This agricultural device introduces an innovative approach to soil treatment that restores the fertility of depleted soils, which currently depend on chemical fertilizers to keep up with global food production needs. The new technology is based upon the concept of bioenergetics, whereby soil is conceived as the main factor that needs to be balanced in order to increase natural soil fertility, crop production, and food quality. This scientifically-based farming technology utilizes horizontal tillage—as opposed to conventional tillage—to reduce the entropy of the soil-plant-atmosphere system, helping regenerate biological memory and natural soil fertility. This new technology has been successfully tested on various kinds of terrains and crops, and its application progressively turns nature into the main factor of production equation, allowing us to reduce agrochemical dependency and production costs, and allowing us to overcome the apparent dichotomy that now exists between high food production needs and environmental care.

The present invention is directed to an agricultural device that restores soil fertility. This innovation is based on a scientific concept that considers the entropic and bioenergetic balance as basic components of an advanced model of sustainable agricultural production which helps to feed the growing world population, in harmony with the environment. It is a new technology system consisting of a set of devices and methods for the ecological treatment of the soil, which has been proven in practice.
One of the most surprising mistakes we made in the history of mankind is not having understood quickly enough, the predominant role of entropy in the degradation and depletion of our soil.
The solution to the economic, energy and environmental crisis facing humanity is linked to the understanding of the connection at thermodynamic and quantum level, between economic growth, the increase of entropy, as well as, the regeneration processes of life and of raw materials in the soil-plant-atmospheric interactive system.
Entropy is a thermodynamic property whose formula is: S=Q/T, where S is the entropy, expressed in Kcal/K, the amount of heat Q exchanged Kcal and T the absolute temperature in degrees Kelvin at which heat is transferred.
Entropy is a measure of the amount of energy which is degraded in the form of heat and can never recover its ability to generate useful work. Soil richness and entropy vary inversely, so that when one increases the other decreases.
Man has tried to compensate the increase in the entropy of the soil by increasing the amount of chemical fertilizers applied. This technique is only a short-term solution, but in reality it only delays and worsens the problem supposedly intended to solve.
Soil is one of the most powerful forces of nature known to man, for it is where the mineral content is transformed into biological material. It is a primary force of nature with ability to transform the world.
Soil is a system whose components are minerals and living organisms, in which we find the key that determines the planet's ability to produce energy, food and raw materials necessary to sustain life.
This occurs by the transformation, at the ambient temperature and pressure, of the solar radiation, minerals and water, in biological energy.
Biological systems of land and sea are intimately connected and, through photosynthesis of plants, are the ones who have the ability to transform the electromagnetic waves from the sun into usable biological energy, all of which occur through natural processes highly efficient energy transfer in a quantum dimension.
When biological systems degrade and fail, the planet is disconnected, discharged and lose their ability to process and store energy from the sun, becoming an increasingly poorer place because of the increase of entropy.
Connectivity is a basic component of the structure of living systems. But when it is altered and degraded, it changes patterns of energy transport and feedback recycling operation, causing a kind of heat death of the system. This is what occurs in soils that lose their biological components, leaving only an inert substrate and becomes dependent on an external artificial source for operation.
The energy on the soil is passed from one to another living species, which act as transmission wires and transformers to ensure the biological process of energy recharge the planet, but the technologies used by conventional agriculture are destroying the biological capacity of the soil, which gradually becomes an empty, sterile container, which depends almost exclusively on the agrochemicals. Empty soils produce "empty foods" that become the hidden cause of many diseases.
The true potential of the soil fertility is not in its content of chemical elements, much less on the fallacy that the amount of fertilizer applied, but in its entropic ability to process and store energy.
Every year, worldwide, tens of millions of tons of fertilizer applied to agricultural soils in an attempt to increase their fertility. However, every day the world's soils are poorer and more dependent on chemicals, and as a result it is increasingly more costly to produce less. Note, that in order to produce each ton of nitrogen fertilizer over a ton and a half of oil equivalent needs to be consumed.
The enormous economic growth that mankind has achieved has taken place at the expense of the depletion of oil and other nonrenewable fossil fuels, which were formed by nature, from photosynthetic and microbiological processes of plants that lived millions of years ago.
As fossil fuels and other raw materials that we inherit from nature are exhausted, we are entering a new era in which economic growth will become more dependent on what we achieve in the farm fields.
Sustainable growth and future economic development cannot be achieved with solutions and raw materials of the past.
We must move from a model of economic growth based on the processing and consumption of existing raw materials to a model of economic growth based on technologies regeneration and transformation of new raw materials, where the soil will become the first link in productive chains and the main source of wealth.
Since 1934 Henry Ford could envision a future where essential fuels and raw materials for industrial development would be produced in the farmland and prophetic words of wisdom he declared as follows:
"I foresee the time when industry shall no longer denude the forests which require generations to mature, nor use up the mines which were ages in the making, but shall draw its raw material largely from the annual products of the fields. I am convinced that we shall be able to get out of the yearly crops most of the basic materials which we now get from forest and mine [Modern Mechanix (1934)]."
In soils of Amazonia, despite being regarded as low fertility, the lush green landscape of the planet was formed, without a single gram of fertilizer. However, when these soils are subjected to conventional agricultural management technologies they rapidly degrade and lose their productive capacities.
Stated in other words, is not a problem of lack of chemical fertilizers, it is a problem of biophysical and thermodynamic processes, which are regenerated by restoring energy balanceand entropy in the ground.
Plant nutrition is not as simple as the application and absorption of nutrients; it is a quantum interactive process of exchange of matter, energy and genomic information between plants and all living species that inhabit in the biosphere.
During my 40 years of research, I have been upgrading my technology based upon my discovery of an ecological method by which the entropy is reduced and the richness of the earth is regenerated. It is based on the disconnection and connection of the soil layers through which the anisotropic stratification is induced, which is essential to regenerate natural gradients of life and soil fertility, all of which allows capture and storage of energy and the reduction of entropy in the biosphere.
I found a way to achieve this by cutting the soil transversely to the force of gravity and the prevailing direction of the flow of energy on earth.
I designed a set of Aerodynamic Cutting Device (ACD), (FIG. 1, FIG. 2.1-2.4) to implement and structure in the most efficient way, an entropic system of sustainable agricultural technologies, all of which is the subject of the present invention.
The second law of thermodynamics states that energy always flows from a system or layer with high energy density to another system or layer with a lower energy density. This law is essential to the functioning of life in the soil and other components of the biosphere.
The impact of new technology in the induction of the formation of layers with different Bioenergetic density (anisotropic stratification), is the key to reducing the entropy, and regenerate the life and fertility of soils.
This method allows to gradually overcoming the serious disadvantage of conventional technologies, which depend on the increasing use of chemicals in food production, biofuels and other products that are essential to modern society. Through implementation and understanding of biological, quantum and thermodynamic principles behind it, unprecedented technological change will occur in the world's agricultural production.
The scientific basis and technological solution of the present invention are based on a revolutionary concept that recognizes thermodynamics and quantum nature of the biophysical processes involved in soil fertility, the productive potential of the land, and the entropy balance of the soil-plant-atmospheric system. It allows progressively reduction of dependence on agrochemicals in the production of food, biofuels and other commodities essential to the economy. The new technologies have been successfully tested in practice, and are comprised of a set of devices and methods for ecological soil treatment, which are able to reduce the entropy of the soil, by regulating the magnitude and intensity of propagation of energy through its layers. This is achieved by an Aerodynamic Cutting Device (ACD) which cuts the soil layers transversely to the force of gravity and the predominant direction of energy flow directions, which causes a cyclical process of disconnection and reconnection of the layers, and induce stratification and anisotropy indispensable to regenerate natural gradients of life and fertility in the soil. The system is further comprised of a novel Mechanism of Protection Against Obstacles (PMO) with automatic reverse, and a Versatile Agricultural Device (VAD) for multiple agricultural tasks, as well as, new more efficient Assembly Regulation, and shank Positioning Mechanism (ARPM), adjustable set up depending on task to be perform and arrangement of shanks, and the Integral Coupling Mechanism (ICM) to different types of tractors.

