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A lot of science is about trying to find the best questions. Because the best questions can lead us to better answers. So, in the spirit of better questions here goes.

By loosening environmental regulations aimed at pollution prevention or remediation, the mandarins reporting to POTUS 45 have apparently made the calculation decided that some resulting uptick in pollution is justified by the jobs created thereby.

Question 1: For any given relaxation in regulations that result in an adverse biological, chemical or physical insult to the environment, what is the limit of tolerable adverse effect?

Question 2: How will the upper limit of acceptable environmental insult be determined?

Question 3: Will the upper limit of acceptable environmental insult be determined before or after the beginning of the adverse effect?

For a given situation there should be some ratio of jobs to acceptable environmental damage.

Example: By relaxing the rules on the release of coal mining waste into a river, X jobs are created and, as a result, Y households are denied potable drinking water. What is an acceptable ratio of X to Y?

Those are enough questions for now. Talk amongst yourselves.

I’m a fan of Gold Rush on the Discovery Channel and have been since the beginning. Aside from the producers constant over-dramatization and spreading the content a little too thin over the time block, I’d have to say that my main criticism would be with the miners themselves.

What I would throw on the table is the observation that there is a troublesome lack of analytical data supporting the miner’s choices of where to dig a cut. The few episodes where core samples have been taken, useful data was obtained and decisions made therefrom. But the holes were paid for grudgingly and the range covered too miserly. A sufficiently capitalized operation would be sure to survey the ore body and make the decision to bring in the heavy equipment on the basis of data.

Obviously they have been chronically short of capital for their operations. Fortunately for them, over the last 2 seasons they have been able to upgrade their wash plants, trommels, and earth moving equipment. Must be the TV connection.

But I suppose it is the very lack of capitalization that forms the dramatic basis of the show. Without scarcity there would be no drama. Without the conflicting personalities and dubious decision making there would be only a documentary on gold mining.

I have to imagine that the recent collapse in gold prices will get folded into the dramatic context in the next season.

I truly wish Parker Schnabel, the Hoffman crew, and the Dakota boys the best of luck in their efforts. What the viewers can’t see are the 10,000 details and problems that remain on the editing room floor.

Any questions?

It is a crying shame that we (the rest of the world) did not think to encourage Iran and other states to develop thorium-based nuclear power many years ago. The thorium fuel cycle provides nuclear-powered steam generation, but is largely absent the use of fissile isotopes in the cycle which may be used for nuclear proliferation.  Thorium-232 is more abundant that uranium-(235 + 238) isotopes and does not require isotopic separation as uranium does.

The great exploration boom in progress with rare earth elements would facilitate thorium supply. Thorium and uranium are commonly found in rare earth ores and, to the dismay of extractive metallurgists since the Manhattan Project, these elements tend follow along in rare earth extraction process. The isolation of thorium was developed long ago.  Point is, since so many rare earth element extraction process streams are either in operation or are pending, now is the time to accumulate thorium.

At present however, thorium is a troublesome and undesired radioactive metal whose isolation and disposal can be quite problematic. The best process schemes partition thorium away from the value stream as early in the process as possible and channel it into the raffinate stream for treatment and disposal in the evaporation pond.

The specific activity of natural thorium is 2.2 x 10^-7 curies per gram (an alpha emitter). The specific activity of natural uranium is 7.1 x 10^-7 curies per gram.  Alpha emitters pose special hazards in their handling. Dusts are a serious problem and workers must be protected especially from inhalation or ingestion. While alpha’s are not difficult to shield from, their low penetration through ordinary materials or even air makes them a bit more challenging to detect and quantitate relative to beta’s and gamma’s. In spite of the mild radioactivity of thorium, managing the occupational health of workers is known technology in practice in the nuclear industry.

Regrettably, most of the world’s nuclear power infrastructure is geared to uranium and plutonium streams. Thorium, the red-headed stepchild of the actinides, is thoughtlessly discharged to the evaporation ponds or to the rad waste repository- wherever that is- to accumulate fruitlessly. If we’re digging the stuff up anyway, why not put it to use? It is a shame and a waste to squander it.

I just can’t get over the absolute wierdness of being in a crowd, say at the airport, where a large fraction of people are jabbering into a phone plastered to their ear or they are standing, walking, sitting, or pacing with heads bowed down, pecking and stroking their mobile communication device. It is a kind of enchantment. A portal to other coordinates in the continuum. It allows us to receive or deliver stress all the damned time. Nobody is safe from the possibility of belligerent assholes reaching out for you while waiting at a stoplight or well-meaning associates braindumping all over your eardrum as you search aisle 5 at the supermarket for a can of chickpeas.

