Patent Publication Number: US-2016229697-A1

Title: Activated Carbon Production at Biomass-Fueled Steam/Electric Power Plants

Description:
BACKGROUND OF THE INVENTION 
     At a typical steam/electric biomass power plant, various types of woody fuels, typically hogged trees and trimmings, are combusted to produce steam, and a steam turbine drives a generator to produce electric power. Electrical generation capacity of biomass plants (excluding municipal solid waste) in the U.S. totals about 7.5 GWe. Most of these burn hogged forest residue and lumber mill waste. About half of the plants in the U.S. are in the Northeast, and several are in California. They produce renewable-source electric power, and nominal electric generation capacities range from 2.5 MWe to over 200 MWe; although most are in the range of 10 to 25 MWe. 
     Although some biomass plants have a captured secure fuel source, for example from owned tree farms, many biomass plants are challenged with sourcing enough fuel during economic downturns, for example when lumber production is reduced. Another challenge is the low and variable price paid by many electric utilities for base load renewable-source electric power. Some plants are placed in idle shutdown for years at a time until economic conditions improve. Ash disposal and particulate matter emissions have also posed problems for some biomass plants. 
     An object of the invention is to retrofit existing biomass plants with activated carbon production facilities, with fuel gas from the pyrolysis and activation processes replacing solid fuel as an energy source for steam generation, thus improving the profitability and environmental profile of the combined operation. 
     Pyrolysis (destructive distillation) of organic materials consists of heating to approximately 950° F. in the absence of oxygen for a time sufficient to drive off volatile materials (gases, vaporized liquids, and vaporized tars), leaving a char consisting of fixed carbon and ash. Pyrolysis has been practiced in various forms for thousands of years, mostly in batch retorts producing charcoal. Several continuously-operating pyrolysis processes are well known in industry. The term “pyrolysis” as used in this invention is distinct from “torrefaction”, which also operates in the absence of oxygen but at much lower temperatures in the range of 450 to 550° F. The benefit of pyrolysis over torrefaction is the production of a volatile fraction with much lower moisture content and production of char with much higher fixed carbon content and lower residual tars. 
     In a similar process known as gasification, a controlled amount of air is admitted and partially combusts the feedstock, and a low heating value syngas is produced. A 10-MWe biomass plant in Chowchilla, California utilized two rabble-arm gasifiers in series, producing enough syngas to operate that plant and enough char to fuel a similar size biomass plant nearby. The Chowchilla plant has been dismantled, although gasification is being considered for biomass plants elsewhere due to reduced particulate emissions. The char produced in a gasification plant generally contains too little fixed carbon to be suitable for activation. 
     Pyrolysis char can be processed by a number of known and commercially proven means into a high-value activated carbon product, typically by contacting with steam at approximately 1300° F., where about half of the fixed carbon is converted into a combustible syngas consisting of carbon monoxide and hydrogen through the well-known water gas reaction. Other means of activation, such as chemical activation, wherein the material is impregnated with activating chemicals such as zinc chloride, phosphoric acid, or potassium hydroxide, then heated in an inert environment and finally washed, are not the subject of this invention. 
     The ash that otherwise would be produced as a residue of solid fuel combustion is instead retained in the activated carbon product, and so particulate matter emissions from a biomass plant retrofitted according to the invention will be much reduced. Furthermore, much of the fixed carbon in the activated product, and in any biochar produced as a byproduct and used agriculturally, can be considered as sequestered since activated carbon is commonly regenerated, not incinerated, and biochar is stable in the soil environment. Thus, there is potential for reduction of greenhouse gas emissions and also sale of carbon credits. 
     No biomass plant in the U.S. known to the inventors utilizes pyrolysis and char production, or subsequent activation, as means of generating fuel gas for the steam/electric power generation process as described in the invention. 
     The market for activated carbon in air and water pollution control, gold ore refining, and numerous industrial and food processing purification processes, is very large. Market report abstracts obtained from internet searches value the annual worldwide market at about $7.5 billion, and growth is projected at 10% per year or more over the next several years. Most activated carbon is produced from coal and some is produced from wood, but many grades preferred in industrial purification applications are produced from coconut shells in China and Southeast Asia. Activated carbon produced from walnut shells and almond shells, reportedly similar in quality to that derived from coconut shells, is available from several manufacturers in mainland China according to an internet search. To the inventors&#39; knowledge, there are no full-scale activated carbon production facilities in the U.S. using nut shell or similar feedstocks. 
     There are several large scale activated carbon producer/distributors in the U.S., including Calgon Carbon, Mead Westvaco, Cabot, and Carbon Activated, and sale of activated carbon from nut shells and hardwood at adequate prices is not expected to be difficult. A distributor has offered a purchase price of approximately $1,000 per ton for activated carbon from walnut shells equivalent in quality to that made from coconut shells, and pricing for grades certified for potable water treatment and food processing can range up to $2,500 per ton. 
     Approximately 175,000 tons of walnut shells and 720,000 tons of almond shells were generated in 2013 in California, according to the USDA National Agricultural Statistics Service, most of this in the Sacramento and San Joaquin Valleys. Plantings of these nuts are increasing. Walnut shells are processed and sold wholesale in various size and purity grades for up to $2,000 per ton and more, for a number of different uses such as oil adsorption from petroleum industry wastewaters, grit blasting media, pet bedding, and cosmetic base. Some walnut shells and nearly all of the almond shells are sold un-processed at a much lower price for lower-value uses such as biomass plant fuel and cattle bedding. Approximately 60,000 tons of other nut shells suitable for activated carbon (pistachio, hazelnut, and pecan) were generated in 2013 in Oregon, California, and southern/southwestern states according to USDA data, with evidently little sales potential. Hardwood orchard trimmings and whole trees from orchard removal are a good feedstock for activated carbon. Walnut and almond trees and trimmings are now purchased by biomass plants in the Sacramento and San Joaquin Valleys for about $20 per ton hogged and delivered. Prices paid for orchard wood in California are decreasing, down to zero in some localities, due to the recent and continuing closures of biomass plants because of insufficient revenue from power sales. Smaller amounts of olive pits and pits from stone fruits (peach, plum, cherry, apricot, nectarine, etc.) are purchased by biomass plants and would constitute good activated carbon feedstock as well. Rice hulls and tire crumb are other candidate feedstocks for char and activated carbon production, although the market for the resulting products has not been quantified. 
     An adequate long-term supply of high and consistent quality feedstock at a reasonable price is key to the successful operation of an activated carbon production plant according to the invention. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWING AND TABLES 