Agricultural device for restoring soil fertility


Provided is a method and system for reliably multicasting a data transmission from a server to one or more clients, which may be connected via a control channel and a multicast data channel. In one example, the method includes sending a first data transmission to the clients over the multicast data channel. A response is received over the control channel from at least some of the clients. The response identifies data not received by the responding client. In some examples, the response may indicate that all the data was received. The server determines a minimum retransmission data set based on the responses. The minimum retransmission data set includes at least some of the data not received by the client during the first data transmission. The minimum retransmission data set is sent over the multicast data channel and received by the clients that did not receive it during the first data transmission.

This disclosure relates generally to multicast data transmission and, more specifically, to a method and a system for ensuring complete transmission of multicast files with minimum retransmissions.
A computer network generally has at least one computer (a server) that provides services to other computers (clients) via the network. Traditionally, network communications have employed a unicast transmission model in which a separate connection is made between a server and each of its clients. This model works particularly well when each client has unique demands of the server. However, when each client is receiving the same data, multiple copies of the same information packet can flood the network, causing congestion and escalating bandwidth requirements.
Multicasting may alleviate some of the problems associated with unicasting by enabling a server to transmit a single packet of information that may be received by multiple clients who have requested the information. Multicast enabled switches and routers permit the single packet of information to be copied so that only a single packet need be forwarded through each branch of the network to reach the clients requesting the information. Although multicasting may be used in a wide variety of applications in which large amounts of information are being sent to multiple clients, multicasting generally used for applications in which many clients want the identical data simultaneously. Such applications may include live audio or video transmissions, multi-user games, and real-time stock tickers.
Despite the benefits of multicasting for some applications, present implementations of multicasting do not enable a server to receive performance information back from clients, and therefore, transmission reliability may be sacrificed. Current methods of multicasting may also result in unrecoverable data loss.
Therefore, what is needed is an improved method and a system for the complete transmission of multicast files. It is also desirable to maintain efficiency by minimizing retransmissions.

Method and system for reliable multicast data transmission


A portable support system having a portable support having a first end and a second end. The first end includes a tapered portion, and the second end includes a footing structure. The system also includes a receiving member having a support cone configured to receive the tapered portion. The support cone has a tapered inner surface and a tapered outer surface. The inner surface and outer surface are engagable with mating tapered surfaces. The receiving member is capable of attachment to one or both of a frame and a panel for use as a platform.

Portable structures, such as stages or platforms, must be capable of being assembled and disassembled into relatively small units that can be compactly and quickly loaded onto trucks or airplanes for transport. The portable structures must be capable of being assembled and disassembled by personnel with little or no technical skill. The portable structures support a large amount of weight and are subjected to external conditions, lateral forces, loud vibrations, and substantial wear.
The portable structures are generally comprised of systems of primary and secondary supports that provide the necessary stability. These systems are often comprised of supports requiring use of tools, such as wrenches and screwdrivers, to assemble and disassemble the portable structures. Locking mechanisms for supports have been used; however, they are difficult to assemble and disassemble, subject to misalignment, require a plurality of pieces, require tools for certain adjustments, do not offer adequate stability, do not have easily replaceable parts, and do not work well in conjunction with other parts of the portable structures.
Portable structures typically used in the art include those structures that have perpendicular members extending from the platform, which are attached at the joints between decking members. The structures known in the art suffer from the drawback that they are cumbersome to assemble, subject to misalignment, causing instability in the structure, and are subject to lateral forces during use.
What is needed is a portable support and a platform system that are easily assembled and disassembled with little or no technical skill, is not substantially subject to misalignment, requires few pieces, can be substantially assembled and disassembled by hand, offers the necessary stability, has replaceable parts, and works in conjunction with the other parts of the portable structure.

Portable locking support and platform system


An apparatus including a basis that has a plurality of wells associated therewith for defining a plurality of electrochemical cells; at least two electrodes sealingly disposed in each electrochemical cell; and circuitry for providing an electrical connection between an electrical source and each said cell. A particularly preferred apparatus employs at least one printed circuit board secured to the base. In a preferred method, candidate materials are introduced into the apparatus and their respective performances are analyzed.

The present invention relates to the high throughput synthesis and characterization of materials for electrochemical cells.
The search for improved electrochemical performance has stimulated research into improved materials for use in such applications. One approach to such research is addressed in commonly owned U.S. Pat. No. 6,187,164 (Warren et al; issued Feb. 13, 2001), hereby incorporated by reference. Another approach is addressed in PCT WO 00/77279 (Published Dec. 21, 2000), also incorporated by reference. The advances achievable through the above disclosures have stimulated further investigation into the development of additional high throughput techniques for performing electrochemical performance research.
The present invention provides yet another attractive high-throughput approach to electrochemical performance research. The invention is premised upon the discovery of an improved apparatus and methodology for defining electrochemical cells, pursuant to which many different electrolyte materials, electrode materials, electrochemical additives, current densities, catalysts, or the like may be the subject of high-throughput experimentation. The present invention advantageously may be employed to synthesize libraries of materials, to characterize libraries of materials or both.
In general, the apparatus of the present invention includes a base including a plurality of wells associated therewith for defining a plurality of electrochemical cells; at least two electrodes sealingly disposed in each electrochemical cell; and circuitry for providing an electrical connection between an electrical source and each said cell. A particularly preferred apparatus employs at least one printed circuit board secured to the base. In a preferred method, candidate materials are introduced into the apparatus and their respective performances are analyzed.

Synthesis and characterization of materials for electrochemical cells


An inhibitor mixture containing, as components, a) at least one nitroxyl radical (derivative), b) at least one phenol (derivative) and c) at least one chemical compound which contains at least one phosphorus atom which has the oxidation state +3 is preferably used for stabilizing compounds capable of free radical polymerization.

