NZ716910B2

NZ716910B2 - Hydropyrolysis process

Info

Publication number: NZ716910B2
Application number: NZ716910A
Authority: NZ
Inventors: Larry G Felix; Martin B Linck; Terry L Marker; Michael J Roberts
Original assignee: Gas Technology Institute
Priority date: 2011-08-02
Filing date: 2012-07-26
Publication date: 2017-10-03

Abstract

hydropyrolysis process comprising: introducing biomass and hydrogen into a hydropyrolyzer comprising one or more reactors; sufficiently deoxygenating the biomass to provide a vapor product of the hydropyrolyzer comprising, in the gaseous state, deoxygenated condensable hydrocarbons, non-condensable gases, and water; cooling the vapor product to condense a liquid organic phase and a liquid aqueous phase comprising at least one species of the vapor product, including ammonia (NH3), that is solubilized in the liquid aqueous phase; and phase separating the liquid aqueous phase from the liquid organic phase and obtaining a gas phase NH3 product or an aqueous NH4OH product from the aqueous phase. e gases, and water; cooling the vapor product to condense a liquid organic phase and a liquid aqueous phase comprising at least one species of the vapor product, including ammonia (NH3), that is solubilized in the liquid aqueous phase; and phase separating the liquid aqueous phase from the liquid organic phase and obtaining a gas phase NH3 product or an aqueous NH4OH product from the aqueous phase.

Description

HYDROPYROLYSIS PROCESS Field of the Invention This invention relates to a process that removes hydrogen sulfide (H2S) from product vapors g a hydropyrolysis reactor via reaction with ammonia (NH3) to form ammonium sulfide. In addition, the process converts hydrogen sulfide to ammonium e.

Description of Related Art The process of the t invention relates to removal of H2S from the effluent vapors exiting a hydropyrolysis reactor. Hydropyrolysis reactors are known in the art.

Commercially, H2S is commonly removed from vapor streams via the Claus process, in a Claus plant. In the Claus Process, H2S is oxidized to form sulfur dioxide (SO2) and then the sulfur dioxide is reacted with more H2S to produce water (H20) and elemental sulfur.

The overall reaction is: 2 H2S + O2  S2 + 2 H2O This process is well-known, and has been widely d in the ng and reforming of petroleum products. However, the process is complex, and often involves le reaction steps. Moreover, the process can be most efficiently applied to streams containing 25% or more of H2S, on a molecular basis. If streams containing ammonia, as well as H2S are processed in a Claus plant, the ammonia is oxidized along with the H2S. This is not desirable, because a is a potentially-valuable reaction product of the hydropyrolysis s.

A significant n of the product vapor stream from the hydropyrolysis reactor comprises water vapor and hydrocarbons with boiling points below 70 s 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 te product stream. When the product vapor stream is cooled, water vapor in the product vapor stream ses to form liquid water, and a significant fraction of any H2S and any NH3 in the product vapor stream go into solution in the liquid water. The resulting aqueous solution then contains ammonia and sulfide 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 ,207,927 Gillespie, U.S. Patent 5,470,486. The ch taught by Marinangeli AH26(13073655_2):MBS et a1., involves passing an aqueous 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 oxygen-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 ntially free of sulﬁde compounds is thus obtained, since all sulﬁde compounds have been ted to e compounds.

SUMMARY OF THE INVENTION In the hydropyrolysis reactor ofthe process of the present invention, a biomass feedstock is converted into a stream containing the following: 1. Deoxygenated condensable hydrocarbons (with properties corresponding to those of gasoline, diesel and kerosene) 2. Non-condensable hydrocarbon vapors (such as methane, , propane and butane), 3. Other ndensable vapors (CO2, CO, and hydrogen), 4. Water and species which are soluble in liquid water, such as ammonia (NH3), and en sulfide (H28).

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

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 g 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 hydropyrolysis in the hydropyrolysis reactor associated with the present invention, some portion of the hydropyrolysis product stream from the reactor may be sent to a steam reformer, and there d with steam to produce en.