         FIG. 1  is a diagram of the process according to the invention, and KEY TO  FIG. 1  contains the description of the components (letters) and flow streams (numbers). TABLE 1 presents a mass balance and TABLE 2 presents an energy balance for the process depicted in  FIG. 1  assuming walnut shell feedstock. TABLES 1 and 2 do not include Streams  20  (High pressure steam),  21  (Stack gas), or  22  (Electric power); these are treated in the detailed description of the invention hereinafter. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     Refer to  FIG. 1  and KEY TO  FIG. 1 . According to the invention, at a biomass plant, the existing combustion chamber (k), boiler (l), turbine generator (m), and stack gas handling equipment (n) are continued in service, while the existing fuel storage and handling equipment (a) is re-purposed as storage and feedstock handling means for a new activated carbon production plant. The existing bottom ash handling equipment is removed. 
     Feedstock ( 1 ), after pre-processing and size reduction as necessary for convenient feeding, at a maximum moisture content of typically 7%, is pyrolysed typically in a continuously operating externally heated rotary kiln or parallel-operating kilns (b) at typically 950° F. using equipment and procedures common in industrial practice. The volatile pyrolysis products driven off in vapor and gaseous form ( 3 ) are maintained at a minimum temperature (typically 600° F.) sufficient to prevent condensation throughout subsequent handling and combustion. The char discharged from the pyrolyser undergoes size reduction typically in a roll crusher (c) such that the crushed char is readily fluidized. A small fraction of finely divided char ( 18 ), too small for the fluidization process, is collected for further processing and sale in forms such as charcoal briquettes and biochar, or pelletized to a size suitable for fluidization. The remainder ( 2 ), along with char fines ( 4 ) removed from the pyrolysis products typically by a cyclone (d), is activated in a directly heated vertical single- or multi-stage fluidized bed reactor or parallel-operating reactors (f) operated in continuous or sequential batch mode at typically 1300 to 1350° F. using equipment and procedures common in industrial practice. Low pressure steam ( 13 ) at typically 50 psig and 350° F. is drawn from the existing steam turbine and is introduced into the activation reactor(s) and serves as the reactant to activate the carbon. Product carbon ( 9 ) is collected, further sized, and packaged for sale. Activated carbon fines ( 12 ) are removed from the activation offgas ( 10 ) typically in a cyclone (e) and are added to the product carbon or char. 
     De-dusted pyrolysis volatiles ( 5 ) are divided into a fuel gas stream ( 6 ) for the pyrolyser burner (g), a fuel gas stream ( 7 ) for the boiler burner (i), and a fuel gas stream ( 8 ) for the activation reactor burner or burner set (h). De-dusted activation offgas ( 11 ) is directed to the boiler burner or, alternatively, used as the means of heating the pyrolyser. Combustion air ( 14 ), ( 15 ), ( 16 ) for burners (g), (h), (i), and combustion chamber overfire air, is provided by an atmospheric air forced draft blower (j). A small amount of high-temperature flue gas from the pyrolyser burner ( 17 ) at typically 950° F. is added to the hot combustion chamber offgas powering the existing boiler (i). High-pressure steam ( 20 ), at typically 650 psig and 750° F., drives the turbine generator producing electricity ( 22 ) sold to the power utility. 
     Since all fuel gas is de-dusted and the ash content in the feedstock is carried offsite as a component of the carbon products, the existing bottom ash handling equipment in the combustion chamber (k) can be removed. The biomass plant&#39;s stack gas handling equipment, including flue gas recirculation and selective catalytic reduction process for control of nitrogen oxides and heat recovery, heat recovery steam generator, particulate removal equipment (baghouse, electrostatic precipitator, etc.), and sulfur oxides control process, as they exist at specific plants, remain in service. Since according to the invention the particulates in the fuel gas have been nearly eliminated prior to combustion, particulate matter emissions in the stack gas ( 21 ) are expected to be reduced by over 85% compared with emissions from the original biomass plant. For biomass plants where emissions of sulfur oxides are limited by permit, common practice is to feed crushed limestone into the combustion chamber where it is calcined, the calcium reacting with the sulfur oxides to form calcium sulfate (gypsum), and the gypsum disposed of as a component of flyash. Application of the invention will render the produced gypsum recoverable for sale as byproduct agricultural gypsom since there will be very little flyash. 
     Projected economic and environmental benefits resulting from application of the invention are presented for a specific example in the preferred embodiment. 
     Preferred Embodiment 
     Refer to  FIG. 1 , KEY TO  FIG. 1 , and TABLES 1 and 2. In the preferred embodiment of the invention, an example biomass plant with a nominal power production rating of 10 MWe is retrofitted with activated carbon production and associated fuel gas generation facilities using walnut shells as an example feedstock. Walnut shells at 7% moisture ( 1 ) are fed at a constant rate of 10 dry tons per hour into the externally heated rotary kiln pyrolyser (b), producing char and raw gas. Char exiting the roll crusher (c) contains about 5% fines by weight ( 18 ), or 341 lb/hr, for further processing without activation. The activation burner set (h), typically one burner per stage in a multiple-stage fluidized bed activation reactor (f), is operated at stoichiometric or slightly sub-stoichiometric oxygen ratio so as to avoid combusting the char, and provides the heat and most of the fluidization energy. Steam is injected at a rate considerably in excess of stoichiometric ratio. Based on literature values and preliminary testing, it is assumed that about 50% of the char is lost through reaction with the process steam ( 13 ). Combined with the small amount of activated carbon fines from the activation offgas cyclone, the overall weight yield of saleable activated carbon from dry feedstock, ( 9 ) plus ( 12 ), is expected to be about 17%. 
     A typical biomass plant generates nominally 1 MW of electric power for each wet ton per hour of variable moisture content biomass fuel combusted. If a 10-MWe biomass plant is retrofitted with activated carbon production facilities according to the invention, processing 10 dry tons per hour of walnut shells, it is estimated that about 5.6 MWe can be generated, or just over half of the original plant&#39;s nominal electric power production rate, while producing 1.7 tons per hour of activated carbon at an assumed $1,000 per ton sale price. Base load renewable-source power is currently purchased by investor-owned utilities in California for between $32 and $50 per MWh. The assumption made for this example is that the average price paid is $40 per MWh. Furthermore, it is assumed that fuel for the biomass plant can be obtained for $20 per wet ton, but that unprocessed walnut shells for activated carbon will cost $60 per dry ton in order to secure a long-term supply. For this example, assuming an 8,000-hr. operating year, the quantity of walnut shells needed (wet basis) is 86,000 tons per year, amounting to about half of what is currently produced in California. 
     Using the above assumptions, assuming an 8,000-hr. operating year, estimates of annual gross margin (revenue from sales of power and activated carbon less cost of feedstock) for the existing 10-MWe biomass plant compared with the same plant retrofitted according to the invention, are presented in the following table. The small revenues from sale of ash from the existing plant, and of char and gypsum from the retrofitted plant, are not included. 
     
