Formulation, Interfaces, Rheology and Processes since 1978...
The FIRP Laboratory began its activities in 1978 to carry out applied research on Interfacial Phenomena and Oil Recovery (hence the name “FIRP”), in consultation with PDVSA in general and INTEVEP in particular, dedicating itself to issues such as improved oil recovery, transport of extra heavy crude and fuel formulation
emulsified marketed at the end of the 80s by PDVSA as “orimulsion”. At the beginning of the 90s the oriented basic research of the FIRP group made it clear that the phenomenology of emulsified systems could be described in the same way that the oil is a crude oil, an organic solvent, or lanolin, olive or linseed oil. As a consequence, it became clear that the know-how developed could be used to solve a wide variety of problems in various sectors.
Responding to the demand for support from the oil industry...
When the FIRP Lab received the award-grant from Fundacite in 1995, it was in a period of mutation and expansion both in number of members and in themes. In the late 1990s, researchers at the School of Chemical Engineering were working on other problems according to a broadening demand for industry support.
oil company, particularly in the field of drilling muds, asphalt emulsions and dehydration of crude oil. Additionally, and thanks to the incorporation of researchers from the Faculties of Pharmacy, Sciences and Medicine to the group, research began on other applications of emulsions and foams such as pharmaceuticals and cosmetics, food, paints, detergents and softeners, among others. Despite the diversification of applications and “clients”, the members of the group maintained a cohesion in terms of
concerted work methods, business-like organization and administration and interdisciplinary cooperation that was reinforced by the training of a dozen people at the doctoral level through international cooperation with centers in Europe, the USA and Japan.
Dedicated to Development and training for academics and industrialists...
In 2000 the FIRP group was an association of 25 ULA professors, of which 16 had a doctoral training and also of which 8 had industrial experience. Group activities were reorganized to gain efficiency, in particular to increase the level of dedication of researchers, to train younger staff, to generate their own income that allowed
protect the activities of the highlands of the conventional financing offered by the CDCHTA and the FONACIT, and to provide a personnel training service to both the academic and industrial sectors.
The FIRP group changed its name, and FIRP became the abbreviation for Formulation, Interfaces, Rheology and Processes, which made it possible to internationalize the name and broaden the subject, in particular to emphasize the word Formulation, which had become a field in which the laboratory was recognized nationally and internationally, and the word Processes denoting the
applied and pragmatic orientation of group policy.
Services provided by the FIRP Laboratory
During all the years of Labor we have carried out a great diversity of services, for a large number of companies and multinationals. For confidentiality reasons the client is not mentioned, nor the specific characteristics. Below are some of the services provided:
1. Formulation of a self-emulsifiable concentrate, A company had a problem in the formulation of a self-emulsifying oil concentrate for agro-industrial use (application of pesticides), in particular, because of the use of an aromatic oil, therefore a toxic oil, and because the emulsifier could not be obtained in Venezuela anymore. We reformulated a microemulsion based on a “green” oil and with surfactants and additives that were obtained in Venezuela. The company could even export their products because they are much more “friendly” for the environment.
2. Formulation of a “rolling oil”, A transnational company had stability problems with an emulsion that was used for cooling and lubrication in the lamination of hot aluminum plates. Poor lubrication was due to an irregular thickness of the sheet and the need to recycle to foundry more than 10%. We made the diagnosis of the evolution of the emulsion when applied on the hot plate (evaporation of the water, affinity change of the surfactant by change of temperature, inversion of the emulsion) and we were able to explain the problem. We gave elements to the company to modify its formulation and we formed a staff in an internship of several months, who became experts in tribochemistry of rolling oils.
3. Formulation, a product to clean wells, The oil porous media tend to clog with emulsions, foams or suspensions, particularly by the penetration of a drilling fluid, which reduces the permeability for the production of crude oil or gas. We have formulated systems to inject as a “pill” in order to reduce or eliminate capillary effects, by forming a microemulsion or achieving ultra-low interfacial tension. In some cases it has even been possible to dissolve solid particles and increase the production of a well from 500 to 10,000 barrels per day.