The present invention relates to an inhibitor composition and its use for stabilizing substances capable of free radical polymerization, and a mixture containing the inhibitor composition.
Many compounds which have one or more vinylically unsaturated groups have a pronounced tendency to free radical polymerization. Such compounds are also used specifically as monomers for free radical polymerization. At the same time, however, the pronounced tendency to free radical polymerization is a disadvantage in that undesired free radical polymerization of the vinylically unsaturated compounds can occur both during storage and during chemical and/or physical processing (for example distillation or rectification), in particular under the action of heat and/or light. Undesired free radical polymerization can have various adverse effects, especially if polymer is precipitated. For example, in the distillation of vinylically unsaturated compounds, polymer formed by free radical polymerization may be deposited on the surface of the evaporator usedxe2x80x94the tendency to free radical polymerization is particularly pronounced there owing to the high temperature. Polymerization in the region of the surface of an evaporator generally means that a polymer layer forms on the surface. Owing to the insulating effect of the polymer layer, the heat transfer is reduced in an undesired manner. Undesired polymer formed by free radical polymerization can, however, also block the internals of rectification columns, which causes undesired pressure drops. The deposition of polymer may finally necessitate stoppage of the rectification process, since the deposited polymer has to be removed in order to continue the rectification.
It is therefore general practice to add compounds which act as inhibitors or retarders of free radical polymerization to vinylically unsaturated compounds capable of free radical polymerization and mixtures which contain such compounds. While inhibitors suppress the free radical polymerization, including their complete reaction with free radicals, retarders slow down the free radical polymerization. Inhibitors and retarders are generally combined under the general term stabilizers. Below, however, both inhibitors and retarders are to be understood as meaning inhibitors. The use of inhibitors or retarders is of importance both during storage and during chemical and/or physical treatment (for example in distillation) of vinylically unsaturated compounds capable of free radical polymerization.
U.S. Pat. No. 4,187,382 relates to a process for the esterification of organic diols with acrylic acid. It is recommended to pretreat the diol with triphenyl phosphite in order thus to reduce the tendency of the reaction mixture to free radical polymerization. A phenolic polymerization inhibitor is proposed as a further inhibiting component.
DE-A 29 13 218 discloses a process for the preparation of acrylates or methacrylates, in which the polymerization inhibitor used comprises organic phosphites together with phenolic polymerization inhibitors.
The abovementioned inhibitor compositions contain phosphorus compounds which have phosphorus in the oxidation state +3 and further phenolic compounds. One object is further to improve the action of such systems in the stabilization of vinylically unsaturated compounds.
It is an object of the present invention to provide a highly active inhibitor composition which contains chemical compounds having phosphorus in the oxidation state +3 and/or phenolic compounds. This inhibitor composition should be particularly effective in that the inhibiting effects of the components present in it should reinforce one another in a synergistic manner.
We have found that this object is achieved by providing an inhibitor composition containing, as components, a) at least one nitroxyl radical (derivative), b) at least one phenol (derivative) and c) at least one further chemical compound which contains at least one phosphorus atom which has the oxidation state +3.
The oxidation state of an atom within a covalent compound is to be understood as meaning a number which has a positive or negative sign and indicates the charge which the atom would have if the bonding electron pairs of the covalent bonds in which the atom participates were assigned to the more electronegative bonding partner in each case. In the case of electron pairs of covalent bonds between two identical atoms, each atom contains one electron. The electronegativity is to be regarded here as a measure of how strongly an atom in a molecule attracts bonding electron pairs which are bonded to the atom. The electronegativities relevant at present are those according to H. R. Christen, Grundlagen der allgemeinen und anorganishcen Chemie, Verlag Sauerlxc3xa4nder, Aarau, Diesterweg-Salle, Frankfurt am Main (1973). For the most important elements of the Periodic Table, these electronegativities have the following values:
Be (1.5); B (2.0); H (2.1); C (2.5); Si (1.8); Ge (1.7); N (3.0); P (2.1); As (2.0); Sb (1.8); O (3.5); S (2.5); Se (2.4); Te (2.1); F (4.0); Cl (3.0); Br (2.8); I (2.4).
In particular, orthophosphorous acid or an ester of orthophosphorous acid may be used as compounds (component c)) which contain at least one phosphorus atom having the oxidation state +3. Esters of orthophosphorous acid are also referred to as phosphites. Orthophosphorous acid can also be present as a salt (generally as an alkali metal or ammonium salt). Preferred bonding partners of phosphorus are the elements C, S, O, N and/or H.
Phosphonites (esters of phosphonous acid), in particular those known as stabilizers, are also suitable.
Particularly suitable phosphites (i.e. the esters of orthophosphorous acid) and phosphonites (esters of phosphonous acid) include, for example, triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythrityl, diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythrityl diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythrityl diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythrityl diphosphite, diisodecyloxypentaerythrityl diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythrityl diphosphite, bis(2,4,6-tris(tert-butylphenyl)) pentaerythrityl diphosphite, tristearyl sorbityl triphosphite, tetrakis(2,4-di-tert-butyl-phenyl) 4,4xe2x80x2-biphenylene diphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4xe2x80x2-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphosphocine, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite and bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite.
Esters of orthophosphorous acid (phosphites) of the formula (I) or esters of phosphonous acid (phosphonites) of the formula (II)
are advantageously used,
where R, Rxe2x80x2 and Rxe2x80x3 may be identical or different and are organic radicals, in particular C1-C20-alkyl, hydroxy-C2-C4-alkyl, halo-C2-C4-alkyl, in particular chloroalkyl, C6-C10-aryl, in particular phenyl, or C1-C8-alkyl-substituted aryl (in particular C1-C4-alkyl-substituted phenyl). Furthermore, two of the three organic radicals R, Rxe2x80x2 and Rxe2x80x3, together with the phosphorus and the two oxygen atoms, may form a heterocyclic structure (for example having 5 or 6 atoms).
Trimethyl, triethyl, tributyl, trihexyl, trioctyl, triphenyl, tri-p-cresyl, trixylyl, tritolyl and tri-xcex2-chloroethyl phosphite may be mentioned by name. However, dimethyl, diethyl, dibutyl, dioctyl, diphenyl, ditolyl and dixylyl phosphite are also inhibitors suitable according to the invention. Particularly suitable are the species known under the trade names Irgafos(copyright) 168 (producer Ciba AG), Irgafos(copyright) P-EPQ (producer Ciba AG) or Ultranox(copyright) 626 (producer GE-Speciality Chemicals GmbH):
Other suitable chemical compounds which contain at least one phosphorus atom which has the oxidation state +3 are the derivatives of phosphonous acid R*xe2x80x94P(OH)2, where R* is alkyl (preferably C1- to C8-alkyl) or aryl, in particular C6-C10-aryl (preferably phenyl), and the derivatives of phosphonous acid of the formula (III)
where R** is independent of R*, and R* and R** are each alkyl (preferably C1- to C20-alkyl) or aryl, in particular C6-C10-aryl (preferably phenyl).
Derivatives of the oxygen-containing phosphorus compounds described above which contain at least one phosphorus atom having the oxidation state +3 and in which one or more O atoms have been replaced by S or NR* (R* has the same meanings as those mentioned above) are also suitable.
In addition to one or more chemical compounds which contain at least one phosphorus atom having the oxidation state +3, the inhibitor composition according to the invention contains, inter alia, as further component (further inhibitor component), at least one nitroxyl radical (derivative) as component a).
A preferably used nitroxyl radical (derivative) is 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine.
According to the invention, suitable nitroxyl radical (derivatives) (also referred to as N-oxyl radicals) are in principle all compounds which have at least one  greater than Nxe2x80x94Oxe2x80xa2 group. The nitroxyl radical (derivatives) may also be produced in situ from other compounds, for example by H abstraction from hydroxylamines or by an addition reaction of C radicals with nitrones. However, they can also be produced in situ from aromatic amines which are derived from aniline or phenylenediamine. Nitroxyl radical (derivatives) suitable according to the invention are in particular those which are derived from a secondary amine which carries no hydrogen atoms on the xcex1-carbon atoms (i.e. the N-oxyl groups are derived from corresponding secondary amino groups).
Such suitable, stable nitroxyl radical (derivatives) derived from a secondary amine are, for example, those of the formula (IV)