       
         
           
               
               
               
               
               
             
               
                   
                   
               
               
                   
                   
                 Activated 
                   
                   
               
               
                   
                 Power 
                 carbon 
                 Cost of 
                 Gross 
               
               
                   
                 revenue 
                 revenue 
                 feedstock 
                 margin 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Existing 
                 $3.2 MM/y 
                 nil 
                 &lt;$1.6 MM/y&gt; 
                 $1.6 MM/y 
               
               
                 biomass 
               
               
                 plant 
               
               
                 Retrofitted 
                 $2.2 MM/y 
                 $13.6 MM/y 
                 &lt;$4.8 MM/y&gt; 
                 $10.6 MM/y 
               
               
                 plant 
               
               
                   
               
            
           
         
       
     
     With respect to particulate matter (PM) emissions, an operating permit for an existing 22-MWe biomass plant in northern California was reviewed. This permit limits the combined PM10 and PM2.5 emissions to 30.73 lb/hr. In the case of the example 10-MWe plant in the preferred embodiment, this translates to a permitted 14 lb/hr. As retrofitted according to the invention, the total PM in the flue gas is only 1.8 lb/hr as shown in TABLE 2, Stream 19, entries for “Ash (lb/hr)”, constituting an 87% reduction relative to permit limits even without operating any emissions control equipment. For an 8,000-hr. operating year, this translates to a reduction of nearly 49 tons per year. Pollution credits for PM reduction are sold in California for up to $50,000 per ton/y; therefore, the pollution credits according to the preferred embodiment of the invention could potentially be worth as much as $2.4 million. 
     Major equipment necessary to retrofit a 10-MWe biomass plant according to the preferred embodiment would include four parallel identical pyrolyser/activation reactor lines, due to size limitations of available equipment and to allow for operational flexibility, with one line dedicated as an installed spare to allow for breakdowns and major equipment cleanouts during the operating season. The pyrolysers would be approximately 12 ft. dia. and 60 ft. long, and the activation reactors would be approximately 10 ft. dia. and 40 ft. tall. The activated carbon plant would be located adjacent to the existing combustion chamber, and occupy a footprint approximately 100 ft. square (¼ acre), approximately 5% of the total area of a typical 10-MWe biomass plant. 
     The scope of the preferred embodiment includes installations scaled appropriate to biomass plants of various sizes, including activation plant capacity sufficient to utilize all of the biomass plant&#39;s rated electric power production capacity. In the case of the example for walnut shells in the preferred embodiment, 17.7 dry tons per hour of shells would have to be processed in order to utilize all of the 10-MWe rated capacity. 
     The scope of the preferred embodiment also includes utilization of other feedstocks suitable for production of high quality activated carbon, including but not limited to dried spent walnut shell media from oil adsorption; pure and mixed streams of other nut shells such as hazelnut, pecan, almond, pistachio, brazil nut, macadamia, and coconut; pure and mixed streams of stone fruit and olive pits; dried hardwood and softwood; rice hulls; tire crumb; lignite; and coal. 
     Alternative Embodiments 
     Although from a business perspective it is advantageous to utilize a biomass plant&#39;s existing facilities and active permits when retrofitting according to the invention, the same effect can be achieved by constructing a new purpose-built plant as an alternative embodiment of the invention. 
     In the numerous cases where two identical boiler/generator trains exist at a biomass plant, an alternative embodiment of the invention is to retrofit one of these according to the invention, with the other remaining in service combusting solid biomass fuel or idled for future retrofitting. 
     Municipal solid waste incineration plants combust some cellulosic residues and generate electricity using steam turbines, and they are treated in this invention as an alternative embodiment having a potential for partial retrofitting to produce activated carbon from a new source of suitable feedstock. 
     An alternative embodiment of the invention is to introduce spent activated carbon either alone or along with char into the activation reactor for re-activation and sale as a component of product carbon. 
     An alternative embodiment of the invention is to utilize natural gas as a supplemental fuel in the biomass plant&#39;s combustion chamber, augmenting the fuel gas derived from the pyrolysis and activation processes. 
     An alternative embodiment of the invention is to feed solid biomass fuel into the biomass plant&#39;s combustion chamber to augment the fuel gas derived from the pyrolysis and activation processes. In this embodiment, the bottom ash handling equipment would be retained. 
     An alternative embodiment of the invention is to omit the activation reactor and produce only biochar for sale. 
     The scope of the invention includes application of all known and commercially proven methods for continuous pyrolysis and steam char activation other than those specified herein, including but not limited to vertical rabble-arm pyrolysers, inert gas internally heated rotary kilns, fluidized bed pyrolysers or low temperature gasifiers, externally heated rotary kiln activation / reactivation reactors, sequential batch operation of activation reactors where multiple processing lines are installed, and the Continuous Ablative Reactor according to U.S. Pat. No. 5,770,017. 