Generally, it will be desirable to send some or all of the non-condensable 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 hydropyrolysis process associated with the present invention, may thus be reduced or ated. Note that H28 will be t in the product vapor stream from the hydropyrolysis process whenever sulfur is present in the feedstock, and the presence of the H28 creates l problems.

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

The present invention describes a process which allows the H28 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 associated with the present invention produces a product stream that contains water vapor, H28, and NH3 in particular quantities that make it possible to obtain the ite conditions for H28 removal via sion to (NH4)ZSO4. ntially all the H28 captured in the aqueous stream is reacted with NH3 to form (NH4)2S. In addition, a s 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 uent conversion of (NH4)2S to SO4. The stream can then be reacted with oxygen in a thermal, non—catalytic sion zone to substantially convert the ved (NH4)2s to (NH4)ZSO4 and thiosulfate. The stream can be further ted with oxygen and an oxidizing catalyst in accordance 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 5,207,927 (Marinangeli, et al.). By employing either technology, within the ranges of pH, oxygen to sulfur mole ratio, pressure, temperature, and liquid hourly space velocities taught in these patents, an aqueous stream containing NH3 and (NH4)2SO4 is thereby obtained, and these compounds can then be recovered and sold as izer. A variety of methods for obtaining ammonium sulfate from an aqueous stream containing ammonium sulfite and dissolved ammonia are currently in use and the examples cited above serve to illustrate that established technologies exist for effecting this conversion.

These ammonia-derived compounds that can be recovered and sold as fertilizer can be mixed with char produced by this process and ized to produce a product to provide fertilize and amend soils. Likewise these ammonia-derived compounds produced by this process that can be recovered and sold as fertilizer can also be mixed with char and other essential soil nutrients and minerals and pelletized to produce a product to e improve, fertilize, and amend soils. It should also be obvious to one skilled in the art that these ammonia-derived compounds that incorporate char and other essential soil nutrients and ls can be prepared in time-release formulations to avoid repetitive applications in an agricultural setting.

A stream of product vapor, from which substantially all the H2S has been removed, is also obtained. This stream of vapor can then be handled in various ways, including use as a fuel to raise steam or directing it into a steam reformer.

In a first aspect of the present invention, there is provided a hydropyrolysis process comprising: introducing biomass and hydrogen into a hydropyrolyzer comprising one or more reactors; sufficiently deoxygenating the biomass to provide a vapor product that exits the hydropyrolyzer at a temperature such that all constituents of the vapor t are ined in the gaseous state, the vapor product comprising deoxygenated condensable hydrocarbons, noncondensable gases, and water; g the vapor product to condense a liquid c phase and a liquid aqueous phase comprising at least one s of the vapor product, including ammonia (NH3), that is solubilized in the liquid aqueous phase; and phase separating the liquid aqueous phase, comprising the solubilized NH3, from the liquid organic phase and treating the liquid aqueous phase to obtain a gas phase NH3 t or an aqueous NH4OH t.

In a second aspect of the present invention, there is provided a method for preparing an ammonia product, comprising: processing biomass in a hydropyrolyzer to obtain solid char and a heated vapor product that exits the hydropyrolyzer at a temperature such that all tuents of the vapor product are maintained in the s state, the vapor product AH26(13073655_2):MBS comprising hydrogen, carbon monoxide, carbon dioxide, deoxygenated condensable hydrocarbons, and water vapor; cooling the heated vapor product to se, as separate liquid phases, an organic phase and an aqueous phase comprising NH4OH that is formed from the dissolution of NH3 from the heated vapor product into the aqueous phase; and separating the liquid phases and ing the ammonia product as a gas phase NH3 product or an aqueous NH4OH product from treating of the aqueous phase.

In a third aspect of the present invention, there is provided a gas phase NH3 product or an aqueous NH4OH product made by the process of the first or second aspect.