where
R1, R2, R5 and R6 are identical or different straight-chain or branched, unsubstituted or substituted alkyl groups and
R3 and R4 are identical or different straight-chain or branched, unsubstituted or substituted alkyl groups or
R3CNCR4 is an unsubstituted or substituted cyclic structure.
Examples of suitable compounds are those stable nitroxyl radical (derivatives) of the formula (IV) in which R1, R2, R5 and R6 are (identical or different) C1- to C4-alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, linear or branched pentyl, phenyl or substituted groups thereof and R3 and R4 are (identical or different) C1- to C4-alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, linear or branched pentyl or substituted groups thereof or, together with CNC, are the cyclic structure
where n is an integer from 1 to 10 (frequently from 1 to 6), including substituted cyclic structures of this type. Typical examples are 2,2,6,6-tetramethyl-1-oxylpiperidine, 2,2,5,5-tetramethyl-1-oxylpyrrolidine and 4-oxo-2,2,6,6-tetramethyl-1-oxylpiperidine.
The N-oxyl radical (derivatives) of the formula (IV) can be prepared from the corresponding secondary amines by oxidation, for example with hydrogen peroxide. As a rule, they can be prepared as a pure substance.
The nitroxyl radical (derivatives) suitable according to the invention include in particular piperidin- or pyrrolidin-N-oxyls and di-N-oxyls of the following formulae (V) to (XII):
where
m is from 2 to 10,
-R7, -R8 and -R9, independently of one another, are each
M⊕ is a hydrogen or an alkali metal ion,
q is an integer from 1 to 10,
R1xe2x80x2, R2xe2x80x2, R5xe2x80x2 and R6xe2x80x2, independently of one another and independently of R1, R2, R5 and R6, are the same groups as R1,
R10 is C1- to C4-alkyl, xe2x80x94CHxe2x95x90CH2, xe2x80x94Cxe2x89xa1CH, xe2x80x94CN,
R11 is an organic radical which has at least one primary, secondary (e.g. xe2x80x94NHR1) or tertiary amino group (e.g. xe2x80x94NR1R2) or at least one ammonium group xe2x80x94N⊕R14R15R16X∪, where X∪ is F∪, Cl∪, Br∪, HSO4∪, SO42∪, H2PO4∪, HPO42∪ or PO43∪ and R14, R15 and R16 are independent organic radicals (e.g. independently of one another and independently of R1, the same groups as R1),
R12, independently of R11, has the same meanings as R11 or is xe2x80x94H, xe2x80x94OH, C1- to C4-alkyl, COO∪M⊕,mxe2x80x94Cxe2x89xa1CH,
xe2x80x83or hydroxyl-substituted C1- to C4-alkyl (e.g. hydroxyethyl or hydroxypropyl) or
R11 and R12 together are the oxygen of a carbonyl group and
Preferably, R1=R2=R5=R6=R1xe2x80x2=R2xe2x80x2=R5xe2x80x2=R6xe2x80x2=xe2x80x94CH3.
Typical examples of N-oxyl radical (derivatives) suitable according to the invention are 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 1-oxyl-2,2,6,6-tetramethyl-4-methoxypiperidine, 1-oxyl-2,2,6,6-tetramethyl-4-ethoxypiperidine, 1-oxyl-2,2,6,6-tetramethyl-4-trimethylsilyloxypiperidine, 1-oxyl-2,2,6,6-tetramethyl-piperidin-4-one, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 2-ethylhexanoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl benzoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl (4-tert-butyl)benzoate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) n-butylmalonate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N,Nxe2x80x2-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)adipamide, N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)caprolactam, N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)dodecylsuccinimide, 2,4,6-tris[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl]-s-triazine, N,Nxe2x80x2-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)-N,Nxe2x80x2-bisformyl-1,6-diaminohexane, 4,4xe2x80x2-ethylenebis(1-oxyl-2,2,6,6-tetramethylpiperazin-3-one) and tris(2,2,6,6-tetramethyl-1-oxylpiperidin-4-yl) phosphite and additionally 1-oxyl-2,2,6,6-tetramethyl-1,2,3,6-tetrahydropyridine.
Further suitable typical examples (in the corresponding structural formulae, H atoms are not shown) are:
According to the invention, mixtures of N-oxyl radical (derivatives) can of course also be used.
The inhibitor composition also contains at least one phenol (derivative) (phenol as such is also suitable as phenol derivative) as a further componentxe2x80x94component b). A preferably used phenol derivative is a phenol or cresol in which one or more hydrogen atoms have been substituted by tert-butyl groups, in particular 2,6-di-tert-butylcresol, or hydroquinones, in particular hydroquinone monomethyl ethers. Phenols or cresols in which one or more hydrogen atoms have been substituted by isopropyl groups, such as thymol or carvacrol, are also suitable. Pyrocatechol and its derivatives and resorcinol and its derivatives are also suitable. As described above, suitable dihydric phenols are also hydroquinone and its derivatives, in particular ethers of hydroquinone, such as hydroquinone monomethyl ether. Naphthols, such as xcex1-naphthol and vitamin E are also suitable. Moreover, phenols which are linked to one another via alkyl bridges, such as bisphenol A, are also suitable. In general, suitable phenol derivatives are compounds which can form an oxyl radical which is bonded to an aromatic system. This is effected by homolytic cleavage of an oxygen-hydrogen bond, the oxygen atom being bonded to an aromatic system. Particularly preferred phenol derivatives are of the following structural formula (XIII):
Here, R1, R2, R3, R4 and R5 are identical or different and are each H, halogen, C1- to C20-alkyl or aryl, SO3H, SO3xe2x88x92M+, OH, SH, O-alkyl, O-aryl, S-alkyl, S-aryl, NH-alkyl, NH-aryl, NO, NO2, NHxe2x80x94OH, NH2, COOH, CN, Oxe2x80x94COxe2x80x94R6, Oxe2x80x94COxe2x80x94Oxe2x80x94R6, NHxe2x80x94COxe2x80x94R6, CN(xe2x80x94OH)xe2x80x94(R6), COxe2x80x94Oxe2x80x94R6 or COxe2x80x94NHxe2x80x94R6, where R6 is H, halogen, C1- to C20-alkyl or aryl, SO3H, SO3xe2x88x92M+, OH, SH, O-alkyl, O-aryl, S-alkyl, S-aryl, NH-alkyl, NH-aryl, NO, NO2, NHxe2x80x94OH, NH2, COOH or CN.
The inhibitor composition containing one or more chemical compounds which contain at least one phosphorus atom having the oxidation state +3, and one or more nitroxyl radical (derivatives) and one or more phenol (derivatives) has a particularly good stabilizing effect. Regarding the effect as inhibitor in free radical polymerization, the novel inhibitor composition has synergistic propertiesxe2x80x94species of the three different inhibitor components reinforce one another in their inhibiting effect. Accordingly, the inhibiting effect of the novel composition is better than the inhibiting effect which would be present, for example, in the presence of the individual components alone or as the sum of the individual effects.
It is advantageous that the novel inhibitor composition also displays its activity in the presence of molecular oxygen.
Particularly suitable inhibitor compositions are to be discussed below. Components which are contained in these inhibitor compositions are shown in the Table belowxe2x80x94the combination of the following components proves particularly advantageous:
The particular advantage of the novel inhibitor compositionxe2x80x94the xe2x80x9cthree-component combinationxe2x80x9dxe2x80x94is that overall only a small amount of inhibitor is required.
In rectification and distillation processes, comparatively less polymer is deposited if the novel inhibitor system is used, so that the corresponding plants have to be shut down less frequently for cleaning work. Moreover, the inhibitor system having a synergistic effect ensures that a smaller amount of monomer is consumed by polymerization and thus lost.
Of course, the inhibitor composition may also contain further components inhibiting free radical polymerization, in addition to the inhibitors describedxe2x80x94phosphorus compounds, nitroxyl radical (derivatives) and phenol (derivatives). Examples of such other free radical polymerization inhibitors are organic nitroso compounds, such as N-nitrosoarylamines. These inhibitor compositions also have activity in the presence of molecular oxygen.
The inhibitor compositions are used in accordance with the invention for the stabilization of pure substances which have at least one vinylically unsaturated group or of mixtures which contain at least one substance which has at least one vinylically unsaturated group. The inhibitor composition is also effected in the presence of oxygen.
According to the invention, a mixture containing at least one compound which has at least one vinylically unsaturated group and a novel inhibitor composition is also provided.
The mixture contains, as a rule, one or more chemical compounds which contain at least one phosphorus atom having the oxidation state +3, in a total concentration of from 1 to 5000 ppm, preferably from 5 to 1000 ppm, and one or more nitroxyl radical (derivatives) in a total concentration of from 1 to 3000 ppm, preferably from 5 to 300 ppm, and one or more phenol derivatives in a total concentration of from 1 to 3000 ppm, preferably from 5 to 1500 ppm.
Compounds which have at least one vinylically unsaturated group are to be understood as meaning in particular those capable of free radical homo- and/or copolymerization. These are, for example, olefins, such as isobutene, ethylene or propylene, vinylaromatic monomers, such as styrene, xcex1-methylstyrene, o-chlorostyrene or vinyltoluenes, conjugated C4-C8-dienes, such as butadiene or isoprene, and esters of vinyl alcohol and monocarboxylic acids of 1 to 18 carbon atoms, such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate or vinyl stearate. In particular, xcex1,xcex2-monoethylenically unsaturated mono- and dicarboxylic acids of 3 to 6 carbon atoms, especially acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, the esters of the abovementioned carboxylic acids and alkanols of 1 to 12, preferably 1 to 4, carbon atoms, in particular methyl, ethyl, n-butyl, isobutyl, tert-butyl and 2-ethylhexyl acrylate and methacrylate, dimethyl maleate or di-n-butyl maleate, are also suitable.