     The scope of the invention includes processing of feedstock prior to pyrolysis by means such as drying, de-stoning, and size reduction; and removal of less desirable feedstock constituents, for example removal of almonds, hulls, and the soft outer shell layer from as-received almond shell feedstock. 
     From the general principles and detailed description of the invention presented herein, those skilled in the art will readily comprehend the various modifications to which the invention is susceptible. Therefore, the inventors desire to be limited only by the scope of the following claims and legal equivalents thereof. 
     KEY TO FIG.  1   
     Components 
     a. Feedstock storage and feeding means (part existing) 
     b. Continuously operating pyrolysis means 
     c. Size reduction and sizing means 
     d. Pyrolyser cyclonic gas/solid separation means 
     e. Char activator cyclonic gas/solid separation means 
     f. Continuously operating char activation means 
     g. Pyrolyser gaseous fuel burner 
     h. Char activator gaseous fuel burner or burner set 
     i. Boiler gaseous fuel burner 
     j. Atmospheric air forced draft blower 
     k. Existing biomass plant combustion chamber 
     l. Existing biomass plant boiler 
     m. Existing biomass plant steam turbine generator and condenser 
     n. Existing biomass plant stack gas treatment equipment 
     Flow Streams 
       1 . Walnut shells (example for TABLES  1  and  2 ) 
       2 . Crushed char 
       3 . Raw pyrolysis gas 
       4 . Pyrolyser cyclone solids 
       5 . De-dusted pyrolysis gas 
       6 . Pyrolysis burner gas 
       7 . Boiler fuel gas 
       8 . Activator burner gas 
       9 . Product carbon 
       10 . Activation offgas 
       11 . Dedusted activation gas 
       12 . Activator cyclone solids 
       13 . Process steam 
       14 . Pyrolyser burner air 
       15 . Activator burner air 
       16 . Boiler burner air 
       17 . Pyrolyser flue gas 
       18 . Char fines 
       19 . Combustion gas 
       20 . High pressure steam 
       21 . Stack gas to atmosphere 
       22 . Electric power 
     
       
         
           
               
             
               
                 TABLE 1 
               
               
                   
               
               
                 Mass Balance for FIG. 1 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
            
               
                   
                 Stream Number 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 1 
                 2 
                 3 
                 4 
                 5 
                 6 
                 7 
                 8 
               
            
           
           
               
               
            
               
                   
                 Stream Name 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 Walnut 
                 Crushed 
                   
                 Cyclone 
                 Dedusted 
                 Pyrolysis 
                 Boiler 
                 Activator 
               
               
                   
                 Shells 
                 Char 
                 Raw Gas 
                 Solids 
                 Gas 
                 Burner Gas 
                 Fuel Gas 
                 Burner Gas 
               
               
                   
               
               
                 Temperature, ° F. 
                 70 
                 150 
                 950 
                 950 
                 950 
                 950 
                 950 
                 950 
               
               
                 Pressure, psia 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Total Gas Flowrate (lb/hr) 
                 — 
                 — 
                 14,540 
                 — 
                 14,540 
                 775 
                 6,386 
                 7,390 
               
               
                 Total Flowrate, scfh 
                 — 
                 — 
                 196,341 
                 — 
                 196,341 
                 10,463 
                 86,468 
                 99,787 
               
               
                 Total Flowrate, scfm 
                 — 
                 — 
                 3,272 
                 — 
                 3,272 
                 174 
                 1,441 
                 1,663 
               
               
                 C, (lb/hr) 
                 10,102.7 
                 5,462.9 
                 4,352.3 
                 97.7 
                 4,254.6 
                 226.7 
                 1,865.5 
                 2,162.3 
               
               
                 H, (lb/hr) 
                 1,426.1 
                 317.8 
                 1,091.6 
                 5.7 
                 1,085.9 
                 57.9 
                 476.1 
                 551.9 
               
               
                 O, (lb/hr) 
                 9,611.4 
                 434.5 
                 9,154.0 
                 7.8 
                 9,146.2 
                 487.4 
                 4,010.4 
                 4,648.4 
               
               
                 N, (lb/hr) 
                 92.8 
                 25.8 
                 65.6 
                 0.5 
                 65.2 
                 3.5 
                 28.6 
                 33.1 
               
               
                 S, (lb/hr) 
                 15.8 
                 4.4 
                 11.2 
                 0.1 
                 11.1 
                 0.6 
                 4.9 
                 5.6 
               
               
                 Ash (lb/hr) 
                 256.7 
                 239.0 
                 5.1 
                 4.3 
                 0.9 
                 0.05 
                 0.4 
                 0.4 
               