4. Residual fuel emulsion,
One company used orimulsion, which is 70% extra heavy oil emulsion in water, as boiler fuel. When the manufacture of this product was abandoned by PDVSA-BITOR, the company wanted to replace the product with a heavy hydrocarbon emulsion with equivalent characteristics from the operational point of view. We formulated a refining residue emulsion, and designed the emulsification conditions to achieve a substitution product with similar characteristics. Furthermore, the residual refining stream (waste) was valorized since the combustion of an emulsified system reduces the effluent problems.
5. Emulsification of a viscous resin to make a paint (alkyd with one company, polyurethane with another, and manufacture of a polydimetil solixano-silicon mastic with a third one),
Polymer resins used in paints or mastics are often extremely viscous and the manufacture of an emulsified paint with adequate droplet size (a few microns) cannot be done by very energetic agitation for technical and cost issues. It is necessary to carry out a phase inversion process, which is a physicochemical and hydrodynamic instability that propagates by introducing a small amount of water in a tank of viscous resin, and stiring slowly for several hours, until inversion conditions are achieved. In 20% of the cases the final product was not satisfactory, which represented a considerable cost of products out of specification. Our know-how accumulated during the last 10 years in terms of inversion of abnormal emulsions and on the influence of the formulation, the composition and the emulsification protocol, allowed us to recommend changes in the process and the installation of controls that allowed reducing considerably the batchs out of specification.
6. Adjustment of a product with undesirable characteristics, Over time certain formulated products tend to produce precipitates, others tend to lose their homogeneity and to separate into several phases, or to change color. This happens in particular when its formulation had to be changed to adapt it to the availability of a new raw material. Eliminating precipitate formation, phase separation, or color change, usually requires making a diagnosis about what is producing it. It can be a chemical reaction, an incompatibility between substances of the product, or an insufficient stabilization of the dispersion. Then the product must be reformulated accordingly to obtain a similar property without the inconvenience detected. We have solved numerous problems of this type, among others a transparent shampoo that became opaque, a cleaning liquid that produced a precipitate, a paint that formed lumps, a food sauce that lost its viscosity.
7. Formulation of a stable emulsion, We have often helped companies to increase the stability of an emulsion, or to control the size of the drops. This has been the case of parenteral emulsions in which there should not be drops larger than microns, of asphalt emulsions that must be stable in the cask but break quickly in contact with the rock aggregate, of nanoemulsions for veterinary vaccines or cosmetic creams, or emulsified paints whose rheology must be well controlled. It has also been the case of a nanoemulsion to disperse nutrients (vegetable triglyceride oils) in fermentation media for the production of antibiotics, in which case the emulsion should not have a strong antifoam action.
8. Wettability setting, We have treated various types of materials to change their surface wettability by adsorption. For example, lignite is an organic material that can be considered as a medium matured coal. To be used as a viscosifying element in the form of suspension or suspoemulsion it must follow a surface treatment to render it wettable to water or oil as the case may be. The bottle transport chains in a bottling plant should be lubricated, but of course not with oil that would contaminate the bottles; in fact, it is done with a thin hydrophobic adsorbed layer. The dust that flies everywhere in a mining exploitation can be controlled by producing its agglomeration, or by changing its wettability or surface charge.
9. Use of pulp residue, The black pulp liquors contain substances derived from lignin which are potential dispersing agents of emulsions, suspensions and foams. We have carried out studies for an oil company and several paper companies to adapt the pulp residues of the latter to their desirable characteristics as dispersing agents for drilling fluids or emulsifiers. Another study has shown that products obtained by modification of lignin may possess adequate properties.
10. Formulation adjustment to break emulsions or foams, In certain cases, it is desired to break emulsions and separate the water from the oil. Achieving the physicochemical conditions for an emulsion or foam to be unstable requires first a diagnosis, and then the design of an additive that counteracts stabilization. We have solved this type of problem in many instances. For example, several service companies that sell demulsifiers for crude oil and that must adjust a formula for a very well defined segregation; or when a polyelectrolyte additive must be dosed to produce the flocculation of undesirable materials (oils, proteins) in aqueous effluents. We are not limited to formulation; we also offer process design, for we have chemical engineers and an expert team that works with micro, ultra or nanofiltration membranes.
11. Formulation of specials foams / detergents, soaps or cleaning detergents have been modified and formulated for special uses such as those containing aseptic or bactericidal products and are used in hospitals, to clean food sales carts in the street or for domestic applications.