However, precursor aldehydes, nitriles and amides of the abovementioned xcex1,xcex2-monoethylenically unsaturated mono- and dicarboxylic acids of 3 to 6 carbon atoms, for example acrolein, methacrolein, acrylonitrile, methacrylonitrile, acrylamide and methacrylamide, are also suitable. Monomers, such as vinylsulfonic acid, vinylphosphonic acid, N-vinylimidazole and N-vinylpyrrolidone, are also suitable.
The novel inhibitor composition is suitable as an additive both for stabilization during storage and for process stabilization (preparation, purification and chemical reaction) of at least one vinylically unsaturated group. The latter also applies in particular to distillation processes, which as a rule take place at from 50 to 300xc2x0 C., preferably from 50 to 200xc2x0 C., particularly preferably from 50 to 150xc2x0 C.
Stabilization using the novel inhibitor composition is particularly suitable in the case of the distillation (rectification) of (meth)acrylic esters (in particular the abovementioned typical examples), during their separation by distillation or rectification from product mixtures such as those which result from acid-catalyzed esterification of (meth)acrylic acid with alcohols, in particular alkanols (especially C1- to C12- or C1- to C8-alkanols), before and/or after removal of the acid catalyst.
However, said inhibitor composition is also suitable for stabilizing the abovementioned (meth)acrylic ester-containing mixtures which contain neither esterification catalyst nor acrylic acid nor methacrylic acid itself. Such (meth)acrylic ester-containing mixtures are formed, for example, by the abovementioned esterification product mixtures after, for example removal of the acid catalyst by extraction and/or rectification and after appropriate removal of the excess (meth)acrylic acid.
A (meth)acrylic ester-containing mixture subjected to distillation or rectification can be stabilized by adding the inhibitors to the mixture before the distillation.
In addition, stabilization can be effected by adding an inhibitor at the top of the column. Of course, the entire stabilization may also be effected exclusively by adding an inhibitor at the top of the column.
The various components of the novel inhibitor composition may be added in succession simultaneously or in premixed form. The abovementioned also applies to the other inhibitors if the inhibitor composition comprises them.
The components of the inhibitor composition may also be added at different feed points. For example, components of the inhibitor system can be added at the top of the rectification column and other components of the inhibitor system can be added at the bottom and/or to the feed of the rectification column. This applies both to those rectifications in the course of which the (meth)acrylic ester is isolated via a top takeoff, via a bottom takeoff and/or via a side takeoff. In the case of continuous isolation of (meth)acrylic esters by distillation (rectification), it may also be expedient to carry out the novel process in such a way that at least one inhibitor component to be fed in is added not continuously but merely from time to time, i.e. at recurrent intervals (e.g. at the top of the column, at the bottom and/or in the feed).
Everything stated about stabilization during the isolation of (meth)acrylic esters from acid-catalyzed esterification mixtures by distillation (rectification) also applies in the same way to isolation of (meth)acrylic acid or (meth)acrolein from mixtures containing them by distillation (rectification).
(Meth)acrylic acid is obtainable, inter alia, by catalytic gas-phase oxidation of alkanes, alkanols, alkenes or alkenals which contain 3 or 4 carbon atoms. (Meth)acrylic acid is particularly advantageously obtainable, for example, by catalytic gas-phase oxidation of propane, propene, tert-butanol, isobutene, isobutane, isobutyraldehyde or methacrolein. However, other possible starting compounds are those from which the actual C3-/C4-starting compound is first formed as an intermediate during the gas-phase oxidation. An example is the methyl ester of tert-butanol.
These starting gases, as a rule diluted with inert gases such as nitrogen, CO, CO2, saturated hydrocarbons and/or steam, are mixed with oxygen and then passed at elevated temperatures (usually from 200 to 400xc2x0 C.) and, if required, superatmospheric pressure over transition metal (e.g. Mo-, V-, W- and/or Fe-containing) mixed oxide catalysts and converted by oxidation into (meth)acrylic acid.
Owing to the numerous simultaneous and subsequent reactions taking place in the course of the catalytic gas-phase oxidation and because of the inert dilution phase to be used concomitantly, however, the catalytic gas-phase oxidation gives not pure (meth)acrylic acid but a reaction mixture which essentially contains (meth)acrylic acid, the inert diluent gases and byproducts and from which the (meth)acrylic acid has to be isolated. In addition to byproducts, such as acetic acid, which are comparatively simple to remove from (meth)acrylic acid and are less troublesome in subsequent uses of the (meth)acrylic acid, the reaction mixture also frequently contains lower aldehydes, such as formaldehyde, acetaldehyde, acrolein, methacrolein, propionaldehyde, n-butyraldehyde, benzaldehyde, furfural and crotonaldehyde, which are closely related to (meth)acrylic acid and are therefore difficult to separate from (meth)acrylic acid, and may additionally contain maleic anhydride (the total amount of these byproducts, which are frequently very troublesome in subsequent uses, is as a rulexe2x89xa62% by weight and in generalxe2x89xa70.05% by weight, based on the amount of (meth)acrylic acid contained in the reaction mixture).
It is also feasible to isolate acrylic acid from the reaction mixture of the catalytic gas-phase oxidation of propylene and/or acrolein by countercurrent adsorption using a high-boiling inert hydrophobic organic liquid. The inhibitor composition can be injected directly into the gas stream or into the apparatus for the countercurrent adsorption. Suitable organic liquids for the countercurrent adsorption include higher alcohols or esters thereof (in particular those with (meth)acrylic acid). The process is essentially carried out in such a way that the reaction mixture is fed countercurrently to the descending adsorption liquid in a conventional adsorption column, the readily volatile byproducts which can be easily separated off are then substantially removed from the liquid discharge of the adsorption column, essentially composed of acrylic acid, the adsorbent and byproducts, by stripping with inert gas in a desorption column, and thereafter the liquid discharge of the desorption column, containing the (meth)acrylic acid and the adsorbent as main components, is treated by rectification to isolate crude acrylic acid.
The problem of isolation of (meth)acrylic acid by rectification also arises when the (meth)acrylic acid is first taken up in water from the reaction gases of the catalytic gas-phase oxidation and the water is then separated off by rectification from the aqueous (meth)acrylic acid-containing mixtures with addition of an organic azeotropic entraining agent.
However, the problem also exists in the preparation of pure acrylic acid (purity greater than 99.7% by weight) from crude acrylic acid (purity greater than 99% by weight) by rectification.
The novel inhibitor composition can be used in the case of all of the abovementioned rectification problems. Of course, the novel inhibitor composition can also be used in the extraction of the (meth)acrylic acid from the reaction mixture of the gas-phase oxidation. The inhibitor composition can be injected directly into the gas stream. Stabilization is also recommended with the separation of mixtures containing (meth)acrylic acid or its esters by crystallization.
(Meth)acrolein is obtainable in a manner corresponding to (meth)acrylic acid, for example by catalytic gas-phase oxidation. However, the oxidation is not continued after the first oxidation stage. Rather, the (meth)acrolein contained in the reaction gas mixture is as a rule first isolated from the reaction gas mixture by extraction with water and then obtained from the aqueous solution by distillation (rectification). For all process steps mentioned, the novel inhibitor composition is suitable for stabilization.
The synergistic activity of the novel inhibitor composition is applicable essentially independently of the pH and both to low temperatures (e.g. room temperature) and to elevated temperatures, as are usual, for example, in thermal physical separation processes as well as for chemical reactions taking place at elevated temperatures.
In particular, the abovementioned applies to the stabilization of (meth)acrylic acid and/or its esters, whose ethylenically unsaturated double bond is particularly active with respect to free radical polymerization.
As a rule, the inhibitor composition is chosen so that the components contained in said composition are completely soluble in the substance to be stabilized, in the amount thereof which is used. Frequently, they are added not as pure substance but as a suspension, emulsion or solution. Particularly suitable solvents and/or dispersing media are those substances which are part of the system to be stabilized, i.e., for example in chemical reactions, such as esterifications, all starting materials and products.
The Example which follows illustrates the invention.