In a fourth aspect of the present invention, there is provided a hydropyrolysis process comprising: introducing a biomass feedstock and hydrogen into a hydropyrolyzer comprising one or more reactors, wherein sulfur is present in the biomass feedstock; sufficiently deoxygenating the biomass to provide a vapor product that exits the hydropyrolyzer at a temperature such that all constituents of the vapor product are maintained in the s state, the vapor product comprising deoxygenated condensable hydrocarbons, non-condensable hydrocarbons and H2S, and water; cooling the vapor product to obtain a condensed liquid c phase, a condensed liquid aqueous phase, and a cooled vapor phase comprising at least a portion of the H2S; separating the condensed liquid organic phase, the condensed liquid aqueous phase, and the cooled vapor phase; ng the cooled vapor phase to substantially remove the H2S and obtain a treated vapor phase comprising at least a portion of the ndensable hydrocarbons; and subjecting the treated vapor phase to steam reforming, in order to generate reformer hydrogen from the non-condensable hydrocarbons.

BRIEF DESCRIPTION OF THE DRAWINGS These and other objects and features of this invention will be better understood from the following detailed description taken in conjunction with the drawings wherein: shows a process flow diagram according to one preferred embodiment of this ion, in which H2S is ed in a y aqueous stream containing NH3, and oxidized in a reactor to form (NH4)2SO4. shows a s flow m ing to one preferred embodiment of this invention, in which H2S that still s in the cooled vapor product stream is captured in a sorbent bed. shows a process flow diagram according to one preferred embodiment of this invention, in which the H2S remaining in the cooled vapor t stream is captured and AH26(13073655_2):MBS sent into the oxidation reactor along with the primary aqueous stream, promoting more complete overall sion of H2S to (NH4)2SO4.

AH26(13073655_2):MBS shows a process flow diagram ing to one preferred embodiment of this invention, in which the treated aqueous product , containing water, NH3, and (NH4)ZSO4, 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 s NH3 and H28 from the primary aqueous stream prior to the introduction of the aqueous stream to the oxidation reactor. shows a process ﬂow diagram according to one preferred embodiment of this invention, which incorporates both an H28 removal unit, associated with the cooled vapor product stream, and a sour—water stripper am of the oxidation reactor.

DETAILED PTION OF THE PRESENTLY PREFERRED EMBODIMENTS FIGS. 1-6 show various preferred embodiments of the subject invention shows a process ﬂow diagram, illustrating the simplest embodiment of the process of the present invention, in which HZS is captured in a primary aqueous stream containing NH3, and oxidized in a reactor to form (NH4)2SO4. Product streams in this embodiment include a cooled vapor stream comprising ily process , and containing some HZS, a liquid stream comprising ily condensed hydrocarbons, a second vapor stream sing 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 areintroduced into a hydropyrolizer 110, which produces a solid, carbonaceous t 113 (referred to as char) and a product vapor stream 114. The solid product 113 ses primarily aceous residue, remaining after the hydropyrolysis of the biomass ock 111. The product vapor stream 114 leaves the hydropyrolizer 110 (which may comprise a single reactor, or multiple reactors in series) at a temperature that is characteristic 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 signiﬁcantly higher than this minimum. The product vapor stream 114 primarily comprises: 1. Deoxygenated condensable hydrocarbons (with properties corresponding to those of gasoline, diesel and kerosene) 2. Non-condensable hydrocarbon vapors (such as methane, ethane, propane and butane), 3. Other non-condensable vapors (CO2, CO, and H2), 4. Water and species which are e in liquid water, such as ammonia (NH3), and en sulﬁde (H2S).

The vapor stream is passed through a condenser 120, or other device, or other set of devices, n the temperature of the vapor stream is reduced to a point where substantially all the condensable arbons 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 condensable hydrocarbon t 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 primarily H2, non—condensable hydrocarbons, CO2, CO, and H28.

The primary aqueous stream 133 leaving the separator comprises primarily water, NH3, and ammonium sulﬁde ((NH4)28). 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 ion in such a manner that the pH of the primary aqueous stream 133 is approximately 12, meaning that the concentration of NH3 (as NH40H) in the stream is great enough to e a ly—basic solution. This is helpful, in part, to help stabilize the H28 and se its solubility in the aqueous stream. It is also a red condition for the operation of the oxidation 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 oxidation reactor, 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 S in the primary aqueous stream 133 is substantially completely oxidized.

