California Studies CoalTL

 
We have previously documented for you the work of Nobel Laureate George Olah, at the University of Southern California's Loker Institute, on the recycling, the profitable conversion, into useful hydrocarbons, of Carbon Dioxide.
 
Somewhat surprisingly, USC, and Dr. Olah and some of his colleagues, have also been involved in the development of technology to convert our abundant coal into the liquid fuels we need, as the enclosed documents attest.
 
Like much about the very real processes which exist for converting coal into liquid fuels, this USC work is not well-published, even though Dr. Olah won the Nobel Prize, in 1994, for his innovative work in hydrocarbon chemistry. The public reports of USC's work which do exist, like those documenting the FMC company's liquefaction of coal in New Jersey for the USDOE, are sparse and incomplete; and, they provide only an outline, at best, of what had to have been a much more detailed and more extensive body of knowledge that was generated.
 
In any case, we present below some very brief passages excerpted from the quite complex presentation of coal liquefaction chemistries studied by USC, as linked above, with a link to one of Dr. Olah's coal liquefaction reports, accompanied by a brief excerpt, following. Comment inserted and appended:  
 
"PRELIMINARY EXAMINATION OF COAL LIQUEFACTION PRODUCTS
 
I. Schwager and T. F. Yen
University of Southern California
Chemical Engineering Department
University Park
Los Angeles. California 90007
 
INTRODUCTION
 
The three direct general processes for converting coals to liquid fuels are: catalyzed hydrogenation, staged pyrolysis, and solvent refining. Each of these processes results in the production of a coal liquid which contains a variety of desirable and undesirable components. The desirable coal liquids are the oils-saturated and aromatic hydrocarbons plus nonpolar nonhydrocarbons, and the non-hydrocarbons. The undesirable species are the asphaltenes and the carbenes-high molecular weight highly aromatic solids, and the carboids-polymerized coke-like materials. The undesirable elements: metals, sulfur, nitrogen, and oxygen are generally present in higher concentration in the asphaltene and carboid fractions. Under hydrogenolysis conditions, the conversion of coal to oil has been suggested to proceed via the following sequence: Coal-Asphaltene-Oil. Therefore, asphaltene generation and elimination are of great importance in the liquefaction process. A study of the chemical and physical properties of asphaltenes may lead to the discovery of ways to reduce or eliminate asphaltene build-up in coal liquids and to thereby increase the yields of desirable coal liquefaction products, In this work, coal liquids from representative liquefaction processes have been separated by solvent fractionation, and the fractions are being examined by various analytical and physical techniques. Particular attention is being directed toward asphaltene separation, purification and characterization. 
 
RESULTS AND DISCUSSION
 
A solvent fractionation scheme for separating coal liquid products into five fractions (oil, resin, asphaltene, carbene, and carboid) is shown. Representative coal liquid samples produced via the three direct coal liquefaction processes were separated into the five fractions described above. For the catalyzed hydrogenation product produced in the Synthoil process, the product composition is about 61% oil, 22% resin, 13%asphaltene, 0.6% carbene, and 3%carboid. The staged pyrolysis filtered product' from the FMC Corporation's COED process has a product composition of about 26% oil, 48% resin, 15% asphaltene, 1%carbene and lack carboid. The solvent refined coal (SRC) produced by Catalytic Inc. based on PAMCO's SRC process affords about 4% oil, 15% resin, 45% asphaltene, 2%carbene, and 9%carboid. The results found in this work are in good agreement with those reported recently for solvent fractionation of a Synthoil catalytic hydrogenation product, and a non-catalytic SRC product.
 
SUMMARY

A preliminary examination of coal liquefaction products from four different coal liquefaction processes has been carried out. Each coal liquid has been separated into five different fractions by solvent fractionation. It may be seen that heteroatoms and metals are generally concentrated in the asphaltene and carboid fractions."
 
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First, above, the "heteroatoms" would be Sulfur, and related contaminants. Moreover, the abstract begs reading of the complete work, if all the copies haven't been stuffed down a depleted oil well somewhere, to gain a clearer understanding of the results and their implications. Perhaps the important point to be taken from this is that, yes, coal can be liquefied into products suitable for refining. And, they know that even in Southern California, if not in Appalachia.
 
