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Am I dying?!
Am I dying?!
Hey guys.... We'll I've been feeling like crap for a long time.....I was starting to think it was all in my head but now I'm not so sure. I've been researching hypothyroidism for awhile and I was nearly convinced that was my problem. I went to the doc and was tested but everything came out 'normal'. We also tested testosterone and that came out extremely low at 188! anyway, here are some of my symptoms:
anxiety/ panic
lighthead/ dizzy sometimes
shortness of breathe somtimes
slow pulse (as low as 44)
borderline high blood pressure sometimes stage 1
poor memory
feeling sad a lot
grumpy/ irritable
low sex drive
fatigue/ tired all the time
no focus/ concentration
brain fog
lack of motivation
ringing in the ears (tinnitus)
low body temp (96.8, early morning in bed)
metabolic syndrome (high chol, high triglyc, high LDL, Low HDL)
last 1/3 of eyebrows seem to be thinning
anyway, here is blood work done:
hemoglobin 15.6 (13.2-17.1)
hemotocrit 45.9 (38.5-50)
mcv 87.7 (80-100)
mch 29.8 (27-33)
mchc 34.0 (32-36)
rdw 14.5 (11-15)
platelet count 272 (140-400)
absolute neutrophils 4433 (1500-7800)
" lymphocytes 2338 (850-3900)
" monocytes 474 (200-950)
" eosinophils 118 (15-500)
" basophils 37 (0-200)
neutrophils 59.9%
lymphocytes 31.6%
monocytes 6.4%
eosinophils 1.6%
basophils .5%
total chol 219 (125-200)
Trig 280 (<150)
chol/hdlc 7.8 (<5)
ldl/hdl 4.8
t4 free 1.0 (.8-1.8)
estradiol 23 (13-54)
t3 free 330 (230-420)
total testosterone 188 (250-1100)
total free T 2.7 (1.5-2.2%)
free T 50.8 (35-155)
doctor ordered follow up on LH, ACTH, and Prolactin
sodium 140 (136-146)
potassium 4.3 (3.6-5.2)
chloride 102 (98-109)
glucose 83 (60-99)
calcium 9.5 (8.5-10.5)
bun 12 (<23)
creatinine 1.0 (<1.5)
tot bilirubin 1.3 (.2-1.3)
Alk phosphate 79 (40-125)
tot protein 8.0 (6.2-8.3)
albumin 4.7 (3.7-5.2)
glubulin 3.3 (2.1-3.7)
A/G ratio 1.4 (1-2.5)
bicarbonate 26 (21-30)
chol 202
triglycerides 102
since 2008 I have been eating healthier, cut out soda, much less candy, eating 6-7 meals a day instead of 2 or 3. I'm baffled why my Chol has increased, my HDL decreased, LDL increased, and tri's more than doubled!
I really thought I had hypothyroid but doctor say I'm ok but Testosterone is horrible. I don't what the rest of the bloodwork means any thoughts or suggestions? Advice? Thanks!
The lipids reading at the bottom of the top post was from 2006.
- Stats
- 6'4" 190 lbs.
- Join Date
- Oct 2009
- Age
- 35
- Posts
- 25
- Rep Power
- 81
- Level
- 4
- Lv. Percent
- 93.93%
[B]Low HDL(the good kind) cholesterol. A major risk factor for heart disease.
[B]Borderline high LDL(the bad kind) cholesterol - If you have other risk factors you may want to talk to your doctor about this... IE a history or family history of heart disease / diabetes / etc...
Your triglycerides are high. Reduce your intake of alcohol considerably. Even small amounts of alcohol can lead to large changes in plasma triglyceride levels.Reduce the saturated fat, trans fat and cholesterol content of your diet. Don't eliminate them, but you should probably cut back.
How old are you? What is your other medical history like? Have you done steroids in the past? Are you on any other medication?
Your lipid panel at the bottom of the top post is MUCH better than your current levels. What has changed in your diet in the past 3 years? It sounds like your diet has gone down the ****ter... as you were normal before and now you have borderline / high cholesterol / triglycerides / etc...
Thanks for the reply and help!
I don't drink any alcohol at all. I even cut out all soda. I thought my diet had improved since last labs. I started working out 4 days a week and set up a 30p 50c 20f percent diet. I eat about 3100c a day with around 71g of fat. It's all good kind. 1/2 of it comes from peanut butter. Some from nuts. I take fish oil. I don't get it.
Oh yeah, I'm 38 and 5'8" 180lbs with about 19%bf. I started taking lexapro 15mg/day for anxiety. That's all the meds I take. And never taken any steroids.
Thanks again for your help!
And I only eat white meat. Chicken and fish. I ocassionaly eat a whole egg and 1/2 cup of egg whites.
- Stats
- 6'4" 190 lbs.
- Join Date
- Oct 2009
- Age
- 35
- Posts
- 25
- Rep Power
- 81
- Level
- 4
- Lv. Percent
- 93.93%
Okay. I was just going off your profile where you said you drink and smoke. If you don't drink then hmm...
Did you do your blood test after fasting for 8-12 hours or had you eaten that day?
I would talk to your doc about your cholesterol levels. He/She is going to have a better idea if you should be taking medication and or changing your diet significantly. 30p 50c 20f is a fine diet split, especially if you're able to meet your Calorie needs eating the clean food you mentioned. (I have a hard time personally)
You need to ask your doctor if he is willing to prescribe Testosterone &/or hCG. If your gonads work but your brain isn't telling them to make enough test, then you should consider asking for hCG therapy. If your gonads DONT WORK (IE your LH / FSH levels are high but test levels are low) then you are going to be looking at Test + hCG therapy ideally.
Ask your doctor straight up if he is willing to help you get your hormone levels to an optimal level. If he/she is not then you should probably look around for an anti-aging clinic or maybe a DO that will help you out (DOs seem to be more open minded as compared to MDs, in my experience)
If he/she is willing to put you on testosterone but not willing to put you on hCG, then your gonads will shrink. You'll feel better though.
So again: Wait for your FSH / LH test results. if they are low then you could consider hCG therapy to stimulate your gonads into making more testosterone naturally. If they are high then you should probably inquire about Testosterone + hCG therapy to replace your deficient testosterone and keep your gonads from shrinking.
Fixing your testosterone levels will likely help with your mood / sex drive / low energy levels / etc... as that is a VERY common side effect.
Thanks. Yes, I was fasting for 10 hours prior to blood draw. I can't figure out why my lipids are so bad. Maybe genetics. I think I've also heard that they will improve with trt. I hope so.
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subset: commoncrawl


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Eddie Murphy Shares His "Ultimate Vision" for a Live Music/Standup Show
"My fantasy I always be having when I think about getting onstage is to do everything. If I came back and did stand-up again, I can't just be like the other standup comics. To have a real hot band, play some tracks for about 40 minutes, the curtain drops and then you do an hour of jokes? That's a unique-ass show. [Laughs] That's the ultimate vision."
– Eddie Murphy fantasizes about a possible return to the standup stage in a new interview with Rolling Stone.


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Product lifecycle management (PLM) is the process of managing the entire lifecycle of a product from its conception, through design and manufacture, to service and disposal. PLM integrates people, data, processes and business systems and provides a product information backbone for companies and their extended enterprise.
It is one of the four cornerstones of a corporation's information technology structure. All companies need to manage communications and information with their customers (CRM-Customer Relationship Management), their suppliers (SCM-Supply Chain Management), their resources within the enterprise (ERP-Enterprise Resource Planning) and their planning (SDLC-Systems Development Life Cycle). In addition, manufacturing engineering companies must also develop, describe, manage and communicate information about their products.