               
                 Total 
                 21,505 
                 6,484 
                 14,680 
                 116 
                 14,564 
                 776 
                 6,386 
                 7,401.844 
               
               
                 Feedstock Moisture (%) 
                 7 
               
               
                 Solids Feed Rate 
               
               
                 Dry Feed (lb/hr) 
                 20,000 
               
               
                 Water in Feed (lb/hr) 
                 1,505 
               
               
                 Component Flow Rates 
               
               
                 CO (lb/hr) 
                 — 
                 — 
                 1,758.7 
                 — 
                 1,758.7 
                 93.7 
                 771.2 
                 893.8 
               
               
                 CO2 (lb/hr) 
                 — 
                 — 
                 3,326.0 
                 — 
                 3,326.0 
                 177.2 
                 1,458.4 
                 1,690.4 
               
               
                 H2 (lb/hr) 
                 — 
                 — 
                 55.6 
                 — 
                 55.6 
                 3.0 
                 24.4 
                 28.3 
               
               
                 CH4 (lb/hr) 
                 — 
                 — 
                 352.6 
                 — 
                 352.6 
                 18.8 
                 154.6 
                 179.2 
               
               
                 C2H2 (lb/hr) 
                 — 
                 — 
                 0.6 
                 — 
                 0.6 
                 0.0 
                 0.3 
                 0.3 
               
               
                 C2H4 (lb/hr) 
                 — 
                 — 
                 6.2 
                 — 
                 6.2 
                 0.3 
                 2.7 
                 3.1 
               
               
                 C2H6 (lb/hr) 
                 — 
                 — 
                 283.2 
                 — 
                 283.2 
                 15.1 
                 124.2 
                 143.9 
               
               
                 C3 (lb/hr) 
                 — 
                 — 
                 9.7 
                 — 
                 9.7 
                 0.5 
                 4.2 
                 4.9 
               
               
                 C4 (lb/hr) 
                 — 
                 — 
                 1.3 
                 — 
                 1.3 
                 0.1 
                 0.6 
                 0.6 
               
               
                 C5 (lb/hr) 
                 — 
                 — 
                 1.5 
                 — 
                 1.5 
                 0.1 
                 0.7 
                 0.8 
               
               
                 H2O (lb/hr) 
                 — 
                 — 
                 5,717.4 
                 — 
                 5,717.4 
                 304.7 
                 2,506.9 
                 2,905.8 
               
               
                 H2S (lb/hr) 
                 — 
                 — 
                 6.9 
                 — 
                 6.9 
                 0.4 
                 3.0 
                 3.5 
               
               
                 NH3 (lb/hr) 
                 — 
                 — 
                 33.8 
                 — 
                 33.8 
                 1.8 
                 14.8 
                 17.2 
               
               
                 N2 (lb/hr) 
                 — 
                 — 
                 0.0 
                 — 
                 0.0 
                 0.0 
                 0.0 
                 0.0 
               
               
                 SO2 (lb/hr) 
                 — 
                 — 
                   
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 NO x  (lb/hr) 
                 — 
                 — 
                   
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 O2 (lb/hr) 
                 — 
                 — 
                   
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Total Gas (lb) 
                 — 
                 — 
                 11,553 
                 — 
                 11,553 
                 616 
                 5,066 
                 5,872 
               
               
                 Number of lb moles 
                 — 
                 — 
                 517 
                 — 
                 517 
                 28 
                 228 
                 263 
               
               
                 Average Molecular weight 
                 — 
                 — 
                 22.33 
                 — 
                 22.33 
                 22.33 
                 22.23 
                 22.33 
               
               
                 Condensible Liquids (lb/hr) 
                 — 
                 — 
                 2,987.05 
                 — 
                 2,987.05 
                 159.18 
                 1,309.74 
                 1,518.13 
               
               
                 Ash (lb/hr) 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Char (lb/hr) 
                 — 
                 6,484.34 
                 139.30 
                 115.96 
                 23.34 
                 1.24 
                 10.23 
                 11.86 
               
               
                 Steam (lb/hr) 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Feedstock (lb/hr) 
                 21,505 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Total (lb/hr) 
                 21,505 
                 6,484 
                 14,680 
                 116 
                 14,564 
                 776 
                 6,386 
                 7,402 
               
               
                   
               
            
           
           
               
               
            
               
                   
                 Stream Number 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 9 
                 10 
                 11 
                 12 
                 13 
                 14 
               
            
           
           
               
               
            
               
                   
                 Stream Name 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                   
                   
                 Dedusted 
                   
                   
                   
               
               
                   
                 Product 
                 Activation 
                 Activation 
                 Act. Cycl. 
                 Process 
                 Pyrolyser 
               
               
                   
                 Carbon 
                 Off-Gas 
                 Gas 
                 Solids 
                 Steam 
                 Burner Air 
               
               
                   
               
               
                 Temperature, ° F. 
                 1350 
                 1350 
                 1350 
                 1350 
                 350 
                 100 
               
               
                 Pressure, psia 
                 — 
                 — 
                 — 
                 — 
                 50 
                 — 
               
               
                 Total Gas Flowrate (lb/hr) 
                 — 
                 41,239 
                 41,239 
                 — 
                 6,600 
                 2,900 
               
               
                 Total Flowrate, scfh 
                 — 
                 692,801 
                 692,801 
                 — 
                 139,031 
                 38,369 
               
               
                 Total Flowrate, scfm 
                 — 
                 11,547 
                 11,547 
                 — 
                 2,317 
                 639 
               
               
                 C, (lb/hr) 
                 2,953.7 
                 4,769.2 
                 4,721.2 
                 48.0 
                 — 
                 — 
               
               
                 H, (lb/hr) 
                 67.2 
                 1,572.1 
                 1,571.0 
                 1.1 
                 738.6 
                 3.1 
               
