH26(10987121_1):RTK

20. A hydrocarbon fuel made by the method of claim 1.

21. A method for processing biomass into hydrocarbon fuels, said method being according to claim 1 and substantially as herein described with reference to any one of the es.

22. A method for processing biomass into hydrocarbon fuels, said method being according to claim 1 and substantially as herein described with reference to any one of the anying drawings. Gas Technology Institute By the Attorneys for the Applicant SPRUSON & FERGUSON Per: AH26(11370162_1):RTK