Following is the report of additional research into coal liquefaction undertaken by USC's George Olah:
 
 
"Title: Superacid catalyzed coal conversion chemistry. Final technical report, Sept. 1, 1983-Sept.1, 1986.
 
Author: Olah, G.A.
 
Publication Date: January 1, 1986
 
Report Number: DOE/PC/60810-T10; DOE Contract Number: FG22-83PC60810
 
Research Organization: Univ. of Southern Calif., Los Angeles (USA). Loker Hydrocarbon Research Inst. 
 
Abstract:
 
This research project involved the study of a raw comparatively mild coal conversion process. The goal of the project was to study model systems to understand the basic chemistry involved and to provide a possible effective pretreatment of coal which significantly improves liquefaction-depolymerization under mild conditions. The conversion process operates at relatively low temperatues (170/sup 0/C) and pressures and uses an easily recyclable, stable superacid catalysts (HF-BF/sub 3/). It consequently offers an attractive alternative to currently available processes. From the present studies it appears that the modification of coal structure by electrophilic alkylation and subsequent reaction of alkylated coal with HF-BF/sub 3/-H/sub 2/ system under mild conditions considerably improves the extractability of coal in pyridine and cyclohexane. On the other hand, nitration of coal and its subsequent reaction with HF-BF/sub 3/H/sub 2/ decreases the pyridine and cyclohexane extractability. Study of model compounds under conditions identical with the superacidic HF/BF/sub 3//H/sub 2/ system provided significant information about the basic chemistry of the involved cleavage-hydrogenation reactions."
 
Note that Olah's reportage was of coal research done, for at least three years, under contract to our own, US, Department of Energy.
 
And, as in other coal conversion research undertaken by our US DOE, as we've reported, Olah was studying "mild" coal conversion processes; a term which we take to imply lower energy requirements, and thus lower costs, to effect the transmutation. 
 
Odd, isn't it, that our Federal DOE would contract with the University of Southern California to study the conversion of coal into liquid fuels? It's like the US Department of Transportation contracting with WVU to study the molding of beach sand into surf boards.
 
In any case, the work is detailed, and the full reportage of it is beyond the scope of our purpose here, which is to document the fact, that: Multiple technologies exist, including the FMC, SRC and Synthoil processes named by Schwager and Yen, and about which we have previously reported, which, if coupled with the Carbon Dioxide recycling technologies we have documented for you, including some elaborated in other work by USC's George Olah, could enable the United States to end her reliance on foreign petroleum, thereby ushering in an era of domestic economic abundance, and improving the environment while doing so.
 
What we have so far been unable to document is any good reason why all of that isn't already being done on a broad-based industrial scale.

Wyoming Liquefies Pittsburgh Coal

 
The lengths to which our government has gone to hide, obfuscate and confuse the subject, and the truth, of coal-to-liquid conversion technology would be amusing, if the matter weren't so critical to the security of the United States, and to the prosperity of US Coal Country.
 
Two links and two excerpts are enclosed. We'll insert and append some explanatory notes, though they shouldn't really be needed. The implications, we think, are rather obvious.
 
First, an excerpt from the above link: 
 
"Title: Effects of Solvent Characteristics on Wyodak Coal Liquefaction. Annual techhnical progress report.
 
Author: Silver, H.F.; Hurtubise, R.J
 
Publication Date: May 15, 1978
 
Research Organization: Wyoming University, Laramie, Wyoming
 
Abstract:
Wyodak coal liquefaction runs have been completed using nine different solvents derived from Wyodak coal recycle solvent from the Wilsonville, Alabama SRC plant. Results suggest that the effectiveness of the solvents studied tends to improve as the boiling range of the solvent increases. Further, mildly hydrogenated Wyodak solvents appear to be more effective than either unhydrogenated or severely hydrogenated solvent. In addition, 13 additional solvents have been prepared from a Kentucky coal-derived recycle solvent produced at the SRC plant in Tacoma, Washington; from Pittsburgh Seam coal-derived anthracene oils from the Clairton works of U.S. Steel; and from Hanna coal-derived in situ coal gasification tars produced at Hanna, Wyoming. Coal liquefaction runs have been initiated using these solvents. Open column and high-performance liquid chromatography have been used to separate monophenols from recycle solvents. Fluorescence spectroscopy has been employed for identification and characterization of the monophenols. Nitrogen type analysis shows that nitrogen compounds in coal-derived liquids contain a high percentage of quinoline types which may be difficult to remove."
 