Driving yesterday, I took defensive measures as a dipshit in a red Ford Expedition overshot a turn while closing in on me. The distracted driver chose to complete a task on the handheld device before putting the oversized killing machine back between her yellow and white lines. I know this because the driver plastered the phone to her ear as she looked up when I passed by.

It has been 2 months now since I powered down my Facebook account. Facebook is a colossal time suck. It is a kind of gravitational well that can pull wandering bodies into orbit and lock them into some perverse synchrony for purposes unknown. Facebook is a kind of electronic teat that nurses us and keeps us from having to face our dark thoughts in quiet moments.  It is also a perfect venue for those who just have to broadcast their thoughts in every waking moment.

As a Facebooker, I was pretty boring. I don’t have photos of grandchildren or garden flowers to post. I’m a serial science nerd and nobody wants to hear about that. Okay, that’s fine. I soon realized that Facebook was only providing delayed and fragmented social awkwardness that I could be having face to face in real time and without having to pay for electricity. So I pulled the plug.

There is considerable handwringing over hydraulic fracturing fluids and their potential effects on “the environment”. I use quotes in ironic fashion because I see very little parsing of the issue into relevant components. The chemical insult to the environment is highly dependent on both the substances and the extent of dispersion. But I state the obvious.

There are surface effects at the drill site and there are subsurface effects. A spill on the surface is going to be relatively small due to the limited size of the available tankage on site. I drive by these sites almost daily and can see with my own eyes the scale of the project. A surface spill of materials will be limited in scope.

The subsurface effects are complex, however, and the magnitude of consequences will depend on both the extent of the fluid penetration into aquifers and the nature of the materials in the fluid. Much criticism has been dealt, rightfully I think, over the secrecy claims on the composition of these fluids. The default reply from drillers has rested on trade secrecy. To be sure, the matter of government forcing a company to reveal its art is a serious matter. But the distribution of chemical substances into the environment requires some oversight. Especially when substances are injected into locations where they cannt be readily remediated. The remediation of an aquifer is a serious undertaking which may or may not be effective.

If you want to see what is potentially in frac fluids, go to Google Patents and search “hydraulic fracturing fluid”. A great many patents will be found. This will give the length and breadth of the compositions patented. Of this large list only a few are used in current practice. The potential carrier fluids vary from water to LPG (!). Water is a common component, but brine is said to be preferred. Additives include hydrochloric acid and surfactants. The MSDS documents may be a good source of info. Consider that a substantial threat to ground water may be that it is rendered non-potable rather than outright  toxic.

Agilent is excited about their new 4100 MP-AES system. The initials stand for Microwave Plasma Atomic Emission Spectrometer. The instrument uses the magnetic component of the microwave energy to produce a nitrogen plasma at ca 5000 K, through which the sample is drawn. The monochrometer looks down the axis of the plasma torch. The detector is constructed to suppress blooming.

Pretty cool instrument. The setup includes a nitrogen supply which separates the nitrogen directly from air, so there is no large argon dewar to lug to remote locations like mine sites.

The MP-AES is designed to compete in the AA market. The detection limits are comparable for many elements. The kicker is that there no need for combustion gases or element specific lamps since it is a plasma emission method.

The question I have is this- is there any market left in the replacement of AA? The instrument sells for $53 k, so the pricing is very competitive with or better than ICP. I think that argon based ICP is going to feel the heat of this nitrogen plasma torch.

The bad news for chemists is that you don’t need a chemistry degree to run it. To set up methods, maybe, but the software is designed for operation by non-degreed techs.

Devon Energy has raised $900 million in cash from Sinopec Group for a stake in Devon shale gas plays. These gas projects include the Utica, Niobrara, and Tuscaloosa formations. 

What is interesting is not so much that China has bought its way into the extraction of a resource that the USA has in some abundance. What is more troubling is that China has bought its way up the learning curve in horizontal drilling and fracturing. 

According to the article in Bloomburg Businessweek-

China National Petroleum Corp., Sinopec Group and Cnooc Ltd. are seeking to gain technology through partnerships in order to develop China’s shale reserves, estimated to be larger than those in the U.S.

“In these joint ventures, the partner does typically get some education on drilling,” Scott Hanold, a Minneapolis-based analyst for RBC Capital Markets, said today in an interview.

So, the business wizards at Devon in OKC have arranged to sell their drilling magic to the Sinopec for a short term gain on drilling activity. Way to go folks. Gas in the ground is money in the bank. These geniuses have arranged to suck non-renewable energy out of the ground as fast as possible.  Once again US technology (IP, which is national treasure) is piped across the Pacific to people who will eventually use it to beat us in the market.  Score another triumph for our business leaders!!