Inhibitor composition for stabilizing substances capable of free radical polymerization


A high-flexibility, noncollapsing, lightweight, large-bore, wire-reinforced hose is inside fiber-reinforced PVC tubing that is flexible, lightweight, and abrasion resistant. It provides a strong, kink- and collapse-free conduit for moving large quantities of dangerous fluids, e.g., removing radioactive waste water or processing chemicals.

This invention relates generally to a high-flexibility, lightweight, noncollapsing hose and more particularly to such a hose having a large size and particularly useful as equipment for draining a radioactively contaminated fluid through a noncontaminated, isolated and restricted space with high confidence against kinking, collapse, or leaking even with large relative motion between the inlet and outlet ends of the hose.
In the operation of nuclear facilities, such as nuclear reactors, processing plants for nuclear fuels and related materials, and chemical processing plants, for example, it is necessary to handle radioactively and/or chemically contaminated fluids which in many instances must be conducted, such as for draining purposes, through a noncontaminated, isolated and restricted space without contamination of the surrounding area. Conduction of such contaminated fluids through uncontaminated environments in practice requires the highest confidence that the hose will not kink, collapse, break, or leak even though the hose may be subject to a large amount of motion relative to the inlet and outlet ends of the hose. Any such breaking, or leaking would result in undesirable contamination of the area through which the hose passes which could result in major damage and/or in the requirement to shut down the operation for cleanup and decontamination processing of the area.
Additional problems are also encountered in processing plants for contaminated materials due to the fact that hoses conducting the contaminated liquids or gases pass through inaccessible, restricted spaces requiring extreme flexibility in the hose, but with the assurance that the hose will neither kink nor collapse to close off the flow.

High-flexibility, noncollapsing lightweight hose


The present invention generally relates to a process for the preparation of branched fatty acids from straight chain unsaturated fatty acid feedstocks with a strongly acidic and hydrothermally stable mesoporous aluminosilicate and/or aluminophosphate catalyst materials having mesopores of 15-500 xc3x85 and contain primary and secondary nanosized zeolite structural units in the walls that separate mesopores.