               
                 O, (lb/hr) 
                 79.0 
                 16,610.3 
                 16,609.0 
                 1.3 
                 5,861.7 
                 691.8 
               
               
                 N, (lb/hr) 
                 7.7 
                 18,342.6 
                 18,342.5 
                 0.1 
                 — 
                 2,205.6 
               
               
                 S, (lb/hr) 
                 1.8 
                 8.4 
                 8.3 
                 0.0 
                 — 
                 — 
               
               
                 Ash (lb/hr) 
                 238.4 
                 5.3 
                 1.4 
                 3.9 
                 — 
                 — 
               
               
                 Total 
                 3,348 
                 41,307.830 
                 41,253 
                 54 
                 6,600 
                 2,900 
               
               
                 Feedstock Moisture (%) 
               
               
                 Solids Feed Rate 
               
               
                 Dry Feed (lb/hr) 
               
               
                 Water in Feed (lb/hr) 
               
               
                 Component Flow Rates 
               
               
                 CO (lb/hr) 
                 — 
                 4,922.0 
                 4,922.0 
                 — 
                 — 
                 — 
               
               
                 CO2 (lb/hr) 
                 — 
                 9,512.5 
                 9,512.5 
                 — 
                 — 
                 — 
               
               
                 H2 (lb/hr) 
                 — 
                 704.3 
                 704.3 
                 — 
                 — 
                 — 
               
               
                 CH4 (lb/hr) 
                 — 
                 2.8 
                 2.8 
                 — 
                 — 
                 — 
               
               
                 C2H2 (lb/hr) 
                 — 
                 0.0 
                 0.0 
                 — 
                 — 
                 — 
               
               
                 C2H4 (lb/hr) 
                 — 
                 0.0 
                 0.0 
                 — 
                 — 
                 — 
               
               
                 C2H6 (lb/hr) 
                 — 
                 0.0 
                 0.0 
                 — 
                 — 
                 — 
               
               
                 C3 (lb/hr) 
                 — 
                 0.0 
                 0.0 
                 — 
                 — 
                 — 
               
               
                 C4 (lb/hr) 
                 — 
                 0.0 
                 0.0 
                 — 
                 — 
                 — 
               
               
                 C5 (lb/hr) 
                 — 
                 0.0 
                 0.0 
                 — 
                 — 
                 — 
               
               
                 H2O (lb/hr) 
                 — 
                 7,698.9 
                 7,698.9 
                 — 
                 — 
                 27.3 
               
               
                 H2S (lb/hr) 
                 — 
                 2.9 
                 2.9 
                 — 
                 — 
                 — 
               
               
                 NH3 (lb/hr) 
                 — 
                 22.3 
                 22.3 
                 — 
                 — 
                 — 
               
               
                 N2 (lb/hr) 
                 — 
                 18,291.0 
                 18,291.0 
                 — 
                 — 
                 2,205.6 
               
               
                 SO2 (lb/hr) 
                 — 
                 11.2 
                 11.2 
                 — 
                 — 
                 — 
               
               
                 NO x  (lb/hr) 
                 — 
                 71.0 
                 71.0 
                 — 
                 — 
                 — 
               
               
                 O2 (lb/hr) 
                 — 
                 — 
                 — 
                 — 
                 — 
                 667.5 
               
               
                 Total Gas (lb) 
                 — 
                 41,239 
                 41,239 
                 — 
                 — 
                 2,900 
               
               
                 Number of lb moles 
                 — 
                 1,826 
                 1,826 
                 — 
                 366 
                 101 
               
               
                 Average Molecular weight 
                 — 
                 22.59 
                 22.59 
                 — 
                 — 
                 28.69 
               
               
                 Condensible Liquids (lb/hr) 
                 — 
                 0.06 
                 0.06 
                 — 
                 — 
                 — 
               
               
                 Ash (lb/hr) 
                 — 
                 0.44 
                 0.44 
                 — 
                 — 
                 — 
               
               
                 Char (lb/hr) 
                 3,347.74 
                 68.32 
                 13.91 
                 54.42 
                 — 
                 — 
               
               
                 Steam (lb/hr) 
                 — 
                 — 
                 — 
                 — 
                 6,600 
                 — 
               
               
                 Feedstock (lb/hr) 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Total (lb/hr) 
                 3,348 
                 41,308 
                 41,253 
                 54 
                 6,600 
                 2,900 
               
               
                   
               
            
           
           
               
               
            
               
                   
                 Stream Number 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 15 
                 16 
                 17 
                 18 
                 19 
               
            
           
           
               
               
            
               
                   
                 Stream Name 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                   
                 Activator 
                 Boiler 
                 Pyrolyser 
                 Charcoal 
                 Combustion 
               
               
                   
                   
                 Burner Air 
                 Burner Air 
                 Flue Gas 
                 Fines 
                 Gas 
               
               
                   
                   
               
               
                   
                 Temperature, ° F. 
                 100 
                 100 
                 950 
                 150 
                 2884 
               
               
                   
                 Pressure, psia 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 Total Gas Flowrate (lb/hr) 
                 839 
                 66,356 
                 3,676 
                 — 
                 113,996 
               
               
                   
                 Total Flowrate, scfh 
                 161,718 
                 877,819 
                 931,545 
                 — 
                 1,563,886.52 
               
               
                   
                 Total Flowrate, scfm 
                 5,303 
                 14,630 
                 15,526 
                 — 
                 26,065 
               
               
                   
                 C, (lb/hr) 
                 — 
                 — 
                 226.7 
                 287.5 
                 6,586.7 
               
               
                   
                 H, (lb/hr) 
                 25.3 
                 69.9 
                 60.9 
                 16.7 
                 2,117.0 
               
               
                   