Note several things:
 
They shipped Alabama coal liquids, nine of them, made at the Wilsonville, AL, conversion plant, about which we have earlier reported, all the way to Laramie, Wyoming, for further development work.
 
They transported coal from Kentucky for liquefaction at the Tacoma, WA, coal conversion plant, about which we have also previously reported.
 
They then shipped the Kentucky coal liquids from that Washington plant to Wyoming for additional fiddling around with.
 
And, as we have documented from other sources, well-known coal-derived oils, such as "anthracene", can serve as synergistic hydrogenating solvents in coal liquefaction processes. Wyoming got some of that, as well: From the coking ovens of a steel mill in Pittsburgh, PA.
 
Immediately following the above Annual Report, a quarterly Technical Progress Report was issued, as follows:
 
 
"Title: Effects of Solvent Characteristics on Wyodak Coal Liquefaction. Quarterly Technical Progress Report; May, 1978 -- July, 1978
 
Author: Silver, H.F.; Hurtubise, R.J.
 
Publication Date: August 15, 1978
 
DOE Contract Number: EX-76-S-01-2367; Report Number: FE-2367-10
 
Research Organization: Wyoming University, Laramie, Wyoming
 
Abstract:
Efforts have been directed primarily to utilizing additional distillable solvents for coal liquefaction studies. Work on the identification of hydroaromatics, polycylic aromatics and alkylphenols has been continued."
 
 
And, that seems to be it. Coal and coal liquids shipped from, quite literally, all over the nation for further processing and study at the University of Wyoming got distilled into a two-line Abstract that provides no conclusions and, as far as we've so far been able to determine, goes nowhere.
 
The pattern, and the timing, is fairly consistent with all of the other USDOE-sponsored coal liquefaction development projects about which we have so far reported, and there were, obviously, quite a few of them.
 

Coal to Candle Wax

 
We're submitting this very recent report on South Africa's Coal-to-Liquid conversion giant, Sasol, to make only one point.
 
The excerpt:
 
"Sasol Invests In Wax
 
Sasol, the world's largest fuel-from-coal producer, on Tuesday announced an investment of RB.4 billion to double the Sasol Wax production of hard wax in South Africa.
 
It is in line with Sasol's strategy to leverage advanced proprietary technology (which would be Coal-to-Liquid technology - JTM) and is also aligned with our longer-term plans to significantly grow the chemicals businesses of the Sasol group.

The project will also result in increased production of medium waxes, mostly used by the candle industry in Southern Africa."

The point:

So productive and profitable is the business of making diesel fuel and gasoline from coal, that Sasol can afford to spend 4 billion Rand to start making candle wax out of it, as well.

Maybe they would be kind enough to light a few of those coal wax candles for those of us in US Coal Country - and thus help dispel the shadows Big Oil, aka The Prince of Darkness, has cast upon the truth of practical coal-to-liquid conversion technology.

It's beginning to look as if no one else is going to do it for us.2

FMC Liquefies Coal for USDOE in New Jersey

 

We sent you an earlier report of US Government-sponsored coal liquefaction research which referenced yet more such research being conducted for the Fed by FMC Corporation.
 
Herein are two reports of FMC's work on the somewhat ambiguously-titled "Char Oil Development".
 
They didn't, we conjecture, want the word "Coal" appearing in the titles of any documents related to the production of liquid petroleum products, i.e., "oil".
 
First up is the Final Report, Volume I. Which immediately begs the question: Where are the other volumes?
 
We haven't yet been able to find them. Following the excerpt from the link above are a second link and brief excerpt detailing an earlier progress report on the project.
 
Make note of the dates. Work went on for quite awhile. Where are all the data, and all of the substantive reportage?
 
What are the conclusions and recommendations? And, why, for the last three decades, have we, apparently, done nothing further to develop the technology, given an increasingly hostile and imperious OPEC, and dwindling supplies of much more expensive foreign petroleum?  
 
As follows:
 
"Title: Char oil energy development. Volume I. final report, August 18, 1971--June 30, 1975
 
Author: Jones, J.F.; Brunsvold, N.J.; Terzian, H.D.; et. al.
 
