Category Archives: Chemical Industry

Green Propellants

Notes from the Field-

There appears to be a movement in the gun and rocket propellant field away from perchlorates.  Propellants that are comprised of substances that pose minimal potential for the dispersal of adverse and environmentally persistant substances are referred to as “green propellants”.  Substances that qualify as adverse include arylamines, perchlorates, and certain rheology modifiers. Substances that are thought to be endocrine disrupters have been specially targeted for replacement.

While it may seem absurd to attempt to produce a weapon system having a reduced toxic signature, the  fact is that between practice projectiles and warshots, a good deal of hazardous residues are released in the use of these devices. Reducing the chemical environmental insult is a step in the direction of reduced collateral damage.

One expert in the area of perchlorates said that people with adequate iodine intake shouldn’t worry about perchlorate contamination of water. Hmmm. While that may be true, it sounds like a poor basis for policy.

Mea Culpa

Today I found myself attending a talk on mortar propellants. It was delivered by a shy young woman who looked to be no older than a high school senior- she looked like a babysitter you’d hire to stay at home with the kid while you treated the wife unit to a night out on the town. Yet she was an expert in mortar shell propellants.

Next, I attended a talk on flare compositions delivered by a tiny woman who could barely see above the podium.

I rounded the day off by attending a talk by a woman who presented her results on igniter design and in developing a new explosive propellant manufacturing process. During the Q&A, my questions on ignition mechanisms were answered by yet another woman who was exceedingly knowlegeable in this field.

What I have noticed is that the gun and rocket propellant R&D field is populated with women to a much greater degree than the industrial organic or organometallic chemistry waters in which I normally swim.

Before you fire a rude comment alleging some sexist malfeasance, please understand that I was raised by a single mother as the eldest of 5 kids. That, and having witnessed the birth of my child, I have no doubt whatsoever about the robustness and Ability of women.

That women do this isn’t news. What is noteworthy is the extent to which my ignorance remains so great at age 51. My caveman misconception was that explosives chemistry would not appeal to women. I had mistakenly and foolishly assumed that a career with explosives was largely a male domain and driven by male fascination with power. Holy cats. I was quite mistaken.

I seem to be wrong about  a lot of things these days.

Safety Communication by Walking Around

For people who are working in the chemical process business, there is always the question of adequate information for the safe conduct of a process. How does one fold new process safety details into an organizational structure so as to gain the greatest benefit?

One method is to simply issue memos and rely on management SOP’s for enforcement.  This kind of passive distribution of information must compete with all the other channels of information flowing into the brains of coworkers. Memos that are badly written or bursting with details are sure to be poorly absorbed. Eventually, people cannot reliably digest additional information on top of an already complex task.

The word that always comes up is “communication”. True enough, but too often communication comes in the form of training which consists of a PowerPoint recitation to a passive audience. This is not training- it is a briefing.

Communication often manifests as a memo or as a new folder on some disk drive. Again, this is a passive form of communication that does not necessarily engage the recipient.

I think that effective safety communication requires “management by walking around”. If safety information arises that is critical, then what better way than to walk around and collect disciples of safety? Mobility and strength of personality can be far more effective than even the best memo, SOP, or policy. 

Much of specialized expertise resolves to a finite number of rules and specialized awareness on top of a foundation of more generic knowledge.  Specialized expertise may be difficult to acquire, but in practice it is of finite scope. An engaging and ebullient manager can help people absorb complex information by breaking it down into a hierarchy of pieces and rules. The practice of filing information into a folder and relying on people to go out and look for it is a poor substitute for active engagement.

Software from Symyx

I was interested to learn that Symyx offers a chemical structure drawing package called Symyx Draw 3.1. Naturally, a company as deep into cheminformatics as Symyx is has much to offer in regard to data management. The company offers a large variety of software packages. Unfortunately, I was unable to get any pricing information straight off the web. They require that you contact them for a quotation. Having been in sales, I understand the reasons for this, but it is still less than convenient.

It would be interesting to hear from readers who have used Symyx Draw do a compare and contrast with ChemDraw.