                 O, (lb/hr) 
                 5,736.8 
                 15,826.5 
                 1,179.2 
                 22.9 
                 36,445.8 
               
               
                   
                 N, (lb/hr) 
                 18,291.0 
                 50,460.1 
                 2,209.1 
                 1.4 
                 68,831.2 
               
               
                   
                 S, (lb/hr) 
                 — 
                 — 
                 0.6 
                 0.2 
                 13.2 
               
               
                   
                 Ash (lb/hr) 
                 — 
                 — 
                 0.05 
                 12.6 
                 1.8 
               
               
                   
                 Total 
                 24,053 
                 66,356 
                 3,677 
                 341 
                 113,996 
               
               
                   
                 Feedstock Moisture (%) 
               
               
                   
                 Solids Feed Rate 
               
               
                   
                 Dry Feed (lb/hr) 
               
               
                   
                 Water in Feed (lb/hr) 
               
               
                   
                 Component Flow Rates 
               
               
                   
                 CO (lb/hr) 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 CO2 (lb/hr) 
                 — 
                 — 
                 830.8 
                 — 
                 24,134.3 
               
               
                   
                 H2 (lb/hr) 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 CH4 (lb/hr) 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 C2H2 (lb/hr) 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 C2H4 (lb/hr) 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 C2H6 (lb/hr) 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 C3 (lb/hr) 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 C4 (lb/hr) 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 C5 (lb/hr) 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 H2O (lb/hr) 
                 226.4 
                 624.5 
                 544.4 
                 — 
                 18,918.6 
               
               
                   
                 H2S (lb/hr) 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 NH3 (lb/hr) 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 N2 (lb/hr) 
                 18,291.0 
                 50,460.1 
                 2,205.6 
                 — 
                 68,751.1 
               
               
                   
                 SO2 (lb/hr) 
                 — 
                 — 
                 1.2 
                 — 
                 26.3 
               
               
                   
                 NO x  (lb/hr) 
                 — 
                 — 
                 7.4 
                 — 
                 171.6 
               
               
                   
                 O2 (lb/hr) 
                 5,535.8 
                 15,271.9 
                 87.1 
                 — 
                 1,992.0 
               
               
                   
                 Total Gas (lb) 
                 24,053 
                 66,356 
                 3,676 
                 — 
                 113,993.9 
               
               
                   
                 Number of lb moles 
                 839 
                 2,313 
                 130.82 
                 — 
                 4,121.1 
               
               
                   
                 Average Molecular weight 
                 28.69 
                 28.69 
                 28.10 
                 — 
                 27.7 
               
               
                   
                 Condensible Liquids (lb/hr) 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 Ash (lb/hr) 
                 — 
                 — 
                 0.05 
                 — 
                 1.80 
               
               
                   
                 Char (lb/hr) 
                 — 
                 — 
                 — 
                 341.28 
                 — 
               
               
                   
                 Steam (lb/hr) 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 Feedstock (lb/hr) 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                   
                 Total (lb/hr) 
                 24,053 
                 66,356 
                 3,677 
                 341 
                 113,996 
               
               
                   
                   
               
            
           
         
       
     
     
       
         
           
               
             
               
                 TABLE 2 
               
               
                   
               
               
                 Energy Balance for FIG. 1 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
            
               
                   
                 Stream Number 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 1 
                 2 
                 3 
                 4 
                 5 
                 6 
                 7 
                 8 
               
            
           
           
               
               
            
               
                   
                 Stream Name 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 Walnut 
                 Crushed 
                   
                 Cyclone 
                 Dedusted 
                 Pyrolysis 
                 Boiler 
                 Activator 
               
               
                   
                 Shells 
                 Char 
                 Raw Gas 
                 Solids 
                 Gas 
                 Burner Gas 
                 Fuel Gas 
                 Burner Gas 
               
               
                   
               
               
                 Temperature, ° F. 
                 70 
                 150 
                 950 
                 950 
                 950 
                 950 
                 950 
                 950 
               
               
                 Pressure, psig 
                   
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Heat In 
                 Btu/hr 
                 Btu/hr 
                 Btu/hr 
                 Btu/hr 
                 Btu/hr 
                 Btu/hr 
                 Btu/hr 
                 Btu/hr 
               
               
                 HHV of Fuel 
                 174,330,089 
               
               
                 Sens. Heat in Fuel 
                 −40,668 
               
               
                 Latent + Sens. Heat in Fuel 
                 −10,509 
               
               
                 Moisture 
               
               
                 Latent Heat In Inlet Air 
               
               
                 Sensible Heat in Inlet Air 
               
               
                 Heat added 
                 2,505,427 
               
               
                 Sensible Heat of Product Gas 
                   
                   
                 4,060,860 
                   
                 4,060,860 
                 216,408 
                 1,780,578 
                 2,063,874 
               
               
                 Sensible + Latent Heat of 
                   
                   
                 1,253,542 
                   
                 1,253,542 
                 66,803 
                 549,644 
                 637,095 
               
               
                 Product Tar 
               
               
                 Sensible Heat of Char 
                   
                 142,007 
                 36,482 
                 30,370 
                 6,113 
                 326 
                 2,680 
                 3,107 
               
               
                 Sensible Heat of Ash 
                   
                   
                 0 
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 Sensible Heat of Activated Carbon 
               
               
                 Sensible Heat of Water 
               
               
                 Latent Heat of Water 
                   
                   
                 6,009,224 
                   
                 6,009,224 
                 320,239 
                 2,634,883 
                 3,054,103 
               
               
                 Heat of Adsorption of Water 
                   
                   
                 465,269 
               
               
                 HHV of Gas 
                   
                   
                 26,539,098 
                   
                 26,539,098 
                 1,414,300 
                 11,636,679 
                 13,488,118 
               