The market is like a stomach. It has no brain. It only knows that it wants MORE.    Th’ Gaussling.

 It’s a banner day for American Business.

I’ve turned my attention to reaction calorimetry recently. A reaction calorimeter (i.e.,  Mettler-Toledo RC1) is an apparatus so constructed as to allow the reaction of chemical substances with the benefit of measuring the heat flux evolved. Reaction masses may absorb heat energy from the surroundings (endothermic) or may evolve heat energy into the surroundings (exothermic).

Calorimetry has been around for a very long time. What is relatively recent is the development of instrumentation, sensor, and automation packages that are sufficiently user friendly that RC can be plausibly used by people like me: chemists who are assigned to implement a technique new to the organization.  What I mean by “user friendly” is not this: an instrument that requires the full time attention of a specialist to operate and maintain it.

A user friendly instrument is one engineered and automated to the extent that as many adjustments as possible are performed by the automation and that the resulting sysem is robust enough that operational errors and conflicting settings are flagged prior to commencing a run.  A dandy graphic user interface is nice too. Click and drag has become a normal expectation of users.

An instrument that can be operated on demand by existing staff is an instrument that nullifies the need for specialists. Not good for the employment of chemists, but normal in the eternal march of progress. My impression is that RC is largely performed by dedicated staff in safety departments. What the MT RC1 facilitates is the possibility for R&D groups to absorb this function and bring the chemists closer to the thermal reality of their processes. Administratively, it might make more sense for an outside group to do focus on process safety, however.

In industrial chemical manufacture the imperative is the same as for other capitalistic ventures- manufacture the goods with minimal cost inputs to provide acceptable quality. Reactions that are highly exothermic or are prone to initiation difficulties are reactions that may pose operational hazards stemming from the release of hazardous energy.  A highly exothermic reaction that initiates with difficulty- or at temperatures that shrink the margin of safe control- is a reaction that should be closely studied by RC, ARC, and DSC.

It is generally desirable for a reaction to initiate and propagate under positive administrative and engineeering controls. Obviously, it is desirable for a reaction to be halted by the application of such controls. Halting or slowing a reaction by adjustment of feed rate or temperature is a common approach.  For second order reactions, the careful metering of one reactant to the other (semi-batch) is the most common approach to control of heat evolution.

For first order reactions, control of heat evolution is had by control of the concentration of unreacted compound or by brute force management of heating and cooling.

Safe operation of chemical processing is about controlling the accumulated energy in the reactor. The accumulated energy is the result of accumulated unreacted compounds. Some reactions can be safely conducted in batch form, meaning that all of the reactants are charged to the reactor at once. At t=0, the accumulation of energy is 100 %. A reliable and properly designed heat exchange system is required for safe operation (see CSB report on T2). In light of T2, a backup cooling system or properly designed venting is advised.

The issue I take with the designers of the process performed at T2 is this: They chose to concentrate the accumulated energy by running the reaction as a batch process. This is a philosphical choice. The reaction could have been run as a semibatch process by feeding the MeCp to the Na with a condenser on the vessel. Control of the exotherm could have been had by control of the feed rate and clever use of the evaporative endotherm. A properly sized vent with rupture disc should always be used. These are three layers of protection. 

Instead, they chose on a batchwise process relying on a now obviously inadequate pressure relief system, and the proper functioning of water to the jacket.

No doubt the operators of the facility were under price and schedule pressure. The MeCp manganese carbonyl compound they were making is an anti-knock additive for automotive fuels and therefore a commodity product. I have no doubt at all that their margins may have been thin and that resources may not have been there to properly engineer the process. This process has “expedient” written all over it in my view.

Reactions that have a latent period prior to noticeable reaction are especially tricky. Often such reactions can be rendered more reliable by operation at higher temperatures. Running exothermic reactions at elevated temperatures is somewhat counter-intuitive, but the issue of accumulation may be solved.  

Disclaimer: The opinions expressed by Th’ Gaussling are his own and do not necessarily represent those of employers past or present (or future).

The South Meadow generating station was operated by the Hartford Electric Company in Hartford, CT. The unit described in the 1931 Pop Sci article used 90 tons of mercury in the boiler. The article states that the South Meadow generator produced as much as 143 kWh from 100 lbs of coal, as opposed to an average of 59 kWh from conventional coal fired plants and 112 kWh from exceptionally efficient coal fired plants. The article describes an incident at the plant where a breech of containment from an explosion in the mercury vapor system occurred, releasing mercury and exposing workers to mercury vapor.

The Schiller Mercury Power Station in Portsmouth, NH, is described in this link.


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