In accordance with this ﬁrst embodiment of the process of the t invention, a treatedvaqueous product stream 142 is preferably obtained from the oxidation reactor, 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 , 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 process of the present invention, in which H28 that still remains in the cooled vapor product stream is captured in a t bed. In this case, removal of the H28 remaining in the cooled product vapor stream is substantially complete. illustrates a second embodiment of the s of the present invention.

In this second embodiment an H28 l unit 250 has been added, downstream of the separator 230. The primary cooled vapor t stream 231 passes through the H28 removal unit 250 (which may comprise a sorbent bed, liquid wash, or other similar tus). The H28 in the primary cooled vapor t 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 H28-containing waste being appropriately discarded. illustrates a third embodiment of the process of the present invention.

In this third embodiment, an H28 l unit 350 has been added, downstream 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 completely d, and a secondary cooled vapor product 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 primary aqueous stream 333. In the oxidation reactor, the gaseous H2S stream 352 is brought into contact with the primary aqueous stream 333 and an appropriate catalyst, and forms S, which is then oxidized to form (NH4)2SO4. In this way, a secondary cooled product vapor stream 351, ning only trace amounts of H2S, and comprising ily H2, non-condensable hydrocarbons, CO2, and CO, is obtained. In addition, 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 sour-water stripper 460 in this fourth embodiment of the process of the present invention. This approach allows a gaseous stream 461 comprising primarily NH3 to be recovered, while the water and (NH4)2SO4 are recovered separately from the ater er in a secondary treated aqueous stream 462.

(NH4)2SO4 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 reactor 540, which accepts the primary s stream 533 from the tor. Water, NH3 and H28, and any (NH4)2S formed by the reaction of NH3 and H28, are d in the sour—water stripper 560, and leave the sour-water stripper as a gaseous stream 562. A stream of d liquid water 561 is thereby produced. This puriﬁed water stream 561 is then available as a product . 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, g (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 t with the s 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 forming (NH4)2S, and this solution is then introduced into the oxidation reactor 540, for conversion to SO4. This approach makes a stream of puriﬁed water 561 available, and s a concentrated treated stream 542 of water, NH; and (NH4)2SO4 at the outlet of the oxidation reactor 540. illustrates asixth 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 downstream 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 r apparatus).

The H28 in the primary cooled vapor product stream 631 is substantially completely removed and a secondary cooled product vapor stream 651 sing primarily H2, CO, CO2, and non-condensable hydrocarbon vapors is obtained. As in the third embodiment, the H28 is red, in a stream 652 comprising primarily gaseous H28, and is sent to the oxidation reactor 640.

As described herein above in the ption of the ﬁfth ment, dissolved NH3 and H28, and any S formed by the reaction ofNH3 and H28, are driven out of the primary aqueous stream 633 in the sour—water er 660. Water, NH3 and H23, and any (NH4)2$ formed by the reaction of NH3 and H28, are removed in the sour-water stripper 660, and leave the ater stripper as a gaseous stream 662. A stream of puriﬁed water 661 is thereby produced. This puriﬁed water stream‘66l is then available as a product 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 (NH4)2S, and this solution is then introduced into the oxidation reactor 640, for conversion to (NH4)2SO4. r, 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 H2S in this stream go back into solution forming (NH4)2S, and this solution is then introduced into the oxidation reactor 640, for conversion to (NH4)2SO4. This approach makes a stream of puriﬁed water 661 available, and creates a trated 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 removal unit is also introduced to the oxidation reactor.