Documented benefits include:
Product Lifecycle Management (PLM) is more to do with managing descriptions and properties of a product through its development and useful life, mainly from a business/engineering point of view; whereas Product life cycle management (PLCM) is to do with the life of a product in the market with respect to business/commercial costs and sales measures.
Product lifecycle management (PLM) is the title commonly applied to a set of application software that enables the New Product Development (NPD) business process.
Within PLM there are four primary areas;
Note: While application software is not required for PLM processes, the business complexity and rate of change requires organizations execute as rapidly as possible.
Product Data Management is focused on capturing and maintaining information on products and/or services through its development and useful life. Product and Portfolio Management is focused on managing resource allocation, tracking progress vs. plan for projects in the new product development projects that are in process (or in a holding status). Portfolio management is a tool that assists management in tracking progress on new products and making trade-off decisions when allocating scarce resources.
For simplicity the stages described are shown in a traditional sequential engineering workflow. The exact order of event and tasks will vary according to the product and industry in question but the main processes are:
The major key point events are:
The reality is however more complex, people and departments cannot perform their tasks in isolation and one activity cannot simply finish and the next activity start. Design is an iterative process, often designs need to be modified due to manufacturing constraints or conflicting requirements. Where exactly a customer order fits into the time line depends on the industry type, whether the products are for example Build to Order, Engineer to Order, or Assemble to Order.
Inspiration for the burgeoning business process now known as PLM came when American Motors Corporation (AMC) was looking for a way to speed up its product development process to compete better against its larger competitors in 1985, according to François Castaing, Vice President for Product Engineering and Development. After introducing its compact Jeep Cherokee (XJ), the vehicle that launched the modern sport utility vehicle (SUV) market, AMC began development of a new model, that later came out as the Jeep Grand Cherokee. The first part in its quest for faster product development was computer-aided design (CAD) software system that make engineers more productive. The second part in this effort was the new communication system that allowed conflicts to be resolved faster, as well as reducing costly engineering changes because all drawings and documents were in a central database. The product data management was so effective, that after AMC was purchased by Chrysler, the system was expanded throughout the enterprise connecting everyone involved in designing and building products. While an early adopter of PLM technology, Chrysler was able to become the auto industry's lowest-cost producer, recording development costs that were half of the industry average by the mid-1990s.
Many software solutions have developed to organize and integrate the different phases of a product's lifecycle. PLM should not be seen as a single software product but a collection of software tools and working methods integrated together to address either single stages of the lifecycle or connect different tasks or manage the whole process. Some software providers cover the whole PLM range while others a single niche application. Some applications can span many fields of PLM with different modules within the same data model. An overview of the fields within PLM is covered here. It should be noted however that the simple classifications do not always fit exactly, many areas overlap and many software products cover more than one area or do not fit easily into one category. It should also not be forgotten that one of the main goals of PLM is to collect knowledge that can be reused for other projects and to coordinate simultaneous concurrent development of many products. It is about business processes, people and methods as much as software application solutions. Although PLM is mainly associated with engineering tasks it also involves marketing activities such as Product Portfolio Management (PPM), particularly with regards to New product introduction (NPI).
Imagine, Specify, Plan, Innovate
The first stage in idea is the definition of its requirements based on customer, company, market and regulatory bodies' viewpoints. From this a specification of the products major technical parameters can be defined. Parallel to the requirements specification the initial concept design work is carried out defining the visual aesthetics of the product together with its main functional aspects. For the Industrial Design, Styling, work many different media are used from pencil and paper, clay models to 3D CAID Computer-aided industrial design software.
Describe, Define, Develop, Test, Analyze and Validate
This is where the detailed design and development of the product's form starts, progressing to prototype testing, through pilot release to full product launch. It can also involve redesign and ramp for improvement to existing products as well as planned obsolescence. The main tool used for design and development is CAD Computer-aided design. This can be simple 2D Drawing / Drafting or 3D Parametric Feature Based Solid/Surface Modelling, Such software includes technology such as Hybrid Modeling, Reverse Engineering, KBE (Knowledge-Based Engineering), NDT (Nondestructive testing), Assembly construction.
This step covers many engineering disciplines including: Mechanical, Electrical, Electronic, Software (embedded), and domain-specific, such as Architectural, Aerospace, Automotive, ... Along with the actual creation of geometry there is the analysis of the components and product assemblies. Simulation, validation and optimization tasks are carried out using CAE (Computer-aided engineering) software either integrated in the CAD package or stand-alone. These are used to perform tasks such as:- Stress analysis, FEA (Finite Element Analysis); Kinematics; Computational fluid dynamics (CFD); and mechanical event simulation (MES). CAQ (Computer-aided quality) is used for tasks such as Dimensional Tolerance (engineering) Analysis. Another task performed at this stage is the sourcing of bought out components, possibly with the aid of Procurement systems.
Manufacture, Make, Build, Procure, Produce, Sell and Deliver
Once the design of the product's components is complete the method of manufacturing is defined. This includes CAD tasks such as tool design; creation of CNC Machining instructions for the product's parts as well as tools to manufacture those parts, using integrated or separate CAM Computer-aided manufacturing software. This will also involve analysis tools for process simulation for operations such as casting, molding, and die press forming. Once the manufacturing method has been identified CPM comes into play. This involves CAPE (Computer-aided Production Engineering) or CAP/CAPP – (Production Planning) tools for carrying out Factory, Plant and Facility Layout and Production Simulation. For example: Press-Line Simulation; and Industrial Ergonomics; as well as tool selection management. Once components are manufactured their geometrical form and size can be checked against the original CAD data with the use of Computer Aided Inspection equipment and software. Parallel to the engineering tasks, sales product configuration and marketing documentation work will be taking place. This could include transferring engineering data (geometry and part list data) to a web based sales configurator and other Desktop Publishing systems.
Use, Operate, Maintain, Support, Sustain, Phase-out, Retire, Recycle and Disposal
The final phase of the lifecycle involves managing of in service information. Providing customers and service engineers with support information for repair and maintenance, as well as waste management/recycling information. This involves using such tools as Maintenance, Repair and Operations Management (MRO) software.
Communicate, Manage and Collaborate
None of the above phases can be seen in isolation. In reality a project does not run sequentially or in isolation of other product development projects. Information is flowing between different people and systems. A major part of PLM is the co-ordination of and management of product definition data. This includes managing engineering changes and release status of components; configuration product variations; document management; planning project resources and timescale and risk assessment.
For these tasks graphical, text and metadata such as product BOMs (Bill of Materials) needs to be managed. At the engineering departments level this is the domain of PDM – (Product Data Management) software, at the corporate level EDM (Enterprise Data Management) software, these two definitions tend to blur however but it is typical to see two or more data management systems within an organization. These systems are also linked to other corporate systems such as SCM, CRM, and ERP. Associated with these system are Project Management Systems for Project/Program Planning.
This central role is covered by numerous Collaborative Product Development tools which run throughout the whole lifecycle and across organizations. This requires many technology tools in the areas of Conferencing, Data Sharing and Data Translation. The field being Product visualization which includes technologies such as DMU (Digital Mock-Up), Immersive Virtual Digital Prototyping (virtual reality) and Photo realistic Imaging.