The present invention generally relates to the isomerization of fatty acids with a strongly acidic and hydrothermally stable mesoporous aluminosilicate catalyst.
Fatty acids are the building blocks for various compositions ranging from lubricants, polymers, solvents, cosmetics and the like. Fatty acids are generally obtained by hydrolysis of triglycerides of vegetable or animal origin. Naturally occurring triglycerides are esters of glycerol and generally straight chain, even numbered carboxylic acids, in size ranging from 10-24 carbon atoms. Most common are fatty acids having 12, 14, 16 or 18 carbon atoms. The fatty acids are either saturated or contain one or more unsaturated bonds.
Long, straight chain saturated fatty acids (C10:0 and higher) are solid at room temperature, which makes them difficult to process in a number of applications. Unsaturated long chain fatty acids, however, e.g. oleic acid are liquid at room temperature, so are easy to process, but are unstable because of the existence of double bond(s). Branched fatty acids mimic the properties of the straight chain unsaturated fatty acids in many respects, but do not have the disadvantage of being unstable. xe2x80x9cBranched fatty acidsxe2x80x9d means fatty acids containing one or more alkyl side groups which are attached to the carbon chain backbone at any position. Therefore, branched fatty acids are for many applications more desirable than straight chain fatty acids. Commercial branched acids are not, however, naturally occurring materials.
Currently, branched fatty acids are obtained by isomerization (branching) of the straight chain, unsaturated fatty acids having a corresponding chain length. For example, branched C18:0 is prepared from straight C18:1 (or also C18:2). Various routes are known for said isomerization or branching of fatty acids in the art.
Porous inorganic solids have found great utility as catalysts and separations media for various industrial applications. The openness of their microstructure allows molecules to access the relatively large surface areas of these materials that enhance their catalytic and sorptive activity. Three broad categories of microporous materials are in use today. These categories, which employ details of their microstructure as a basis for classification, are the i) amorphous and paracrystalline solids, ii) the crystalline molecular sieves and iii) layered materials. The detailed differences in the microstructures of these materials manifest themselves as important differences in the catalytic and sorptive behavior of the materials, as well as in differences in properties used to characterize them, such as their surface area, composition, acidity, basicity, the sizes of pores and the variability in those sizes, the presence or absence of X-ray diffraction patterns and the details in such patterns, and the appearance of the materials when their microstructure is studied by transmission electron microscopy, infrared absorption, electron diffraction methods.
Amorphous and paracrystalline materials represent an important class of porous inorganic solids that have been used for many years in industrial applications. Typical examples of these materials are the amorphous silicas commonly used in catalyst formulations and the paracrystalline transitional aluminas used as solid acid catalysts and petroleum reforming catalyst supports. The term xe2x80x9camorphousxe2x80x9d is used here to indicate a material with no long range order and can be somewhat misleading, since almost all materials are ordered to some degree, at least on the local scale. An alternate term that has been used to describe these materials is xe2x80x9cX-ray indifferentxe2x80x9d.
Paracrystalline materials such as the transitional aluminas also have a wide distribution of pore sizes, but better defined X-ray diffraction patterns usually consisting of a few broad peaks. The microstructure of these materials consists of tiny crystalline regions of condensed alumina phases and the porosity of the materials results from irregular voids between these regions. Since, in the case of either material, there is no long range order controlling the sizes of pores in the material, the variability in pore size is typicaly quite high. The sizes of pores in these materials fall into a regime called the mesoporous range, which is generally in the range of from about 13 to 200 Angstroms.
In sharp contrast to these structurally ill-defined solids are materials whose pore size distribution is very narrow because it is controlled by the precisely repeating crystalline nature of the materials"" microstructure. These materials are called xe2x80x9cmolecular sievesxe2x80x9d, the most important examples of which are zeolites. The pore/channel openings of typical zeolites ranges from 3-7.5 angstroms, although larger sizes have been reported.
Finally, layered materials contain layers capable of being spaced apart with a swelling agent, and may be pillared to provide materials having a large degree of porosity. Examples of such layered materials include clays. Such clays may be swollen with water, whereby the layers of the clay are spaced apart by water molecules. Other layered materials are not swellable with water, but may be swollen with certain organic swelling agents such as amines and quaternary ammonium compounds. Examples of such non-water swellable, layered materials include, but are not limited to, layered silicates, magadiite, kenyaite, trititanates and perovskites. Another example of a non-water swellable layered material, which can be swollen with certain organic swelling agents, is a vacancy-containing titanometallate material, as described in U.S. Pat. No. 4,831,006. Once a layered material is swollen, the material may be pillared by interposing a thermally stable substance, such as silica, between the spaced apart layers. Various pillaring materials and methods for pillaring water swellable and non-water swellable layered materials described therein and are known in the art.
Each of these materials does, however, have its limitations. Despite encouraging progress in recent years concerning amorphous and paracrystalline materials, both the acidity and hydrothermal stability at higher temperatures of the current materials are generally lower than those of microporous aluminosilicate zeolites. Crystalline microporous zeolites are very stable, can be made to have strong acidity, and are widely used commercially. However, their applications are limited due to their relatively small channel diameter. Finally, clay catalyzed isomerization suffers from two main disadvantages. First, a considerable amount of undesired side products containing oligomers, saturated straight chain fatty acids and intermediate dimers is formed. A second disadvantage is that the clay catalyst cannot be reused. Accordingly, processes which employ these materials for the preparation of branched fatty acids from straight chain unsaturated fatty acid feedstocks are typically plagued by low yield, undesireable byproduct formation and premature catalyst deactivation.
The present invention has solved many of the problems of the prior art by utilizing a catalyst having the positive attributes of both mesoporous and microporous type catalytic materials.
The present invention generally relates to a process for the preparation of branched fatty acids from straight chain unsaturated fatty acid feedstocks with a strongly acidic and hydrothermally stable mesoporous aluminosilicate and aluminophosphate catalyst materials having mesopores of 15-500 xc3x85 and contain primary and secondary nanosized zeolite structural units in the walls that separate mesopores.
The present invention generally relates to a process for the preparation of branched fatty acids from straight chain unsaturated fatty acid feedstocks with a strongly acidic and hydrothermally stable mesoporous aluminosilicate and aluminophosphate catalyst materials having mesopores of 15-500 xc3x85 and contain primary and secondary nanosized zeolite structural units in the walls that separate mesopores.
In one embodiment, the invention utilizes mesoporous aluminosilicates. However, other mesoporous materials based on other materials such as those comprising transition metals and post transition metals can also be employed. Catalytic materials such as those employable in the context of the present invention are described in Angewandte Chemie Int. Ed. (7, 2001, 1258), J. Am. Chem. Soc. (123, 2001, 5014), J. Phys. Chem. (105, 2001, 7963), J. Am. Chem. Soc. (122, 2000, 8791), Angew. Chem. Int. Ed. (40, 2001, 1255), and Chem. Mater. (14, 2002, 1144) and in Chinese Patent Application No. 01135624.3, which are incorporated herein by reference.
Generally, the synthesis of the mesoporous aluminosilicates and aluminophosphates of the present invention involves the preparation of primary and secondary zeolite building unit precursors, which are subsequently assembled to stable mesoporous zeolites in the presence of surfactant or polymeric templates. Mesoporous zeolites derived from this invention have similar acidity, thermal and hydrothermal stability as conventional zeolites, and also have high catalytic activity.
As an example, highly ordered hexagonal mesoporous aluminosilicates (MAS-5) with uniform pore sizes were synthesized from an assembly of preformed aluminosilicate precursors with cetyltrimethylammonium bromide (CTAB) surfactant. Choice of surfactant is not a limiting feature as most quaternary ammonium salts, phosphonium salts, anionic and non-ionic surfactants, and polymers which form micellar structures in solution are effective. Other examples include, but are not limited to cetyltrimethylphosphonium, octyidecyltrimethylphosphonium, cetylpyridinium, myristyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium, dimethyldidodecylammonium, fatty alkylamines, fatty acids, and mixtures thereof.
The aluminosilicate precursors were obtained by heating aluminosilica gels from the aqueous hydrolysis of aluminum and silicon precursors. As previously mentioned, the present invention is not limited to Al and Si precursors, and other precursors such as certain transition metal candidates can be employed. The aluminosilicate gels are heated at 80xc2x0-400xc2x0 C. for 2-10 hours. The gels had a Al2O3/SiO2/TEAOH/H2O molar ratio of 1.0/7.0-350/10.0-33.0/500-2000. Mesoporous MAS-5 shows extraordinary stability in both boiling water and steam. Additionally, temperature-programmed desorption of ammonia shows that the acidic strength of MAS-5 is much higher than that of conventional mesoporous materials and is comparable to that of microporous Beta zeolite. Analysis and testing of the materials of the present invention suggest that MAS-5 consists of both mesopores and micropores and that the pore walls of the MAS-5 contain primary and secondary structural building units similar to those of microporous zeolites. The unique structural features of the mesoporous aluminosilicates of the present invention are believed to be responsible for the observed strong acidity and high thermal stability of the mesoporous mesoporous aluminosilicates of well ordered hexagonal symmetry.