This sixth ment of the process of the present ion makes a stream of puriﬁed water 661 available, and creates a concentrated treated stream 642 of water, NH3 and SO4 at the outlet of the oxidation reactor 640. It also provides a secondary stream of cooled vapor product 651 which may n minute concentrations of H28, and promotes high overall conversion ofH28 to an (NH4)ZSO4 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 hydropyrolysis of biomass or plastic with the ammonium sulfate recovered from this process to produce an agricultural fertilizer t, as a powder, granulated, or pelletized material that can both improve the quality of a soil for use as an ltural 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 subjected to hydropyrolysis. The tal composition of the wood is presented in Table A, below. The composition is presented on both an overall basis (which es 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 sulfur were present 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 en 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 en 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 t vapor stream constituted 0.18% of the mass of the feedstock, 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 ing products have a greater total mass than the wood that was reacted.

As an example, one might assume that one kilogram of moisture-free, ash-free wood is subjected to yrolysis. In this case, the vapor stream ns 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 NH; and 0.014 moles of H28. The molar ratio of NH3 to H28 is ore 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 adequate to react all the H28 in the stream with NH3, and produce an aqueous on of (NH4)2S.

Further, the interaction with hydrogen in the hydropyrolysis process converts a signiﬁcant fraction of the oxygen in the dry, ee wood into water vapor in the vapor stream leaving the hydropyrolysis process. 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 sufﬁcient to substantially and tely ve all of the NH3 and H28 present in the yrolysis product vapor stream.

While all or almost all of the NH; g the hydropyrolysis reactor ultimately goes into solution in the primary aqueous stream, the solubility of H28 in aqueous solutions depends 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 cantly increase the solubility of H28 in the ne aqueous solution. H28 and NH3 react spontaneously in aqueous solution to form (NH4)2S, though the sulﬁde may be present in a dissociated form. However, 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 remaining concentration 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 of NH; and H28 in the primary s stream will be even lower than they would be if the feedstock were completely dry, meaning that more H28 can be stripped from the cooled vapor stream in the condenser 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 ons of (NH4)28 containing up to 52% by mass of (NH4)2S appear to be commercially available. % moisture 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 s is equivalent, and a second feedstock, 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 re— 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 H28 in the product vapor. The molar ratio ofNH3 to HZS 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 ammonium sulﬁde. As was the case with wood, sufﬁcient water formed, during yrolysis of corn stover, to tely dissolve any ammonium 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 process, and the resulting products have a greater total mass than the feedstock that was d.

Initial Composition Initial Composition, MAF Basis % c (MP) % H M) .1.”— % 0 (MP) % N (MF) % 5 (MP) Table C. Composition of corn typical stover sample Corn Stover Hydropyrolsyis Hot Vapor t 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 on to certain preferred embodiments thereof, and many details have been set forth for purpose of illustration, it will be apparent to those skilled in the art that the invention is susceptible to additional embodiments and that certain of the details described herein can be varied considerably without departing from the basic principles of the invention.

Aspects of the invention are set out below. 1. 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 s vapor stream to a condensation temperature resulting in an aqueous stream; sending the aqueous stream to a tic 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 sulfide. 2. The method of 1 further 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 1 further sing: removing hydrogen sulfide from the cooled t vapor stream. 4. The method of 3 further comprising: sending the hydrogen sulfide to the catalytic reactor, along with the primary aqueous stream, to react with ammonia t in the primary aqueous stream, to form ammonium sulfide and then ammonium sulfate; and recovering the cooled product vapor stream resulting in a high l conversion of hydrogen sulfide to ammonium e.

. The method of 1 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 primarily water and um sulfate. 6. The method of 5 wherein the sour water stripper is positioned upstream of the catalytic reactor.

AH26(10990077_1):RTK 7. The method of 1 further comprising: treating the aqueous stream with a sour water stripper ing 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 reactor. 8. The method of 1 further comprising: treating the aqueous stream with a sour water stripper oned 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 1 further comprising: combining char produced from the hydropyrolysis of the biomass with recovered ammonium sulfate to create a nutrient for lignocellulosic biomass that also is a soil amendment.