User Skills
The broad array of solutions that make up the tools used within a PLM solution-set (e.g., CAD, CAM, CAx…) were initially used by dedicated practitioners who invested time and effort to gain the required skills. Designers and engineers worked wonders with CAD systems, manufacturing engineers became highly skilled CAM users while analysts, administrators and managers fully mastered their support technologies. However, achieving the full advantages of PLM requires the participation of many people of various skills from throughout an extended enterprise, each requiring the ability to access and operate on the inputs and output of other participants.
Despite the increased ease of use of PLM tools, cross-training all personnel on the entire PLM tool-set has not proven to be practical. Now, however, advances are being made to address ease of use for all participants within the PLM arena. One such advance is the availability of "role" specific user interfaces. Through Tailorable UIs, the commands that are presented to users are appropriate to their function and expertise.
These techniques include:-
Concurrent engineering (British English: simultaneous engineering) is a workflow that instead of working sequentially through stages, carries out a number of tasks in parallel. For example: starting tool design before the detailed designs of the product are finished, or the engineer starting on detail design solid models before the concept design surfaces models are complete. Although this does not necessarily reduce the amount of manpower required for a project, it does drastically reduce lead times and thus time to market. Feature based CAD systems have for many years allowed the simultaneous work on 3D solid model and the 2D drawing by means of 2 separate files, with the drawing looking at the data in the model; when the model changes the drawing will associatively update. Some CAD packages also allow associative copying of geometry between files. This allows, for example, the copying of a part design into the files used by the tooling designer. The manufacturing engineer can then start work on tools before the final design freeze; when a design changes size or shape the tool geometry will then update. Concurrent engineering also has the added benefit of providing better and more immediate communication between departments, reducing the chance of costly, late design changes. It adopts a problem prevention method as compared to the problem solving and re-designing method of traditional sequential engineering.
Defence engineering traditionally develops the product structure from the top down. The system engineering process prescribes a functional decomposition of requirements and then physical allocation of product structure to the functions. This top down approach would normally have lower levels of the product structure developed from CAD data as a bottom up structure or design.
In 2008, following the revolution around Web 2.0, one of the key commercial players in PLM introduced the notion of PLM 2.0, which encompasses a social community approach to PLM.
PLM 2.0 is about reuse of Web 2.0 like terminology and concept in the domain of PLM. More than a technology, it is a philosophy where:
Currently, PLM 2.0 is still more an idea and a concept than a reality. But more and more PLM offering will embrace the concepts that has been listed here.
Product and process lifecycle management (PPLM) is a alternate genre of PLM in which the process by which the product is made is just as important as the product itself. Typically, this is the life sciences and advanced specialty chemicals markets. The process behind the manufacture of a given compound is a key element of the regulatory filing for a new drug application. As such, PPLM seeks to manage information around the development of the process in a simlar fashion that baseline PLM talks about managing information around development of the product.
Total spending on PLM software and services is estimated to be above $15 billion a year but it is difficult to find any two market analysis reports that agree on figures. Market growth estimates are in the 10% area.
Looking at segment split, currently most of the revenue generated is in the area of EDA and high end MCAD (each above 15%), followed by AEC, low-end MCAD, and PDM (each above 10%). The other notable segment is CAE at above 5%. It is however predicted that the collaborative PDM and visualization areas will increase in dominance.
There are many companies that supply software to support the PLM process; the largest by revenue are mentioned here. Some companies such as Dassault Systèmes ($1.7B),Siemens PLM Software ($1.4B), Altair Engineering ($0.15B), Agile Software Corporation (now part of Oracle Corporation) and SofTech, Inc. (.011B) provide software products that cover most of the areas of PLM functionality; some like PTC ($0.8B) cover a number of segments; other companies for example MSC Software($0.3B)and Wrench Solutions provide packages specializing in specific topics. One company, Aras Corp offers Microsoft-based open source enterprise PLM solutions, and both Datastay Corp. and Arena Solutions, provide on-demand PLM (Software as a service) solutions. KnowledgeBench provides web-based PLM applications that are used by pharmaceutical and food and beverage manufacturers. Additional unique offerings include Selerant which specializes only in the process industry and provides formulation optimization and regulatory management. Also, Datastay PLM, as well as Omnify Software's PLM, incorporate traditionally disparate systems (quality, training, corrective action/preventive action) to augment support for regulatory compliance across all verticals. Other companies provide web-based PLM solutions mainly for apparel, footwear, accessories, and consumer brand manufacturers, including Centric Software and ecVision.
Independent PLM solution providers such as Atos Origin, SIA Conseil, accenture, Infosys, Integware and Metafore deliver PLM consulting and system integration services and help companies to identify, design, implement and operate appropriate PLM practices, processes and technologies.
There are also companies whose main revenue is not from PLM but do attribute some of their income from PLM software, such as SAP($11B), SSA Global , Oracle Corporation and Autodesk ($1.5B). Other companies in this market, such as Atos Origin, IBM ($88.9B), EDS ($19.8B),NEC ($45B), Accenture, Infosys (INFY), Geometric, Tata Consultancy Services (TCS),WRENCH Solutions (P) Ltd ,ITC Infotech provide outsourcing and consulting services some of which is in the field of PLM. 3DPLM is a joint venture between Dassault systeme and Geometric to develop specialised PLM solutions.
Many of these companies have emerged out of the CAD and PDM market. For a more comprehensive list see List of CAD companies.


text:
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by Michael Crichton
No current Talk conversations about this book.
Good characterizations. Excellent story-line (I didn't read the blurb first, so it was interesting to see what it was about). Great factuality. Thrilling.
It's the nightmare of a lot of people: a passenger aircraft flailing wildly out of control at 35,000 feet, with multiple injuries and fatalities. The aircraft manufacturer is determined to find out what went wrong before the media completely trashes the company, but there is someone else equally determined to prevent the truth from coming out.
As an aviation enthusiast, I was predictably bound to like this. It is a veritable feast of technical details, reports and impressive-sounding acronyms. The story is told in very short, snappy chapters, always ensuring that the reader is oriented in time and place. The protagonist is female, which is a nice bonus and adds even more to the already-high stakes, because she is trying to do her job in a highly male-dominated sphere.
I did wonder why the National Transportation Safety Board would just let the manufacturer investigate the occurrence instead of taking it over themselves, but apparently the NTSB's aviation "go teams" respond only to accidents that occur on US territory or in international waters, and the plane in this story merely landed at LAX. Still, since there were fatalities, I would have thought that the NTSB would want to at least have someone checking up on the investigation. Perhaps they didn't have the budget.
The technology is probably dated somewhat -- I specifically noticed the pagers, but there is probably even more that would be considered ancient history in the world of aviation. The media landscape has also changed significantly: would Norton have even had a chance at containing the story now, in the world of blogs and social media? A similar story set in the present day could be interesting. Airframe was published in 1996, but its themes of aviation safety and the dangers of sensationalist media presenting the story they want instead of the truth are still relevant today.
An airliner travelling from China to the US has an in-air incident, first characterized as turbulence but costing 3 lives plus more than 50 injuries. What follows is an investigation by the plane manufacturer...amidst some contentious opinions from air travel pundits The plane had a well-documented flaw, and everyone was quick to jump on it as the cause. But airliners are designed with redundant systems, and failure is often a series of unlikely, cascading events.
Casey Singleton, an executive for the airplane manufacturer, is charged with leading the investigation. It is not, however, a single investigation of an isolated event. While this is going on, China, the owner of the plane in question, has a contract proposal for a lot of planes that Casey's company is the front-runner. There are some that do not want this deal to go through -- and in her own company! The unions and one upper executive in particular are setting her up to be the fall guy. On top of this, the leading news show is doing a piece -- and seems intent on taking down her company.