Research Organization: FMC Corporation
 
Publication Date: September 01, 1975; Report Number: FE-1212-T-9
 
DOE Contract Number: E(49-18)-1212
 
Abstract:
 
Project COED has been under development by FMC Corporation since 1962. The COED process converts coal to synthetic crude oil, char and gas. The synthetic crude oil is low in sulfur and can be used as feedstock to a refinery or directly as a source of naphtha and fuel oil through simple distillation. The gas can be sold as fuel gas or converted by application of additional technology to pipeline gas or hydrogen. The residual char can be used as a power-plant fuel, or gasified to clean fuel gas for power generation through the application of further technology. Several years of bench-scale development work led to the successful operation of a 100 lb. per hour process development unit followed by the design, construction and operation of a pilot plant designed to process 36 tons of coal per day and to hydrotreat 30 barrels of coal-derived liquid per day. Design capacities have been achieved on all parts of the pilot plant. Significant accomplishments have been demonstrated in solids circulation between multiple fluidized-bed reactors, in the filtration of coal oil and in the upgrading of the coal oil to synthetic crude oil through fixed bed hydrotreating. The COED plant has processed from seven different geographic sources, ranging in ASTM rank from lignite to high-volatile A bituminous coal."
 
And, following, the only Progress Report we have so far been able to find:
 
 
Title: Char Oil Energy Development
 
Affiliation: FMC Corporation; Princeton, NJ
 
Publication: Monthly Reports, April 1968-October 1969; FMC Corp.; Princeton, NJ, Chemical Research and Development Center
 
Publication Date: July, 1974 (Yes, US Government work on coal conversion done in 1968 and 1969 wasn't reported, or "published", until 1974. And, this research, apparently, predates the research included in the Final Report, referenced above, of research performed from 1971 through 1975. - JtM)
 
Abstract:
 
These monthly reports (Apr 68-Oct 69) trace the progress of the development of the COED (charoil-energy-development) process--from bench scale to pilot plant operations at Princeton, New Jersey--by the FMC Corporation under contract (14-01-0001-498) to the Office of Coal Research. Under development since 1962, the COED process converts coal to low-sulfur synthetic crude oil, gas, and char by the fluidized-bed pyrolysis of coal, followed by the hydrotreating of the coal oil to synthetic crude oil. The char can be gasified to give a clean fuel gas for power generation, thus reopening the potential of using high sulfur coals for power generation. Successful operation of a 100 pound-per-hour process development unit led to the design, construction, and operation of a pilot plant at Princeton. The pilot plant can process 36 tons of coal per day and hydrotreat 30 barrels of coal-derived oil daily."
 
Well, 36 tons of coal to 30 barrels of oil doesn't sound all that good, since later technologies we've documented for you can make more than 3 barrels of oil per ton of coal.
 
Still, this was just a "pilot" plant, this is a report of early research and development, and results were encouraging enough that someone kept it operating for another 5 or 6 years, at least; and, it had, at the time of this report, already been operating for 7 years, as in "Under development since 1962, the COED process converts coal to low-sulfur synthetic crude oil".
 
"Coal to low-sulfur synthetic crude oil".
 
Has a nice ring to it, doesn't it? Why haven't we ever heard this particular coal conversion song being played on the stations in West Virginia?
 
And, where are all the other monthly reports, and all the other Volumes of the Final Report? The USDOE sponsored this research, which means we paid for it. It belongs to every US citizen, and especially every US citizen in West Virginia, Pennsylvania, and every other state in US Coal Country.

Ashland Oil Makes 14-cent Gasoline from CoalTL Residues

 
We have recently been reporting on the "Karrick Process" of coal liquefaction, also known, more technically, as the "low-temperature carbonization", or LTC, of coal, which, as we have documented, is being experimented with and developed in other nations, now that the original patents, assigned to US Bureau of Mines scientist Lewis Karrick and a few of his colleagues, early in the last century, have expired.
 
As we have documented, a number of Big Oil petroleum monopolists were inexplicably entrusted by our Federal Government, over the course of decades, with the oversight of several research and development projects that were, for the sake of public perception at least, intended to develop technologies that would enable the United States to convert her abundant coal into needed liquid fuels. 
 
Several oil companies, after gaining experience through government-funded projects, conducted additional research on their own.
 