. The method of 9 further sing: pelletizing the mixture of char and recovered ammonium sulfate to create a densified nutrient for ellulosic biomass that also is a soil amendment. 11. The method of 9 further comprising: pelletizing the mixture of char, recovered ammonium sulfate, and agricultural fertilizers to create a densified nutrient for nourishing lignocellulosic biomass that also is a soil amendment. 12. A method for removal of sulfur from biomass conversion ts comprising: processing the biomass in a hydropyrolysis reactor, resulting in char and a heated s vapor stream containing hydrogen, water vapor, condensable hydrocarbon vapors, noncondensable hydrocarbon , carbon monoxide and carbon dioxide; cooling the process vapor stream to a condensation ature to a cooled and condensed product ; separating the cooled and condensed product stream into a gaseous and liquid component; obtaining a liquid hydrocarbon stream; obtaining an aqueous stream, containing water, a, and ammonium sulfide; obtaining a cooled product vapor stream, containing non-condensable process vapors comprising H2, CH4, CO, CO2, ammonia and en sulfide; AH26(10990077_1):RTK sending the aqueous stream to a catalytic reactor; injecting air into the catalytic reactor thereby oxidizing ammonium sulfide over a catalyst resulting in ammonium sulfate; obtaining an aqueous product stream containing water, ammonia and ammonium sulfate; ating excess water from the aqueous product stream containing ammonium sulfate ing in steam and a concentrate of ammonium sulfate; cooling the concentrate of um sulfate to precipitate out the ammonium sulfate as crystallized um e; and filtering out the crystallized um sulfate. 13. The method of 12 further comprising the step of: stripping ammonia from the s stream containing water, ammonia and ammonium sulfate to create a te purified stream of gaseous ammonia. 14. The method of 13 further comprising the step of: introducing the aqueous stream containing ammonium e a boiler to convert ammonium sulfate to crystallized ammonium sulfate and steam.

. The method of 12 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 15 further comprising the step of: sending the steam passing from the guard bed to a steam reformer. 17. The method of 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 17 further comprising the step of: sending the steam passing from the guard bed to a steam reformer. 19. The method of 12 wherein the catalyst is monosulfonated cobalt phthalocynanine.

AH26(10990077_1):RTK Further aspects include the following. 1. A method for sing 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; separating the process vapor stream into a primary cooled vapor product stream, a liquid hydrocarbon stream, and a y aqueous stream; wherein the primary cooled vapor product stream comprises non-condensable process vapors, H2, hydrogen sulfide, CO, and CO2, the liquid arbon stream comprises condensable hydrocarbons, and the primary aqueous stream comprises water, ammonia, en sulfide and ammonium e; treating the primary aqueous stream with a sour water stripper; concentrating the hydrogen sulfide and ammonia into a cooled s water stream, and a second purified water stream; sending the cooled process water stream to a catalytic reactor; injecting air into the catalytic reactor to obtain a concentrated treated stream containing water, ammonia and ammonium sulfate; and a second gaseous stream ning N2 and O2. 2. The method of 1 further comprising: maintaining the cooled s water 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 1 further comprising: removing hydrogen sulfide from the primary cooled vapor product . 4. The method of 3 further comprising: sending the hydrogen sulfide to the tic reactor, along with the cooled process water stream, to react with ammonia present in the cooled process water stream, to form ammonium sulfide and then ammonium sulfate to form a trated treated stream; and recovering the concentrated treated stream resulting in a high overall conversion of hydrogen sulfide to ammonium sulfate.

. The method of 1 further comprising: AH26(10990077_1):RTK treating the aqueous stream leaving the catalytic reactor with a sour water stripper ing in a gaseous stream comprising ily ammonia and an aqueous stream comprising primarily water and ammonium sulfate. 6. The method of 1 further comprising: combining char ed from the hydropyrolysis of the biomass with recovered ammonium sulfate to create a nutrient for lignocellulosic biomass that also is a soil amendment. 7. The method of 6 further comprising: izing the mixture of char, recovered ammonium sulfate to create a densified nutrient for lignocellulosic biomass that also is a soil amendment. 8. The method of 6 r comprising: pelletizing the mixture of char, recovered um sulfate, and agricultural fertilizers to create a densified nutrient for nourishing lignocellulosic biomass that also is a soil amendment. 9. The method of 1 further sing the step of: introducing the aqueous stream containing ammonium sulfate a boiler to convert ammonium sulfate to crystallized ammonium sulfate and steam.