The late Michael Crichton could write the phone book and make it interesting. While some of the technology covered is already dated (noticeable only by frequent fliers), the story was nevertheless riveting and entertaining. I haven't read all of Crichton's books yet, but I haven't been disappointed by anything that wasn't published before his death.
I'd forgotten how good Crichton's books were and this one is pretty great. It's written from the point of view of Casey a divorced Mom who's a Quality Assurance VP at the fictional Norton Company.
It's an airplane crash thriller with one big change, there's technically no crash of the plan. Which I think makes the story more interesting. Like a murder mystery without a murder.
And this book is a bit of a mystery. Mostly it's a thriller, there are veiled threats from the union at the plant, and brainy thrills as Casey tries to stay ahead of what seems like a plane full of people with all different agendas.
The plot is good, but what's really great about Airframe is Crichton's writing. In this book and in his others he had this knack for putting the science/engineering/technical details in there and not making it all seem like part of the story and not just an exposition dump.
I do wish that there'd been a bit more at the end, the conclusion and tying up of all the stories seemed a bit rushed. Not to mention Crichton never really tied up the ex-husband and their child story which I thought was an interesting subplot.
This is my first Crichton since the Andromeda Strain written so many years ago. Another reason to ignore the professional critics who have not been terribly kind to Crichton in the past few years. I really liked this book. It has a marvelous blend of science, information and a good plot that keeps the pages turning.
It's interesting that many of the reviews I read focused on the aircraft industry. I think the book is more about the media and it's relentless pursuit of the visual and the sound bite at the expense of truth and the whole picture more than about airplanes.
Enroute from Hong Kong to Denver, a brand new Norton-22, a plane clearly modeled on the Boeing 747, pitches and dives like a porpoise before being brought under control. The violent maneuvers kill three passengers and injures 56 others. . The airline's VP in charge of quality assurance — Casey Singleton — has to find out why, before more passengers and the airline's future go into a tailspin. As always in Crichton's expert hands, readers learn a lot about science while becoming enmeshed in the power-plays, office politics, and pressures of the global market and American jobs. Her job is complicated, because, as we gradually learn, powers within the company are trying to manipulate her and to embarrass the company so that the president of the company can be forced out in favor of another. Casey is saddled with a Norton family nephew who turns out to be a spy for one of the other company officers. We learn a great deal about aircraft manufacture and design — I must admit to really loving the technical detail — as Casey tries to figure out why the cockpit reports of turbulence differ from physical evidence of a "commanded slat deployment," something, that even had it occurred at altitude and high speed should not have caused the plane to go out-of-control the way it appears to have done.
Crichton obviously doesn't like lawyers, their stoolies (an ex-FAA employee who testifies for the plaintiffs in injury suits figures prominently in the media's desire to create a nasty story) nor the media, and a character clearly modeled after Mike Wallace has few redeeming qualities. At one point Casey is to be interviewed by the Wallace character, Marty Reardon, and a company PR person comes by to help her prepare a little. "There's only one more thing I can tell you, Katherine. You work in a complex business. If you try to explain that complexity to Marty, you'll be frustrated. You'll feel he isn't interested. He'll probably cut you off. Because he isn't interested. A lot of people complain television lacks focus. But that's the nature of the medium. Television's not about information at all. Information is active, engaging. Television is passive. Information is disinterested, objective. Television is emotional. It's entertainment. . . . [Marty's:] paid to exercise his one reliable talent: provoking people, getting them to make an emotional outburst, to lose their temper, to say something outrageous. He doesn't really want to know about airplanes. He wants a media moment."
Casey's father was a journalist and an old friend of his remarks at the end of the book, "Used to be — in the old days-- the media image roughly corresponded to reality. But now it's all reversed. The media image is the reality, and by comparison day-to-day life seems to lack excitement. So now day-to-day life is false, and the media image is true. Sometimes I look around my living room, and the most real thing in the room is the television. It's bright and vivid, and the rest of my life looks drab. So I turn the damn thing off. That does it every time. Get my life back."
References to this work on external resources.
Wikipedia in English (2)
Amazon.com Amazon.com Review (ISBN 0345402871, Mass Market Paperback)Cruising 35,000 feet above the earth, a twin-engine commercial jet encounters an accident that leaves 3 dead, 56 wounded, and the cabin in shambles. What happened? With a multi-billion-dollar company-saving deal on the line, Casey Singleton is sent by her hard-driving boss to uncover the mysterious circumstances that led to the disaster before more people die. But someone doesn't want her to find the truth. Airframe bristles with authentic information, technical jargon, and the command of detail Crichton's readers have come to expect. Check out Amazon.com's Airframe feature and read an excerpt from the book!
(retrieved from Amazon Mon, 30 Sep 2013 13:24:59 -0400)
Following a series of plane crashes and passenger deaths a frenzied high pressure investigation is ordered with some surprising results.
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Free Prostate Cancer Screenings | Events
The Northwest Cancer Clinic will be offering Free Prostate Cancer Screening Wednesday August 20th, Thursday August 21st, and Friday August 22nd, from 4 pm to 6pm.
Local prostate cancer experts will be on hand to discuss key topics regarding prostate cancer and prostate cancer screening.
The Physician Volunteer Team includes:
- Dr. Robert Chin – Radiation Oncologist, NWCC
- Dr. Sheila Rege - Radiation Oncologist, NWCC
- Dr. Eugene Hong - Radiation Oncologist, NWCC
- Dr. Fred Foss – Urologist, Tri-Cities
- Dr. Naeem Chavla - Urologist, Tri-Cities
- Dr. Animesh Sahai - Urologist, Tri-Cities
The screening is co-sponsored by Quest Diagnostics.
Prostate Cancer Screening is generally recommended for men over 50 and in special circumstances for men over 40. In 2014, about 233,000 American men will be diagnosed with this disease. Prostate cancer is the second most common type of cancer among men in this country.
RSVP to (509) 987-1800 to minimize waiting. Walk-ins are welcome.
For more information on Prostate Cancer go to www.nwcancerclinic.com


text:
Main Street U.S.A.
- The Harmony Barber Shop is tucked away down the first alley to the left.
- The Disney Arcade offers a working, coin-fed nickelodeons.
- Left-side shop windows feature gorgeous character displays.
- Save Alien Encounter for the end of the day.
- The Tomorrowland Transit Authority gives you a taste of all the rides in the "land".
Fantasyland/Mickey's Toontown Fair
- Cinderella Castle holds a chic antique shop.
- Winnie the Pooh has a great motion base on its car.
- The Tea Cups are a must.
- Mickey signs autographs in a small building behind his house in Toontown.
- Hidden Mickey's abound in Pirates of the Caribbean and Jungle Cruise.
- The Enchanted Tiki Birds show now features Iago, the parrot from "Aladdin" and Zazu, the hornbill from "The Lion King".
- Swiss Family Treehouse is back after being renovated.
Frontierland/Liberty Square
- Kids will enjoy watching log boats careen down the flume at Splash Mountain viewing stand.
- The Hall of Presidents is having both good and bad days lately. When operational, it features President Clinton.
- Be sure to read the gravestones while waiting in line for The Haunted Mansion.
Copyright © 2015, Los Angeles Times


text:
An aluminosilicate ceramic, spherical pellet made from spent ceramic catalyst. More specifically, a spherical ceramic pellet made from spent fluid cracking catalyst. The pellets can be made by grinding the catalyst particles, forming them into spherical pellets, and then sintering the pellets. The final product is useful as a proppant in oil and gas well fracturing.