Herein, one of them, Ashland Oil, is documented to have followed up on their CTL development work with the government by demonstrating, and confirming overseas research we have already reported to you, that the carbonaceous residue left behind by the low-temperature carbonization, i.e. Karrick, processing of coal, to obtain liquid hydrocarbons suitable for refining into petroleum replacements, can itself be further processed to obtain even more hydrocarbon liquids amenable to refining. That, even though the focus of Ashland's work in this case was, or was intended to seem, focused on the extraction of a somewhat useful commercial by-product of low-temperature coal carbonization.
 
Excerpt as follows; emphases added, with comment interspersed and appended:
 
"CARBON BLACK FEEDSTOCK FROM LOW TEMPERATURE CARBONIZATION TAR

Donald C. Berkebile, Harold N. Hicks, and W. Sidney Green
Ashland Oil and Refining Company
1409 Winchester Avenue, Ashland, Kentucky 41101
 
About three years ago Ashland Oil and Refining Company management initiated a modest coal liquids research program. This program was aimed at accumulating basic technology and at providing a basis for more extensive studies. During the early stages research consisted primarily of literature surveys and scouting experiments. It was concluded from this initial work that low temperature carbonization (LTC) of coal could supply coal liquids at attractive values when considering the current economic conditions.
 
Discussions with FMC Corporation established' their willingness to cooperate in supplying tar from their LTC-pilot plant for experimental work. The FMC unit was constructed under sponsorship of the Office of Coal Research (OCR) . This project is designated as Char-Oil-Energy-Development and has the acronym of COED.
 
(So, "FMC Corporation" also had a coal conversion program? How many of those were there, anyway? And, why haven't we been informed?)
 
The COED process utilizes multiple stage, fludized-bed pyrolysis with increasing stage temperatures to drive off the volatile matter at controlled rates and temperatures so that a high percentage of the coal is converted to gas and condensable oil products. Coal is crushed and dried and fed to the first stage vessel, where it is fluidized in hot recycle gases generated from combustion of some of the product gas or char. The coal then proceeds from the first stage, which is nominally at 600°F, to the subsequent stages where it is subjected to increasing temperatures of 850, 1000 and 1600OF. Heat for the second and third stages comes from burning some of the char with oxygen in the fourth stage. The gases from the fourth stage flow countercurrent to the solids through the third stage to the second stage, from which most of the volatile products are collected. A small percentage of the volatiles comes from the first .stage. A small amount of char is recycled to the third and to the second stage to help provide the heat necessary to maintain the vessel temperatures. The volatile products from the pyrolysis are condensed and separated.
 
(Note that a part of the Karrick LTC process, as we've earlier documented from other sources, is exothermic. It can provide energy to help drive the conversion process, and, as we have also documented, be harnessed to generate some electricity as a by-product.)
 
The project COED tar that was the feedstock for all work described in this paper was derived from Illinois #6 coal.
 
Ashland's position as a supplier of refinery products and carbon black--through the United Carbon division--had a significant influence on the selection of the research program goals for processing of LTC tar.
 
(We bet it did.)
 
The primary objective of this program was to produce carbon black feedstock from all or a portion of the LTC coal liquids. A product of this nature would require a minimum amount of upgrading and would utilize heretofore unmarketable fractions of the coal liquids. Secondly, emphasis was placed on converting the fractions unsuitable for carbon black feedstock into products compatible with normal refinery operations.
 
(In other words, there were marketable, as opposed to "unmarketable" ... "coal liquids".) 
 
Other researchers have tried many techniques to upgrade LW tar including coking, thermal cracking and hydrogenation. Products ranging from coke to gasoline with some intermediate chemicals are commonly reported in the literature. Probably the point most 'common to the work of these various groups was the fact that the processes were uneconomical. Processes to produce chemicals from LTC coal liquids failed because these materials could not be obtained by simple processing schemes.
 
(So, "products" such as "gasoline" can be obtained from carbonaceous LTC tar residues, but the "processes were uneconomical". We wonder if WVU's West Virginia Process for direct coal liquefaction, using the hydrogen donor, tetralin, if applied to LTC residues, already processed, and porous, as they are, might have more economic success. And, petroleum economics have changed dramatically in the decades since this report was published - to use the term "published" very loosely.)
 