Additionally, the scope of the present invention is not limited to zeolites in general, or to a particular zeolite, as materials other than zeolites can be employed in the context of the present invention. Zeolites are, however, a preferred material to be employed and the use of any known or yet to be discovered zeolites in the formation of the mesoporous materials of the present invention is included within the scope of the present invention. More particularly, using precursors of other zeolite structures, one of ordinary skill in the art could readily tailor make mesoporous zeolites containing the structural features of the particular zeolite chosen. Examples of zeolites which can be employed in the context of the present invention include, but are not limited to, zeolite A, Beta zeolite, zeolite X, zeolite Y, zeolite L, zeolite ZK-5, zeolite ZK-4, zeolite ZSM-5, zeolite ZSM-11, zeolite ZSM-12, zeolite ZSM-20, ZSM-35, zeolite ZSM-23, aluminophosphates including but not limited to VPI-5 and the like, and mixtures thereof.
It is known that the aluminosilicates and/or aluminophosphates employable in the context of the present invention can be metal containing, or non-metal containing. Zeolites may contain elements such transition metals, post transition metals, Ln series and the like. Specific examples include, but are not limited to B, Ti, Ga, Zr, Ge, Va, Cr, Sb, Nb, and Y.
Good selectivity and conversion can be obtained by the process of the present invention if at least part of the isomerization is performed at a temperature of between about 100xc2x0 C. and 350xc2x0 C. In another embodiment, the process of the invention is performed at a temperature of between about 230xc2x0 C. and 285xc2x0 C. Since the conversion is also a function of the reaction/contact time, it is preferred that the fatty acid feedstock is contacted with the catalyst for a period of at least 30 minutes and reaction times of 1-16 hours are typical. An even longer period could be used if the process is operated at a lower temperature.
In general, the amount of catalyst employed in the process according to the invention is between 0.5 and 30% by weight when the process is carried out in batch or semibatch process, based on the total reaction mixture. In another embodiment the amount of catalyst used between 2.5 and 10% by weight. In still another embodiment the catalyst amounts are between 3 and 7% by weight.
When a continuous flow reactor is employed, the weight hour space velocity is between 0.01 and 100. Weight hour space velocity is defined as the weight of feed in grams passing over one gram of catalyst per hour.
Additionally, it has been found that by using the catalyst system according to this invention it is possible to reuse the catalyst. In some cases it may be desired to add fresh catalyst while optionally removing a part of the spent catalyst, and in other cases regeneration of the catalyst may be desired. Regeneration can be effected by various methods known to the skilled artisan. For example, regeneration can be accomplished by utilizing controlled oxidative regeneration and/or by washing with a solvent.
Typical feedstocks comprise fatty acids and esters derived from natural fats and oils. Such feedstocks are predominantly unsaturated linear alkylcarboxylic acids, related esters or mixtures thereof, optionally containing other organics. Since the present process is designed for isomerization or conversion of unsaturated fatty acids into branched fatty acids, it is beneficial if the fatty acid feed comprises of at least about 30% by weight of unsaturated fatty acids. In another embodiment, the feedstock comprises at least 50% by weight of unsaturated fatty acids. Any unsaturated and/or polyunsaturated fatty acid, or mixtures thereof is suitable as a feedstock in accordance with the present invention. In one embodiment, the feedstock comprises oleic acid as the unsaturated fatty acid in an amount of at least 40% by weight. In an alternative embodiment, the feedstock comprises at least 70% by weight oleic acid.
The invention also relates to the branched fatty acids and alkyl esters prepared by the processes described herein. Additionally, the invention contemplates all derivatives prepared from branched fatty acids and alkyl esters prepared by the processes described herein.
Fatty acid alkyl esters and fatty acids are versatile building blocks and conversion of these materials into a wide variety of other surfactants is possible. Some examples of the type of reactions possible are listed below. From these starting materials it is possible to produce non-ionic, anionic and cationic surfactants, all of which is within the scope of the present invention.
The branched fatty acid alkyl esters and fatty acids products of the present invention can be utilized as starting materials to prepare the same derivatives as their linear counterparts. For example, the branched alkyl esters of the present invention are readily converted into fatty acid glucamides and glycerol esters. Alkylation of polyhydridic molecules is possible. An example of this type of reaction would be reaction of a branched methyl ester with sucrose to prepare sucrose esters. Conversion of branched alkyl esters to alpha sulfonates is known. For example, branched fatty acid ester sulfonates (FAES) can be produced from branched methyl esters by sulfonation, followed by bleaching and neutralization. Branched fatty acid alkyl esters can also be converted into other branched alkyl esters by a transesterification reaction. In most cases, the smaller molecular weight alcohol is removed from the reaction mixture forcing the reaction to the desired products.
Branched fatty acids undergo many of the same reactions their linear counterparts as well as linear and branched fatty acid alkyl esters. For example, the branched fatty acid of the present invention may be converted into its"" soap form by neutralization with a base. N-acyl sarcosinates can be prepared from reaction of the branched fatty acid of the present invention fatty acid or its derivatives with sarcosine. Acylated protein hydrolysates are prepared by acylation of protein hydrolysates with branched fatty acids or acid chlorides. The hydrolysates are variable in composition, depending on how they are prepared. These are mild surfactants used in often in personal care formulations. 2-Sulfoethyl esters of branched fatty acids, also known as acyl isethionates, are excellent surfactants. This family tends to be mild to the skin and hard water tolerant. Amido propyl amine and derivatives are prepared from the fatty acid or fatty acid alkyl ester. This family of surfactants has seen commercial application in laundry detergents, dishwashing liquids and many personal care formulations. Condensation of a fatty acid alkyl ester or fatty acid with an alkanolamine results in the formation of an alkanolamide. The alkanolamide and it derivatives have a variety of uses commercially depending on its specific chemical structure. Ethoxylated alkanolamides are used as compatibilizers in formulations. Many alkanolamides and derivatives are used as thickeners and foamers. Branched fatty acids can be alkoxylated with ethylene oxide, propylene oxide and butylenes oxide to make a useful family of non-ionic surfactants. Branched fatty acids can be converted into nitriles which are the building blocks for a large variety of cationic and amine surfactants. Branched fatty acids acan also be used in a reaction to prepare esteramines which are quaternized, esterquats. The major use of esterquats is in household fabric softeners.
Conversion of the branched alkyl esters and branched fatty acids into branched alcohols can also be done. The alcohol is another building block to prepare other types of surfactants. Alcohols are used to prepare alkyl polyglycosides (APGs). These materials offer a hydrophile based on a natural sugar. Conversion of the alcohol into amines and quaternaries occurs readily and is a commercially important reaction in the preparation of cationic surfactants. Non-ionic surfactants are prepared by alkoxylation of alcohols. Common alkoxylation agents are ethylene oxide, propylene oxide and butylene oxide. Conversion of alcohols (with or without alkoxylation) to alcohol sulfates is a commercially important process. The use of alcohol sulfates in laundry is increasing especially in Europe. Other areas of use include shampoos, textile processing and emulsion polymerization. Alcohols can also be converted in phosphate esters. Both mono and di phosphate esters can be favored depending on the reaction conditions. Polyalkoxycarbonates are produced by the reaction of sodium chloroacetate with an alcohol ethoxylate, or from acrylic acid and an alcohol ethoxylate. These can also be made by direct oxidation of the alcohol ethoxylate under carefully controlled conditions.
The aforementioned description is merely illustrative and not intended to limit the scope of the invention. Accordingly, one of ordinary skill in the art would readily recognize that the branched products of the present invention, like their linear counterparts, can be readily employed as starting materials in the preparation of numerous derivatives as illustrated by the following chart. Any and all of the derivatives prepared from the novel products of the present invention are within the scope of the present invention.
The invention will now be illustrated by the following non-limiting examples.
Synthesis of Strongly Acidic and Hydrothermally Stable MAS-5 Containing Beta Zeolite Building Units
A highly ordered hexagonal mesoporous aluminosilicate was synthesized in this laboratory following a procedure similar to that described in Xiao et al""s paper (J. Am. Chem. Soc., 2001, 123, 5014-5021). A proton form MAS-5(H+-MAS-5) was prepared by ion exchange of Na+ for NH4+ from the Na+-MAS-5 mesoporous zeolite, followed by drying and a calcination in air at 500xc2x0 C. for 2 h. This H+-MAS-5 sample has a sharp pore size distribution at xcx9c37 xc3x85 with zeolite beta wall structure at Si/Al (mole ratio) of 25.
Table 1 shows some physical properties of the Na+-MAS-5 sample.
The reaction result of the H+-MAS-5 sample for oleic acid isomerization was presented in the examples below.

Fatty acid isomerization with mesoporous zeolites