1. A spherical ceramic proppant pellet comprising spent fluid cracking catalyst particles, wherein the pellet is formed by:
a. reducing the median particle size of the catalyst;
b. mixing the catalyst particles with water and a binder to form spherical pellets; and
c. sintering the pellets.
2. The proppant pellet of
3. The proppant pellet of
4. The proppant pellet of
5. The proppant pellet of
6. The proppant pellet of
7. The proppant pellet of
8. The proppant pellet of
9. The proppant pellet of
10. The proppant pellet of
11. A method for preparing a spherical ceramic proppant pellet, the method comprising:
a. providing spent fluid cracking catalyst particles;
b. reducing the particle size of the catalyst particles;
c. mixing the catalyst particles with water and a binder to form spherical pellets; and
d. sintering the pellets.
12. The method of
13. The method of
14. The method of
15. The method of
16. The method of
17. The method of
18. The method of
19. The method of
20. A proppant pellet composition comprising pelletized and calcined spent fluid cracking catalyst, wherein the spent fluid cracking catalyst comprises from about 25 to about 80 weight percent silica, and from about 20 to about 75 weight percent alumina.
21. The proppant pellet composition of
22. The proppant pellet composition of
23. The proppant pellet composition of
24. The proppant pellet composition of
25. The proppant pellet composition of
up to about 1000 parts per million copper;
up to about 7000 parts per million vanadium;
up to about 200 parts per million lead;
up to about 7000 parts per million nickel;
up to about 2500 parts per million antimony;
up to about 2 weight percent iron;
up to about 1.5 weight percent sodium; and,
detectable amounts of at least one component selected from the group consisting of platinum, rhenium, sulfur compounds, and rare earth metals.
26. The proppant pellet composition of
27. The proppant pellet composition of
28. The proppant pellet composition of
29. The proppant pellet composition of claims 27 or 28, wherein
the resin of the inner coating is at least one resin independently selected from the group consisting of phenol-aldehyde resins, urea-aldehyde resins, melamine-aldehyde resins, epoxy resins, furfuryl alcohol resins, and copolymers of such resins; and wherein
the resin of the outer coating is at least one resin independently selected from the group consisting of phenol-aldehyde resins, urea-aldehyde resins, melamine-aldehyde resins, epoxy resins, furfuryl alcohol resins, and copolymers of such resins.
30. A method of propping a fracture in a subterranean formation comprising creating a fracture in said subterranean formation, and placing in said fracture a quantity of the proppant pellets set forth in any one of claims 1-10 or 20-28.
This application claims the benefit of the filing date of the U.S. Provisional Application for Pat. Ser. No. 60/236,292, filed Sep. 28, 2000.
The present invention relates to proppant pellets prepared by using alumina-silica containing waste materials from industrial processes. The proppant pellets may be resin coated. The present invention further relates to a method for the manufacture of proppant pellets.
In the completion and operation of oil wells, gas wells, water wells, and similar boreholes, it frequently is desirable to alter the producing characteristics of the formation by treating the well. Many such treatments involve the use of particulate material. For example, in hydraulic fracturing, particles called proppants are used to maintain the fracture in a propped condition. In hydraulic fracturing, proppant particles under high closure stress tend to fragment and disintegrate. At closure stresses above about 5,000 psi, silica sand, the most common proppant, is not normally employed due to its propensity to disintegrate. The resulting fines from this disintegration migrate and plug the interstitial flow passages in the propped interval. These migratory fines drastically reduce the permeability of the propped fracture. Since closure stress varies directly with depth, this means that sand is not a useful proppant material at depths greater than about 5,000 feet.
Sintered bauxite or high grade alumina have been used as proppant materials at well depths greater than 20,000 feet, but these high strength proppants have much higher densities than sand and therefore require high viscosity pumping fluids or high pumping rates. Larger pumping equipment is required, and wear rates on fluid carrying equipment is accelerated. In addition, the raw materials used to make the proppant materials are more costly.
Proppants of intermediate density are known, and work well in the intermediate depths and pressures, i.e., 7,000 to 14,000 feet (5,000-10,000 psi).
Proppant pellets having a specific gravity of less than 3.4 g/cm3 have been made from diaspore clay, bauxite, and/or alumina. Eufala bauxite, a bauxitic-kaolin material, has been used to prepare a proppant with a density of less than 3.0 g/cm3. Also known is a method of making ceramic microspheres for use as proppants from water-soluble salts, mineral compositions or organometallic complexes, and ultrafine bauxite or alumina-containing particles. A low density proppant has been prepared from kaolin clay and amorphous to microcrystalline silica. The raw materials used to make all these intermediate proppants are costly, and a less expensive proppant material is desired.
Resin coated particles have been used in efforts to improve the stability of proppants at high closure stresses. Sand or other substrates have been coated with an infusible resin such as an epoxy or phenolic resin. These materials are superior to sand at intermediate stress levels. However, at high temperature and high stress levels, the resin coated particles still show a decrease in permeability.
A process is known for coating particulates with an infusible resin for use as proppants in fracturing operations. The particulates include sand, nut shells, glass beads and aluminum pellets. The resins include urea-aldehyde resins, phenol-aldehyde resins, epoxy resins, furfuryl alcohol resins and polyester or alkyd resins. The resin coating may be applied by mixing the particles with a melted resin and subsequently cooling the mixture, or dissolving the resin in a solvent, applying it to the particles, and evaporating the solvent. Coupling agents may be added to the system to improve the strength of the resin-substrate bond.
Proppants comprising sand particles with a precured phenol formaldehyde resin coating have been used for propping fractures in subterranean formations.
Although resin coated sands have proven satisfactory in numerous applications, concern exists over their use under high closure stresses. For example, some self consolidating resin coated particles of the prior art do not develop their full strength until the resin coating has cured in the formation. In the event of rapid closure of the fracture, the proppant could be crushed before the resin cured, resulting in decreased permeability. This problem is alleviated by the use of a dual resin coated particle having a reinforcing agent interspersed at the inner resin/outer resin boundary, as described in U.S. Pat. No. 5,422,183 assigned to Santrol, Inc, incorporated herein by reference as if fully written out below.
The present invention utilizes spent ceramic media from petroleum refining operations, where the media provides a catalytic function during "cracking" of the hydrocarbons, while drawing out impurities from the crude oil as it passes through a packed column of ceramic beads. These beads are manufactured by Englehard Corporation, W R Grace and Akzo Nobel as well as other Far Eastern producers and are variously known as fluid cracking catalyst, e-cats, and equilibrium catalyst (hereinafter referred to as "fluid cracking catalyst" or "FCC"). The use of catalytic ceramic media for removing impurities from petroleum products is a long established art. The catalytic media can be regenerated after use as a cracking catalyst several times but eventually is spent, and is discarded as waste material. The present invention uses the FCC as a base material for remanufacturing larger ceramic spheres, which can be used in the hydraulic fracturing of subterranean oil and gas bearing formations.
The present invention provides a spherical ceramic proppant pellet comprising spent fluid cracking catalyst particles, wherein the pellet is formed by reducing the median particle size of the catalyst; mixing the catalyst particles with water and a binder to form spherical pellets; and sintering the pellets.
The present invention also provides a method for preparing a spherical ceramic proppant pellet, the method comprising the steps of providing spent fluid cracking catalyst particles; reducing the particle size of the catalyst particles; mixing the catalyst particles with water and a binder to form spherical pellets; and sintering the pellets.