. The method of 1 further comprising the step of: sending the steam from the evaporation step through a guard bed to remove trace H2S from the steam. 11. The method of 10 r comprising the step of: sending the steam passing from the guard bed to a steam reformer. 12. The method of 9 further sing the step of: sending the steam created by the boiler through a guard bed to remove trace H2S from the steam. 13. The method of 12 further comprising the step of: sending the steam passing from the guard bed to a steam reformer. 14. The method of 1 wherein the catalyst is monosulfonated cobalt phthalocynaninc.

AH26(10990077_1):RTK WE

Claims

CLAIM :

1. A yrolysis process comprising: ucing biomass and hydrogen into a hydropyrolyzer comprising one or more reactors; sufficiently deoxygenating the s to provide a vapor product that exits the hydropyrolyzer at a temperature such that all constituents of the vapor product are maintained in the gaseous state, the vapor product comprising deoxygenated condensable arbons, noncondensable gases, and water; cooling the vapor t to condense a liquid organic phase and a liquid aqueous phase comprising at least one species of the vapor t, including ammonia (NH3), that is solubilized in the liquid aqueous phase; and phase separating the liquid aqueous phase, comprising the solubilized NH3, from the liquid organic phase and treating the liquid aqueous phase to obtain a gas phase NH3 product or an aqueous NH4OH product.

2. The process of claim 1, wherein the hydropyrolyzer comprises multiple reactors in .

3. The process of claim 1 or claim 2, wherein NH3 and H2S are first and second species of said at least one species of the vapor product, wherein said cooling of the vapor product condenses the liquid s phase comprising an initial NH3 amount and an initial H2S amount, and wherein the solubilized NH3 is t in the liquid aqueous phase as an excess amount that remains after reaction of said initial NH3 amount with said initial H2S amount to form (NH4)2S in the liquid aqueous phase.

4. The process of claim 3, wherein treating the liquid aqueous phase comprises catalytically reacting the liquid aqueous phase with oxygen to substantially oxidize the (NH4)2S to (NH4)2SO4.

5. The process of any one of claims 1 to 4, further comprising separating, from the condensed organic and aqueous phases, a cooled vapor phase comprising the non-condensable gases including ndensable hydrocarbons and H2S.

6. The s of claim 5, further comprising treating the cooled vapor phase to substantially remove the H2S. AH26(13073655_2):MBS

7. The process of claim 6, wherein treating the cooled vapor phase comprises contacting the cooled vapor phase with a bed of sorbent or with a liquid wash.

8. The process of any one of claims 5 to 7, further sing ting at least a portion of the cooled vapor phase to steam reforming, in order to generate hydrogen.

9. The process of any one of claims 1 to 3, wherein the treating the aqueous phase comprises subjecting the liquid aqueous phase to sour water stripping to obtain the gas phase NH3 product.

10. The process of claim 9, wherein NH3 and H2S are first and second species of said at least one species of the vapor product, wherein said g the vapor product condenses the liquid s phase comprising an l NH3 amount and an initial H2S amount, and wherein the solubilized NH3 is present in the liquid aqueous phase as an excess amount that remains after reaction of said initial NH3 amount and said initial H2S amount to form (NH4)2S in the liquid aqueous phase, and wherein the gas phase NH3 product is obtained following reacting the liquid aqueous phase with oxygen to substantially oxidize the (NH4)2S to (NH4)2SO4, followed by subjecting the liquid aqueous phase to the sour water stripping.

11. The process of claim 10, n reacting the liquid aqueous phase with oxygen is performed catalytically.

12. The process of any one of claims 5 to 7, wherein the aqueous NH4OH product is obtained following ng the liquid aqueous phase with oxygen to substantially oxidize the (NH4)2S to (NH4)2SO4.