The lab as a shop

Just sent multiple kgs of a rare earth reagent out the door. It may have been one of the larger scaleups of this stuff. I hope it does the job for the customer. Meeting certain specs turned out to be more difficult and time consuming that I had anticipated. But getting it certed and shipped is quite satisfying.

Lots of new projects in the shop for examination and custom synthesis. Some process safety tests, some analytical development, and some synthesis. It’s a good mix and quite diverse in chemical elements.

The ARC, the CHETAH, and the Organikker

Just received a copy of CHETAH 8.0.  This is a program for thermochemical and energy release evaluation and is distributed by ASTM. It will calculate enthalpy of combustion and thermochemical properties of compounds and reactions including- LFL, LOC, MIE, lower limit flame temperatures, maximum flame temperature, fundamental burning velocity, and quenching distance.

I have only had it installed for 2 days, so it’s way too early to give an appraisal. It came highly recommended by several colleagues in the process safety field.  The only snag so far is a balky SMILES input module. This feature was very appealing because it allows one to copy a ChemDraw structure in SMILES format and paste it into the CHETAH GUI. The rep at ASTM gave me a link which ended up offering very cryptic instructions. Naturally, the problem is some obscure setting in Windows.

Until I get this fixed, I’ll have to enter Benson groups by hand. As it happens, I began studying guitar in my spare time, so there are all kinds of new things for my addled brain to stumble over assimilate. So when I’m not picking at strings, I’m picking at Benson groups.

Update 3/5/09:  After a service pack download, the SMILES module is functioning. This is a very powerful tool.

We’ve recently caught up with the times and have been pressing Accelerating Rate Calorimetry (ARC) into service. Or more accurately, paying to have the data collected.  ARC is really quite informative in that it can offer a Time to Maximum Rate (TMR) equation from which a TMR can be determined for any desired temperature. You can calculate an adiabatic delta T as well. I do not know how reliable this number is, but it certainly reminds one of the importance of considering the effect of phi factor in process scale up.

The ARC data I get includes an Antoine curve which can indicate that the accelerated rate behavior is or is not characteristic of classical liquid/vapour equilibrium behavior. What this says to the wary is that other volatiles (besides the subject material) may be generated which are not condensable. This is helpful in considering what kind of controllability is available to the process engineers.

Plea from China

I don’t know what others are experiencing, but I am flooded with desperate email pitches from Chinese chemical manufacturers- “Please, let’s make cooperation!”  Everything from solvents to generic drugs.

A receding tide beaches all boats.

Update:  Just got an offer for bulk Vinblastine Sulfate. Golly, I think I’ll decline. The last thing a guy needs is a few kg of that stuff sitting in a cabinet.

Calamity, Interrupted

JOC will no longer appear in my mailbox. I decided to let go of this icon of my earlier years. Organic Process Research & Development will “arrive”, but this time I have taken a web subscription for $40/year. In the interest of domestic harmony, the rate of paper accumulation will drop somewhat.   The trouble with this form of access to the literature is that I can’t take a journal to the local taco joint where I lunch on occasion.

The recent subscription, the Journal of Loss Prevention, is quite interesting. Lots of articles on the dynamics of explosions and fires as well as studies on calamaties, disasters, and general industrial mayhem. I can dig it.

Both imagination and knowledge are an important part of chemical process safety. A process safety person should have a solid chemistry background to grasp what is happening in a reactor or piece of equipment. Imagination comes in to play when trying to anticipate failure modes leading to initiation and propagation of incidents.

It isn’t possible to anticipate all possible failure modes in a chemical process. And not every failure leads to an incident or casualty. What is possible is to collect as much information as you can for a group to do a process hazards analysis.

A properly facilitated group can unearth many possible failure modes and root causes. Once identified, an effort to remove initiation sources or uncouple possible propagation pathways can be made. The first and best goal is to eliminate a hazardous condition. Management and engineering controls should always be secondary to elimination of a hazardous condition. 

AIChE is a great source of information for process safety.

Update:  The web subscription is quite agreeable to use.

Gold Refining with Borax

According to the GEUS, the Geological Survey Office of Denmark and Greenland, it is possible to concentrate and isolate gold from the ore using borax and charcoal. This method has the immediate benefit of making mercury “redundant” in gold isolation.