The present invention further provides a proppant composition comprising spent fluid cracking catalyst, wherein the spent fluid cracking catalyst comprises from about 25 to about 80 weight percent synthetic silica, and from about 20 to about 75 weight percent alumina. The spent fluid cracking catalyst may optionally further comprise at least one of:
up to about 1,000 parts per million copper;
up to about 7,000 parts per million vanadium;
up to about 200 parts per million lead;
up to about 7000 parts per million nickel;
up to about 2500 parts per million antimony;
up to about 2 weight percent iron;
up to about 1.5 weight percent sodium; and, detectable amounts of a least one component selected from the group consisting of platinum, rhenium, sulfur compounds, and rare earth metals.
FIG. 1 is a graphical representation of the conductivity of an FCC ceramic proppant and a commercial lightweight ceramic proppant at various closure pressures.
The present invention utilizes fluid cracking catalyst, a material rich in alumina and silica, as a ceramic feedstock for producing proppant pellets. The catalyst material is formed into pellets and sintered using conventional methods.
Spent fluid cracking catalysts exist as ceramic beads comprising calcined mixtures of silica (SiO2), alumina (Al2O3), with minor amounts of antimony, copper, nickel, vanadium, lead, rare earth metals, sulfates, sulfides, and trace amounts of other components. Although the exact compositions of commercial FCCs are proprietary, in general a fluid cracking catalyst has four major component systems: zeolite, matrix, binder, and filler.
Zeolite, sometimes called molecular sieve, has a well-defined lattice structure. Its basic building blocks are silica and alumina tetrahedra. Typical zeolites also contain counterions such as sodium, and ammonium ions. Zeolites employed in the manufacture of the FCC catalyst are synthetic versions of naturally occurring zeolites called faujasites. Zeolites with applications to FCC are Type X, Type Y, and ZSM-5. Both X and Y zeolites have essentially the same crystalline structure. The major difference is that the X zeolite has a lower silica/alumina ratio than the Y zeolite. Virtually all of today's catalysts contain Y zeolite or variations thereof. One variation is an aluminum-deficient zeolite, called ultrastable Y, or simply USY. Zeolites are sometimes ion exchanged with rare earth components in order to increase catalytic activity and thermal stability. Rare earth is a generic name for fourteen metallic elements of the lanthanide series, including lanthanum and cerium.
The matrix component of the FCC can also have catalytic activity. Alumina is normally the source for the matrix component. Most FCCs contain an amorphous alumina matrix, but some catalyst suppliers incorporate a form of alumina that has a crystalline structure.
The filler component is a clay incorporated into the catalyst to dilute its activity. Kaolin [Al2(OH)2,Si2O5] is the most common clay used in the FCC catalyst. One FCC catalyst manufacturer used kaoline clay as a skeleton to grow the zeolite in situ.
The binder serves as a "glue" to hold the zeolite, matrix and filler together. The functions of the filler and the binder are to provide physical integrity and mechanical strength. They impact such characteristics of the FCC as density, attrition resistance, and particle size distribution.
Spent fluid cracking catalyst also contains a number of metal contaminants, including nickel, vanadium, iron, antimony and copper. These contaminants originate largely from the heavy, high-molecular weight fraction of the FCC feed. The quantity of these metals on the FCC is determined by their levels in the petroleum feedstock and the catalyst addition rate. Essentially, all these metals in the feed are deposited on the catalyst. Much of the iron on the FCC comes from metal scale from piping.
Another component of spent fluid cracking catalyst is coke, which is carbon that is deposited on the catalyst during cracking.
As metal and carbon contaminants are deposited on the FCC, the catalyst loses its activity and selectivity. Fresh catalyst is added to the reactor unit continually to replace the catalyst lost by attrition and to maintain catalyst activity. In cases where the makeup rate for activity maintenance exceeds catalyst losses, part of the catalyst inventory is periodically withdrawn from the unit to control the catalyst level in the regenerator. This spent catalyst provides a low cost feedstock that is rich in alumina and silica, and according to the invention is remanufactured to produce larger ceramic spheres. The ceramic spheres can be used as proppants in the hydraulic fracturing of subterranean oil and gas bearing formations.
Spent fluid cracking catalysts suitable for the proppant of the present invention therefore primarily contain silica and alumina, and may further contain sodium or other counterions, rare earth elements, carbon, metals such as typically found in petroleum feedstocks, and other contaminants.
The ratio of silica to alumina is a critical factor in the ultimate performance of the proppant product, but can be quite variable in fluid cracking catalysts. A nominal 45/55 silica to alumina weight ratio is quite common in FCCs. Preferred useful ratios by weight of silica to alumina for use as a feedstock material for proppants according to the present invention are about 2:1 to more preferably about 1:1. Spent fluid cracking catalyst suitable for use as a feedstock material comprise 25-80 weight percent silica, preferably 40 to 60, weight percent silica, and even more preferably 45 to 55 weight percent silica. Suitable fluid cracking catalyst for use according to the present invention comprise 20-75 weight percent alumina, preferably 30 to 60 weight percent alumina, and even more preferably 45 to 55 weight percent alumina. Typical ranges of chemical compositions for MET 192 or MET 195 from Metalloy Corporation are shown in Table A.
This chemical analysis is included for example purposes only, and should not be considered as a limitation of the FCC used to produce the proppants of the present invention. In some instances, alumina or silica can be added, such as clay or silica gel, to adjust the silica:alumina weight ratio to 1:1 to 2:1.
The spherical ceramic proppant pellets of the present invention are prepared by a method comprising the steps of providing spent fluid cracking catalyst particles, reducing the particle size of the catalyst particles, mixing the catalyst particles with water and a binder to form spherical pellets, and sintering the pellets. The pellets are preferably screened to provide a suitable median particle size.
Reduction of the particle size of the FCC particles is preferably accomplished by conventional ball milling techniques, including either wet or dry ball milling. The median particle size of the FCC particles after reduction is preferably about 1 to about 10 microns, and more preferably about 2 to about 6 microns, as measured by laser diffraction.
The comminuted FCC particles are then mixed with water and a binder. Suitable binders include, but are not limited to, polyvinyl acetate, methyl cellulose, and polymethylmethacrylate. The amount of water used is preferably 25-45 percent by weight of fluid cracking catalyst, but will vary depending on the composition of the FCC. The amount of binder used is preferably about 0.1% to 0.5% by weight, preferably about 0.2 to 0.25%, but will depend on particle size distribution and shape.
Mixing may be accomplished by conventional methods. Preferably, a Eirich mixer is used, such as an Eirich RVO2. The pellet size is determined by mixer run time. A mix time of 45 seconds to 80 seconds is usually sufficient in the particular equipment used to form well rounded substantially spherical pellets in the size range of 1 mm to 420 microns. After spherical pellets form, the pellets are dried at relatively low temperatures of from about 120 to about 150� C. After drying, the pellets are sufficiently tough to undergo the stress of pneumatic handling and sintering.
Sintering is preferably accomplished using a rotary kiln, although other conventional sintering methods may be used. Pellets are sintered at a temperature of about 1,300� C. to about 1,500� C. The temperature along the kiln will vary but most preferably a temperature of about 1,500� C. is attained for a dwell time of at least about 30 minutes. Sintering causes a reduction of up to 20% in particle size as well as an increase in density in the component products. A finished proppant particle according to the process described above may have a density in the range of about 2 to about 2.7 gm/cm3, depending upon the source FCC and actual sintering temperature. Preferably, the density of the finished proppant particle is from about 2.45 gm/cm3 to about 2.65 gm/cm3.