12. Characterization of oil production waters, After the process of dehydration in the oil industry it is necessary to dispose of the waters that have been separated in this process. In many cases the waters are reinjected into other abandoned wells. These waters must have some special characteristics so that they do not block the formation in which they are injected. That is why they should be characterized in terms of particle size distribution of both crude and solids, density of solids, suspended solids and dissolved solids.
Pillars of FIRP Laboratory
It can be said that at present the FIRP Lab is an association of more than two dozen professors (half with doctorates) who work in various physical environments in an independent and concerted way, to attend to various activities:
1. Applied research and development, that is carried out via contracts through the Technological Advisory and Innovation Unit of the Faculty of Engineering (UAPIT-ULA) or directly as laboratory projects, and that allows to put the accumulated know-how at the service of the oil industrial sector, not only PDVSA but also associated SMEs (formulation of dehydrants, viscosity reducers, emulsified transport, catalytic emulsions, drilling muds) and non-oil (water-based alkyd paints, self-emulsifying insecticides, anti-cellulite cosmetic cream, sun cream, pastes dental, rolling and cutting oils, remediation of environmental problems, etc). This activity occupies approximately 50% of the time of our researchers and allows us to provide a unique technological service in the country, generate our own income, involve our training staff and postgraduate students in “realistic” work and give them a “practical” training. that increases its potential to solve problems in the productive sector, particularly locally or nationally.
2. Fundamental research, whose objective is the creation of knowledge, which allows training relief personnel and postgraduate students, advance in the understanding of the phenomena that are handled in the previous activity, produce publications and disseminate organized knowledge. In general, fundamental research topics are oriented to applied research problems that are confronted in solution development projects. This activity occupies approximately 30% of the time of our researchers and in addition to reinforcing our knowledge and consolidating our scientific competence, it contributes to making the group known nationally and internationally, and to meeting the requirements of the postgraduate diplomas of the staff in training, and publication requirements for various purposes (PPI, PEI, project reports).
3. Training of personnel at multiple levels:
▪ First, through the delivery of conventional undergraduate and postgraduate courses at the ULA and other national universities and abroad through cooperation agreements.
▪ Second, by offering a variety of technical courses and trainings for employees of the public and private productive sector, with a balance of more than 2000 people served in the last 10 years, in particular with unique programs such as one-week extension courses. (more than 100 courses in the last 10 years), or the one called PPEQ (Chemical Specialties Pilot Project to train in 11 months expert formulators for the SME sector that provides service to PDVSA in order to increase the response capacity of this sector).
▪ Tercero, mediante la formación por y para la investigación, a nivel de postgrado del personal joven del propio grupo, y de grupos asociados en ULA y otras universidades nacionales. En los últimos 10 años se atendieron unas 60 tesis de pregrado, 20 de Maestría y 10 de doctorado. El propósito actual, después de ayudar a la creación de un grupo de Separaciones por Membranas en ULA y otro de Petroquímica y Surfactantes en LUZ, es consolidar la creación de un grupo de Sistemas Dispersos y Ambiente en la UDO, y otro de Fenómenos Interfaciales en la USB, y de apoyar la creación y consolidación de un grupo de Polímeros y Coloides en la ULA y otro de Asfaltenos y Surfactantes Naturales en la UC.
▪ Third, through training by and for research, at the postgraduate level, of the young staff of the group itself, and of associated groups at ULA and other national universities. In the last 10 years, some 60 undergraduate, 20 master’s and 10 doctoral theses have been attended. The current purpose, after helping to create a group for Membrane Separations at ULA and another for Petrochemicals and Surfactants at LUZ, is to consolidate the creation of a group for Dispersed Systems and Environment at UDO, and another for Interfacial Phenomena in the USB, and to support the creation and consolidation of a group of Polymers and Colloids at the ULA and another for Asphaltenes and Natural Surfactants at the UC.
4. Development of apparatus for scientific equipment, thanks to a close collaboration with CITEC-ULA, and supported by FONACIT through applied and pragmatic projects such as the Petroleum Agenda. 4 pieces of equipment were developed (rotating drop tensiometer, electrostatic dehydrator, ball drop rheometer, high pressure and high temperature foam column), among which the first two reached the commercial stage and are available for academic and productive sectors at a cost of the order of 50% of the international market.
Our First Seminar Course
In commemoration of our thirty-third anniversary (already a 1/3 of a century!), Here we recall the notes of a seminar held on November 3, 1978.