DISCUSSION
 
An initial quantity of project COED full range coal liquids was obtained from FMC for characterization.
 
Initial Processing Scheme: The tar was-heated until fluid and blended with benzene in a 1:1 volume ratio in order to reduce the tar viscosity sufficiently to permit centrifugation for solids removal and for a subsequent distillation to remove the water.
 
(A lengthy description of processing details is contained in the report. We are not excerpting them, but the processes were focused not only on obtaining carbon black, but on evaluating "the product as a potential refinery reformer charge stock". As it happens, it didn't work too well for carbon black, but was a productive source of additional liquid hydrocarbons when appropriately processed, as revealed following.) 

Hydrotreating-Microreactor  

Because of the high oxygen content of the dry, solids-free tar and its detrimental effect on carbon black yield, it was decided to attempt to selectively hydrotreat the tar with the objective of removing the oxygen, nitrogen and sulfur without ring saturation. Fixed bed, catalytic hydrotreatment of the tar was conducted at a moderate temperature and intermediate pressure in a 3/4 inch diameter reactor. The process was studied by evaluation of composited reactor effluent and off-gas samples from consecutive test periods of 19 to 24 hours duration.
 
A hydrocarbon liquid yield on feed of about 86 weight percent and an aqueous yield of about 3%were obtained. Hetero atom removal based on the feed and composited effluent samples was over 90%for sulfur, over 60% for oxygen, and nearly 40% for nitrogen. Hydrogen consumption for this level of processing was estimated at 1200 to 1500 SCF/bbl. of feed. Material balance data indicated that hetero atom removal accounted for the largest portion of the hydrogen consumed with most of the remaining hydrogen used appearing as cracked products in the off gas.
 
(So, they didn't get the carbon black they were originally, supposedly, looking for, but: "86 ... percent" of the LTC residue feed was converted into, yielded "hydrocarbon liquid".)
 
The hydrotreated composited product was fractionated into ... refinery feedstock and a carbon black feedstock.
 
(There was additional, significant, benefit attributed to the process for the "refinery feedstock", as  follows.)
 
Hetero atom (Sulfur and other contaminants.) concentrations have been reduced sufficiently by this operation to permit processing of the material in conventional refinery units.
 
ECONOMICS
 
The preliminary economics of a commercial scale LTC tar processing facility have been estimated based on a pilot plant and laboratory data. The economics assume a 10,000 ton/day coal car-
bonization unit is located adjacent to the tar processing facility. This unit, while not directly included in the economics, supplies a low cost source of 11,906 bbl/day of full-range LTC tar.
 
A capital investment of $13,100,000 has been estimated for the processing units shown in Figure 3, with the exception of the carbon black facility, which is not included in the economics. A discounted cash flow of 20% can be realized on this investment with full-range LTC tar valued at $1.62/bbl. and the following values placed on the various products:
 
Carbon Black Feedstock -7C/gallon
 
Rt2 Fuel oil -9$/gallon
 
Gasoline Blending Stock -14C/gallon (102+ Octane No.)
 
Benzene -23C/gallon
 
Naphthalene -4.5$/lb.
 
H2 Consumed or Generated -30$/1000 SCF
 
(NOTE: Unless we misread this, when all the products and economics are considered, a "102+ Octane" "Gasoline Blending Stock" was produced from coal LTC residue at a cost of 14 cents per gallon.)
 
The technical feasibility of hydrotreating full-range LX tar to produce a highly aromatic residue boiling above 600°F, with low hetero atom (Sulfur, etc. - JtM) content, has been demonstrated.
 
The lower boiling material from hydrotreating ... is a highly aromatic material ideally suited for processing in conventional refinery equipment to yield valuable products.
 
Preliminary economics, based on pilot plant data, indicate the overall LTC tar processing scheme can realize a good DCF rate of return on investment, when reasonable product values are assumed."
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So, according to Ashland Oil,  we can use USBM scientist Lewis Karrick's LTC process to make liquid petroleum fuel replacements from coal. And, we can further convert the "waste", the carbonaceous residue, from that LTC process into a "material ideally suited for processing" in a conventional oil refinery, at a cost, at the time of this report, of 14 cents per gallon, for "stock" from which gasoline can be blended.
 
Do we have that all about right? And, doesn't the answer to that question spur the birth of a whole bunch of other questions?