Extraction of gold by amalgamation with mercury is a simple means of producing metallic gold in the field.  After contact with gold enriched ore, mercury is evaporated into the air by direct application of a torch flame to the puddle of metal leaving purified gold metal.

It is thought that there are millions of miners who scratch out a subsistance living working a small patch of ground for gold. It’s called small scale mining. In the course of this activity, environmental contamination can accrue to the immediate area as well as the watershed at large. Sadly, the toxicological insult to the miners from exposure to mercury vapor can be severe.

This method is an inexpensive and simple alternative to the mercury process. Perhaps the chemistry community has something to contribute by way of education or improved methods of extraction.

8/25/10  Update.  I have revisited this post and am compelled to comment further.  While I am unable to offer a good chemical explanation for the effect of borax on gold ore, I can say that the use of borax as a flux  for smelting goes back to the 19th century during the American gold rush period.  The process described in the link appears to be a smelting process for enriched ore containing elemental gold, as opposed to sulfide, or sulphuretted ore. The function of a flux is to modify the flow and phase separation properties of host rock so as to partition away from the gold phase or layer.  In other words, a flux modifieds the slag to help the gold to separate cleanly from the rock.

Make or Buy? Gaussling’s 11th Epistle to the Bohemians.

The most important reaction in chemistry is the one in which you transform chemicals into money. Some chemicals convert into a lot of money per kg, others not so much. The kind of money you want to focus on is profit. Just turning cash over at cost wears thin rapidly and is hazardous to your career. At the end of the day, after you’ve paid the raw mat vendors, payroll, and the feds, you want to have a steaming heap of luchre left over as profit.

At some point in the game, everyone in fine chemical manufacturing realizes that you can’t make everything in-house. There are good reasons to consider making as many intermediates as you can. When you buy an intermediate, the vendors price (cost + profit) becomes the cost you plug into the economics. Optimally, you might be able to make the material cheaper than buying it … eventually. But some raw materials are deceptively simple looking. A company can rack up a lot of brain damage and wasted time trying to make certain kinds of materials outside of your skill set.

We used to joke that at some point in process development, you have to shoot the chemist and get on with scale-up. Often, the decision to make-or-buy an intermediate gets to the table only after you try to make it. In process development, it is important to identify the make-or-buy decisions as early as possible. This can save valuable time. While you may end up spending more per unit mass for the material, not having to make it is equivalent to opening up extra capacity in your facility. Ideally, your want precious reactor/equipment hours spent on the highest value added steps. With each successive step, the value of the intermediate becomes greater.

If your make-or-buy decision revolves around a known item of commerce, then the economics and scheduling is relatively easy. You will have to settle on specifications, delivery schedule, shipment details, and pricing. If the material is not TSCA listed, then you will have to get the vendor moving early on a filing with the EPA, if they are in the USA. If you intend to import a non-TSCA listed fine chemical, not for pharma, ag, food, or other covered use, then the importer of record is responsible for the TSCA paperwork. This can take a few months of lead time.

But if the compound is novel and/or proprietary, then it is instantly much more complex. Not only do you have  to deal with the EPA on TSCA filing, but you have to find a vendor who is willing and able to ramp up a new process. They will need specs, projected delivery information, an agreeable price, and quite possibly a lined-out process and analytical methods. If the vendor has available capacity, this might happen as quickly as 3-4 months. More likely than not, this can take 6-9 months.

If your raw material is part of a critical technology or major account, then you may have to consider dual sourcing. If one plant goes down or the quality or delivery drifts beyond what is acceptable, then you still have one facility that can deliver. And, if you have two vendors, you can start a dandy little bidding war between them for your business. Many companies require their purchasing managers to qualify two vendors for crucial materials. You can argue that you should always have two vendors, but many times the amount of business the material feeds into is too small to bother with.

Chemical manufacturing is much more than reaction chemistry. A chemist in manufacturing can find him/herself involved in many kinds of work.   Regulations, chemistry, process safety, engineering, packaging issues, IP, marketing, and process economics add up to the knowledge set that a chemist needs to acquire while heading up the career ladder.