               
                 HHV of Tar 
                   
                   
                 37,264,623 
                   
                 37,264,623 
                 1,985,876 
                 16,339,533 
                 18,939,214 
               
               
                 HHV of Char 
                   
                 89,265,219 
                 1,917,620 
                 1,596,328 
                 321,293 
                 17,122 
                 140,878 
                 163,292 
               
               
                 Heat loss 
                   
                 1,556,241 
                 3,486,602 
               
               
                 Total 
                 176,784,338 
                 90,963,467 
                 81,033,321 
                 1,626,697 
                 75,454,752 
                 4,021,074 
                 33,084,876 
                 38,348,803 
               
               
                   
               
            
           
           
               
               
            
               
                   
                 Stream Number 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                 9 
                 10 
                 11 
                 12 
                 13 
                 14 
               
            
           
           
               
               
            
               
                   
                 Stream Name 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                   
                   
                 Dedusted 
                   
                   
                   
               
               
                   
                 Product 
                 Activation 
                 Activation 
                 Act. Cycl. 
                 Process 
                 Pyrolyser 
               
               
                   
                 Carbon 
                 Off-Gas 
                 Gas 
                 Solids 
                 Steam 
                 Burner Air 
               
               
                   
               
               
                 Temperature, ° F. 
                 1350 
                 1350 
                 1350 
                 1350 
                 350 
                 100 
               
               
                 Pressure, psig 
                   
                   
                 — 
                   
                 50 
               
               
                 Heat In 
                 Btu/hr 
                 Btu/hr 
                 Btu/hr 
                 Btu/hr 
                 Btu/hr 
                 Btu/hr 
               
               
                 HHV of Fuel 
               
               
                 Sens. Heat in Fuel 
               
               
                 Latent + Sens. Heat in Fuel 
               
               
                 Moisture 
               
               
                 Latent Heat In Inlet Air 
                   
                   
                   
                   
                   
                 28,688 
               
               
                 Sensible Heat in Inlet Air 
                   
                   
                   
                   
                   
                 16,114 
               
               
                 Heat added 
               
               
                 Sensible Heat of Product Gas 
                   
                 18,869,183 
                 18,869,183 
               
               
                 Sensible + Latent Heat of 
                   
                 34 
                 34 
               
               
                 Product Tar 
               
               
                 Sensible Heat of Char 
                 1,278,502 
                 26,092 
                 5,311 
                 20,781 
               
               
                 Sensible Heat of Ash 
                 0 
                 139 
                 139 
                 0 
               
               
                 Sensible Heat of Activated Carbon 
               
               
                 Sensible Heat of Water 
                   
                   
                   
                   
                 2,736,438 
               
               
                 Latent Heat of Water 
                   
                 8,091,953 
                 8,091,953 
                   
                 6,937,232 
               
               
                 Heat of Adsorption of Water 
               
               
                 HHV of Gas 
                   
                 64,650,995 
                 64,650,995 
               
               
                 HHV of Tar 
                   
                 800 
                 800 
               
               
                 HHV of Char 
                 44,060,775 
                 899,199 
                 183,020 
                 716,179 
               
               
                 Heat loss 
                   
                 1,550,269 
                   
                   
                   
                   
               
               
                 Total 
                 45,339,277 
                 94,088,666 
                 91,801,437 
                 736,960 
                 9,673,670 
                 44,802 
               
               
                   
               
            
           
           
               
               
            
               
                   
                 Stream Number 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 15 
                 16 
                 17 
                 18 
                 19 
               
            
           
           
               
               
            
               
                   
                 Stream Name 
               
            
           
           
               
               
               
               
               
               
               
            
               
                   
                   
                 Activator 
                 Boiler 
                 Pyrolyser 
                 Charcoal 
                 Combustion 
               
               
                   
                   
                 Burner Air 
                 Burner Air 
                 Flue Gas 
                 Fines 
                 Gas 
               
               
                   
                   
               
               
                   
                 Temperature, ° F. 
                 100 
                 100 
                 950 
                 150 
                 2884 
               
               
                   
                 Pressure, psig 
               
               
                   
                 Heat In 
                 Btu/hr 
                 Btu/hr 
                 Btu/hr 
                 Btu/hr 
                 Btu/hr 
               
               
                   
                 HHV of Fuel 
               
               
                   
                 Sens. Heat in Fuel 
               
               
                   
                 Latent + Sens. Heat in Fuel 
               
               
                   
                 Moisture 
               
               
                   
                 Latent Heat In Inlet Air 
                 237,910 
                 656,332 
               
               
                   
                 Sensible Heat in Inlet Air 
                 133,637 
                 368,672 
               
               
                   
                 Heat added 
               
               
                   
                 Sensible Heat of Product Gas 
                   
                   
                 3,421,276 
                   
                 104,668,360 
               
               
                   
                 Sensible + Latent Heat of 
               
               
                   
                 Product Tar 
               
               
                   
                 Sensible Heat of Char 
                   
                   
                   
                 7,474 
               
               
                   
                 Sensible Heat of Ash 
                   
                   
                 33 
                   
                 1,266 
               
               
                   
                 Sensible Heat of Activated Carbon 
               
               
                   
                 Sensible Heat of Water 
                   
                   
                 572,236 
               
               
                   
                 Latent Heat of Water 
                   
                   
                   
                   
                 19,884,398 
               
               
                   
                 Heat of Adsorption of Water 
               
               
                   
                 HHV of Gas 
               
               
                   
                 HHV of Tar 
               
               
                   
                 HHV of Char 
                   
                   
                   
                 4,698,169 
               
               
                   
                 Heat loss 
                   
                   
                 72,332 
                 81,907 
                 1,357,292 
               
               
                   
                 Total 
                 371,547 
                 1,025,004 
                 4,065,877 
                 4,787,551 
                 125,911,316