After sintering the pellets assume a darker gray color and can be screened by Rotex or other conventional methods into the particle sizes needed. A typical product size is 20/40 mesh, which indicates that 90 weight percent of its pellets are between 0.0167 inches and 0.0331 inches in size. Preferably, 90 weight percent of the pellets are between 0.0232 inches and 0.0331 inches in size.
Spent FCC particles were ball milled to a 4-6 micron median particle size, as measured by laser diffraction. Ten pounds of milled material having a dried, free flowing form was fed to a pellet forming mixer device, specifically an Eirich RVO2. To the test batch, 25% to 45% by weight of water and liquid polyvinyl acetate (PVA) was added in the amount of 0.3% by liquid volume. The addition of PVA added green strength for subsequent sintering.
When spherical pellets formed in the mixer, the machine was stopped and the pellets were transferred to a low temperature convection oven and dried at 120� F. for 1 hour. The specific gravity of the product at this stage was approximately 2.1 gm/cm3.
After drying, the spherical pellets were sintered in a rotary kiln at a temperature of between 1,325� C. to 1,500� C. for about 30 minutes. After sintering, the pellets were screened to 20/40 mesh.
The pellets so formed are surprisingly similar in performance to existing ceramic proppant pellets, albeit with slightly lower crush resistance and lower conductivity with respect to brine and hydrocarbons, as shown in FIG. 1.
Conductivity testing to determine the relative conductivity of the final FCC pellets was followed according to standard StimLab procedures using 2% KCl as the flowing medium. As shown in Table 1, the data indicate that the FCC product, although slightly lower in absolute conductivity, is within 10% of the performance of a typical lightweight ceramic at higher closures (10,000 psi). This is graphically represented in FIG. 1, where line 10 shows the performance of commercial lightweight ceramic proppant, and line 20 show the performance of the FCC ceramic proppant.
Crush numbers were generated at 7,500 psi, according to standard API RP 60 procedures. Crush data, shown in Table 2, indicate a slight decline in crush strength over current lightweight ceramics, but the proppants prepared according to the present invention have performance approximating existing commercial proppant products, and are suitable for commercial use.
It is expected that crush resistance and conductivity of the proppant products prepared according to the present invention, will equal or exceed that of commercial lightweight ceramic proppants, with manufacturing scaleup.
The Krumbein roundness and sphericity of the FCC derived ceramic proppants are approximately 0.9 and are equivalent to commercial lightweight ceramic proppants.
Additional proppant pellets were prepared from spent FCC catalyst according to the above described procedure, with 24 hour wet milling in a ball mill, drying and pressing into pellets. Sintering was conducted at 1300� C., 1400� C. or 1500� C. for 10 minutes. A final density of 99.6% of theoretical was achieved. X-ray diffraction indicated that the pellets contained about 50 to about 60 mol % cristobalite and about 40 to about 50 mol % mullite.
Other proppant pellets prepared according to the process of the present invention were tested for conductivity as described above, and the results of the tests are reported in Table 3, below.
Advantageously, proppant pellets comprising spent fluid cracking catalyst utilize waste materials from the petroleum refining process which would otherwise be costly to dispose of or reclaim. The proppant pellets of the present invention are lightweight, low density materials with crush strength and conductivity approximating those of existing products.
The utility of the FCC ceramic proppant of the present invention can be extended into high stress applications by coating the proppant with a resin coating. The resin coating may be cured or curable. In one embodiment, the FCC ceramic proppant pellets are coated with a resin dissolved in a solvent which is then evaporated. The resin is then cured. In another embodiment, the FCC ceramic proppant pellets are mixed with a melted resin which is then cooled, coating the pellets. The resin coating is then cured. Alternately, the resin coating is curable, but not substantially cured prior to use. In this embodiment, the resin is cured after injection into the well formation by techniques known in the art.
In a preferred embodiment, FCC ceramic proppant pellets are covered with an inner coating of a fusible, curable resin and an outer coating of a substantially cured resin. The resin coated particle can be used as a self-consolidating proppant, and is compatible with the fracturing fluid. If desired, the proppant pellet may further comprise an additional coating of a substantially cured resin which is located on the exterior of the substrate and inside the inner coating. Such particles exhibit enhanced properties such as improved fractionating fluid compatibility.
Resins suitable for the inner and outer coatings are generally any resins capable of being coated on the substrate and then being cured to a higher degree of polymerization. Examples of such resins include phenol-aldehyde resins of both the resole and novolac type, urea-aldehyde resins, melamine-aldehyde resins, epoxy resins and furfuryl alcohol resins and copolymers of such resins. The resins must form a solid non-tacky coating at ambient temperatures. This is required so that the coated particles remain free flowing and so that they do not agglomerate under normal storage conditions.
The preferred resins are the phenol-formaldehyde resins. These resins include true thermosetting phenolic resins of the resole type and phenolic novolac resins that may be rendered heat reactive by the addition of catalyst and formaldehyde. Such resins with softening points of 185� F. to 290� F. are acceptable.
The inner and outer coatings can be formed starting with the same or different type of resins. For example, the inner coating could be produced from a novolac and the outer coat from a resole. Regardless of the type of resin used, the outer resin must be curable at conditions that leave the inner coating curable, i.e., fusible and heat reactive.
A coupling agent as subsequently described is preferably incorporated during manufacture into the resin that is to be used as the inner coating, and may optionally also be incorporated into the resin that is to be used as the outer coating. The coupling agent which has a functional group reactive in the resin system is added in an amount ranging from about 0.1 to 10% by weight of the resin. The preferred range is from about 0.1 to 3% by weight of the resin. When using the preferred phenol formaldehyde resins, the coupling agent is incorporated into the resin under the normal reaction conditions used for the formation of the phenol-formaldehyde resin. The coupling agent is added to the resin after the phenol formaldehyde condensation reaction has occurred and the resin has been dehydrated to the final free phenol and melt viscosity range.
A preferred resin of the inner coating is a phenolic novolac resin. Particularly suitable are phenolic novolac resins manufactured by Georgia Pacific, known as 99NO7, and by OxyChem, known as 24-715. The GP-099N07 resin has a softening point range of 85� F.-100� F. The OxyChem 24-715 exhibits a softening point range of 70� F.-87� F. When either resin is used, it is necessary to add to the mixture a cross-linking agent to effect the subsequent curing of the resin. Hexamethylenetetramine is the preferred material for this function as it serves as both a catalyst and a source of formaldehyde.
The coupling agent to be employed is chosen based on the resin to be used. For phenolic resins, the coupling agents include amino, epoxy, and ureido organo silanes. Epoxy modified gamma-glycidoxypropyltrimethoxysilane has given excellent results when used in the amount of 0.50-1.00% based on the weight of the resin. The use of coupling agents as incorporated into the resin and as applied directly to the particulate substrate is discussed in Graham et al, U.S. Pat. No. 4,518,039, incorporated herein by reference as if fully written out below.
The outer coating of resin is formed from a heat curable resin coating formed over the inner resin. As stated previously, this outer resin must be curable at conditions that do not completely cure the inner coating thus leaving the inner coating curable. The preferred resins for the outer coating are of the resole type. Particularly suitable is a fast curing resole resin manufactured by Georgia Pacific known as 102N68. Resole resins generally are provided dissolved in a methanol and water solution as is Georgia Pacific 102N68. The resin exhibits an extremely fast cure having a 150� C. hot plate cure time of 30 seconds or less. The preferred resole should be in a solution of water and methanol as the solvent system. The organic solids level should be 65-75%, with a water content in the 5-15% level. The hot plate cure time at 150� C. should be in the range of 25-40 seconds.