13. The s of any one of claims 1 to 12, n the biomass contains moisture that contributes to the liquid aqueous phase.

14. The process of any one of claims 1 to 13, n the deoxygenated condensable hydrocarbons are substantially recovered in the liquid organic phase and comprise hydrocarbons having properties corresponding to gasoline, diesel, and kerosene.

15. The process of any one of claims 1 to 14, wherein the biomass contains nitrogen (N) nds and sulfur (S) compounds that, upon reaction with said hydrogen that is introduced into said hydropyrolyzer, form both NH3 and H2S that are present in the vapor product, wherein AH26(13073655_2):MBS an initial amount of NH3 that is present in excess of that required to react with an initial amount of H2S that is present, to form (NH4)2S.

16. The process of any one of claims 1 to 15, wherein said vapor product comprises both NH3 and H2S as first and second species of said at least one species of the vapor product and the liquid aqueous phase comprises more water than is sufficient to ve, into the liquid aqueous phase, (NH4)2S that is formed by the reaction of the NH3 with the H2S.

17. A method for ing an a product, comprising: processing biomass in a hydropyrolyzer to obtain solid char and a heated vapor product that exits the hydropyrolyzer at a temperature such that all tuents of the vapor product are maintained in the gaseous state, the vapor product comprising hydrogen, carbon monoxide, carbon dioxide, deoxygenated condensable hydrocarbons, and water vapor; cooling the heated vapor product to condense, as separate liquid phases, an organic phase and an aqueous phase comprising NH4OH that is formed from the dissolution of NH3 from the heated vapor t into the aqueous phase; and separating the liquid phases and ing the ammonia product as a gas phase NH3 product or an aqueous NH4OH product from ng of the aqueous phase.

18. The method of claim 17, wherein the aqueous phase further comprises (NH4)2S, resulting from the dissolution of both NH3 and H2S from the heated vapor product into the aqueous phase and reaction of a portion of dissolved NH3 with dissolved H2S.

19. The method of claim 17 or claim 18, wherein the hydropyrolyzer comprises multiple rs in series.

20. The method of any one of claims 17 to 19, wherein the ammonia product is a gas phase NH3 product that is obtained by subjecting the aqueous phase to sour water stripping.

21. The method of any one of claims 17 to 20, further sing: separating, from the liquid phases, a cooled vapor phase comprising non-condensable arbons, and steam reforming at least a portion of the non-condensable hydrocarbons to generate hydrogen that is used for the processing of the biomass in the hydropyrolyzer. AH26(13073655_2):MBS

22. A gas phase NH3 product or an s NH4OH product made by the process of claim 1 or claim 17.

23. A hydropyrolysis process comprising: introducing a biomass feedstock and hydrogen into a hydropyrolyzer comprising one or more reactors, n sulfur is present in the biomass feedstock; sufficiently deoxygenating the biomass to provide a vapor product that exits the hydropyrolyzer at a temperature such that all constituents of the vapor product are maintained in the gaseous state, the vapor product comprising deoxygenated condensable hydrocarbons, noncondensable hydrocarbons and H2S, and water; cooling the vapor product to obtain a condensed liquid organic phase, a sed liquid aqueous phase, and a cooled vapor phase comprising at least a portion of the H2S; separating the condensed liquid c phase, the condensed liquid aqueous phase, and the cooled vapor phase; treating the cooled vapor phase to substantially remove the H2S and obtain a treated vapor phase comprising at least a n of the non-condensable hydrocarbons; and subjecting the d vapor phase to steam ing, in order to generate reformer hydrogen from the non-condensable hydrocarbons.

24. The process of claim 23, wherein the hydropyrolyzer comprises multiple rs in series.

25. The process of claim 22 or claim 23, wherein the step of treating comprises contacting the cooled vapor phase with a bed of sorbent or with a liquid wash.

26. The process of any one of claims 23 to 25, further comprising recycling at least a portion of the reformer hydrogen to the hydropyrolyzer. Gas logy Institute By the Attorneys for the Applicant SPRUSON & FERGUSON Per: AH26(13073655_2):MBS