The inner and outer resin coatings may be formed by a variety of methods. For example, the solvent coating process described in U.S. Pat. No. 3,929,191, to Graham et al., incorporated herein by reference as if fully written out below.
Other processes such as that described in U.S. Pat. No. 3,492,147 to Young et al. describes the coating of a particulate substrate with a liquid, uncatalyzed resin composition characterized by its ability to extract a catalyst or curing agent from a non-aqueous solution. As stated above, the preferred resins for use with the instant invention are phenol-formaldehyde novolac resins. When using such resins the preferred coating method is a hot melt coating procedure for forming the inner coat. Such a procedure is described in U.S. Pat. No. 4,585,064, to Graham et al, incorporated herein by reference as if fully written out below. Solvents are preferably used to apply the outer coat. The following is a discussion of typical coating process parameters using the preferred phenol-formaldehyde novolac resins.
The improved high strength particles of this embodiment of the invention are coated in a multi-step process. In the first step a phenol-formaldehyde resin inner coat is formed over the particulate substrate. In the second step an outer coating is formed. The outer coating is then cured at conditions that leave the inner resin curable.
The first or inner coating of resin may be formed on the particulate substrate by first coating the heated substrate with a phenol-formaldehyde novolac resin. This coating is carried out by preheating the particulate substrate to a temperature above the melting point of the particular resin used.
Typically the particulate substrate is heated to 350� F. to 500� F. prior to resin addition. The heated substrate is charged to a mixer or muller where generally from about 1% to about 6%, by weight of substrate, resin is added. The preferred amount of resin based on the weight of substrate is about 2%.
After completion of addition of the resin to the substrate, the substrate and melted resin are allowed to mix in the muller for a time sufficient to insure the formation of a uniform coating of resin on the particulate, usually about 10 to about 30 seconds.
Following this mixing step from about 5 to about 25%, by weight of the resin, of hexamethylenetetramine is added to the substrate resin mixture. The preferred amount of hexamethylenetetramine is about 13% by weight of the resin. After addition of the hexamethylenetetramine the entire mixture is allowed to mull for approximately one minute. Then water is added to quench the reaction of the inner resin coating. The amount of water added and the timing of its addition is adjusted to quench the curing of the inner resin while maintaining sufficient heat in the proppant to cure the outer coating that is added next.
The outer resin is then coated over the inner resin and allowed to substantially cure. Substantially cured, as used herein, is to be interpreted as meaning that the cross-linking reaction of the resin is substantially complete and that at typical downhole temperatures only minimal additional curing takes place. When the outer coating is the preferred resole, its addition is preferably carried out by adding it as a solution in a water/methanol mixture comprising between 15-30% methanol and 5-15% water. The preferred mixture is 6% water and 25% methanol.
As can be appreciated, it is useful in preparing the coated proppant of the present embodiment of the invention to precisely control the heat and mass balance to ensure that a cured outer coating encapsulates a still curable inner resin coating. One skilled in the art will recognize that batch size, equipment used, and resins selected will affect process conditions. Initial process temperature, process intervals, amounts of quench water added and amounts of solvent are all interrelated and may be manipulated to arrive at an optimal process. Although experimentation may be required, optimization is within the level of skill in the art.
In yet another preferred embodiment, the FCC ceramic proppant pellet is coated with a substantially cured inner resin coating and an outer resin coating which may be heat curable, fully cured, or of intermediate nature. A reinforcing agent may be interspersed at the inner resin coating/outer resin coating boundary. Suitable resins include those described above in the previous embodiment.
A key to the increased strength of the resin coated particles of this embodiment is the addition of a reinforcing agent in the boundary region between the inner and outer resin coatings. The reinforcing agents are preferably added after coating the particle with the inner resin coating but before the inner coating is cured.
Suitable reinforcing agents include materials known to act as reinforcing agents in typical engineering resins and composite materials. Common to all suitable reinforcing agents is the requirement that they be of a particle size calculated to give the required properties. For example, various mineral fillers including fumed silicas, silica four, talc, clays, mica, asbestos, calcium carbonate, calcium sulfate, metals and wollastanite are suitable. The size of such reinforcing agents is typically less than 300 mesh. Reinforcing materials of a fibrous or rod like nature should be less than about 0.006 inches and preferably about 0.002 inches in length. Of these, silica flour ground to about 325 mesh is preferred.
Another type of reinforcing agent with utility in the present invention are impact modifiers used in engineering resins and composite materials. Examples of such materials include polyisobutylene, ethylene-vinyl acetate copolymers, ethylene-propylene copolymers and other rubbery materials. Also suitable are the so-called core shell impact modifiers having a rubbery core with a graft polymerized crystalline shell. To obtain the proper particle size cryogenic grinding of the rubbery materials is useful.
In accordance with the method of the present invention, the coated or uncoated free flowing FCC ceramic proppant pellet particles produced as described above may be used as proppants, gravel or fluid loss agents in hydraulic fracturing, frac packing and gravel packs. The application will determine the choice of whether the proppant pellet is resin coated or not, and whether the coatings are cured or curable. For example, a curable coating may be indicated for gravel packing, while in fracturing a substantially cured outer coating may be preferred to prevent interaction with the frac fluid.
In carrying out a hydraulic fracturing operation, a fracture is first generated by injecting a viscous fluid into the formation at a sufficient rate and pressure to cause the formation to fail in tension. The fracturing fluid may be an oil base, water base, acid, emulsion, foam or other fluid. The fracturing fluid may contain several additives such as viscosity builders, drag reducers, fluid loss additives, corrosion inhibitors, cross linkers and the like, known in the art. Injection of the fluid is typically continued until a fracture of the desired geometry is obtained. Preferably the fracture at the well bore is at least 2.5 times the diameter of the largest proppant pellet. A carrier fluid having the proppant suspended therein is then pumped into the fracture. If the particles are resin coated with a curable resin, the temperature of the carrier fluid during pumping operations will be low so as to prevent premature curing of the outer resin coat. The carrier fluid bleeds off into the formation and deposits the proppant pellets in the fracture. The process is controlled by fluid loss agents which are small aggregate particles which temporarily slow the fluid loss to the formation.
After the proppant is placed, the well is shut in with pressure maintained on the formation. As the pressure within the fracture approaches the normal formation pressure, the fracture walls close in on the proppant and apply an overburden stress thereto. Deeper wells exert higher closure stress and require stronger proppants. Some curable resin coated proppants do not develop their full strength until the resin coating has cured in the formation. In the event of rapid closure of the fracture, the proppant could be crushed before the resin cures, resulting in decreased permeability.
When proppant pellets having an inner curable coating and an outer substantially cured coating are used, it is believed that the closure stress ruptures the outer coating exposing the curable inner coating. At the same time ambient formation temperature heats the inner resin coating. Initially, the resin fuses and unites at contact areas between contiguous particles or with the formation walls. As the temperature increases the polymerization reaction proceeds until the resin is cured into an insoluble and infusible crosslinked state. Grain to grain links are formed in pendular regions between adjacent particles and bond the packed particles into a permeable mass having considerable compressive strength.
It should now be apparent that various embodiments of the present invention accomplish the object of this invention. It should be appreciated that the present invention is not limited to the specific embodiments described above, but includes variations, modifications, and equivalent embodiments defined by the following claims.
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