ITME940002A1 - HYDROCARBON, WATER, FUEL AND ADDITIVE COMPOSITIONS - Google Patents

Description

Description of the industrial invention entitled 'Aqueous hydrocarbon compositions, of fuels and additives in the name of

The present invention refers to the formulation of additives which allow: a) to re-stabilize the flocculated and / or precipitated asphaltenes in a petroleum product (generally a residue or a fuel oil), thus making possible the combustion of oils that otherwise could not be burned as such, or the treatment of crude oils containing asphaltenes in certain quantities, h) to reduce the problems of fouling from heavy compounds in equipment in which a fluid flows, preferably hydrocarbons, c) to increase the conversion yields of petroleum / petrochemical plants ; d) to reduce the formation of particulates and / or SOx and / or ΝΟχ in the combustion of fluids and / or solids; e) to reduce the formation of coke on heaters of petroleum / petiolchemical plants; 0 to favor the decoking and / or cleaning of equipment and / or materials. In their formulations, such additives can be dispersed in new types of solvent or have no solvent.

The flocculation of asphaltenes causes considerable operational problems such as, for example, clogging of fuel oil pump filters, clogging of burners, bad combustion in fuel oils, or cs. clogging of equipment in the oil extraction processes.

All the examples reported below are to be considered as illustrative and should not be considered as a limitation of the present invention, in the formulation of fuel oil (OC) containing cracking residues especially those from Visbreakmg. a particular problem is constituted by the established of the fuel obtained.

! residues and residual fuel oils can be considered as a colloidal system in which the asphaltenes form the dispersed phase and the oily medium the continuous phase. Asphaltenes are high molecular weight compounds (PM also f 0000) with a high carbon content and a low hydrogen content; they are in the micellar form. These mycelia and are peppered (i.e. held in suspension) in the oily medium. A third component can normally be identified, the so-called "resins", which are chemically intermediate between the oily medium and the asphals; eni and re-concentrate on the external part of the mi cells. The resins and the oily medium, considered as a single whole, they are called "Maltenians *.

The equilibrium of the asphaltenes / oily medium system depends on something similar to a real "solubility" of the asphaltenes in the oily medium, on the nature of this "solvent" and on the degree of dilution. Generally it can be said that, being high molecular weight products with a highly aromatic character, asphaltenes are more "soluble" in aromatic hydrocarbons than in alitatic ones. If the balance between asphaltenes and oily medium is disturbed (for example by diluting the aromatic solvent with an aliphalic solvent) asphaltenes can agglomerate and precipitate as sludge, ie "flocculation" takes place.

By definition, asphaltenes are those components which precipitate by adding n-peptno (or hexane).

From literature data, the stability of the asphalthereal aggregals is given by n-n interactions between the polyconjugated aromatic systems of adjacent molecules (in this way the asphaltenes are associated in "stacked layers")

In most commercial fuel oil specifications, stability is expressed in terms of "dry sludge will count", which is measured with the ΙΉot Filtration Test (HFT) - evaluated by the SMS 2696-83 method. As stability with asphaltenes decreases in hot conditions, it measures the amount of solids (dry sllidge mostly flocculated asphaltenes) filtered hot (100 ° C) and washed with n-heptane. The current limits of HFT (both existing and potential) are 0.15%.

The stability of the thermal cracking residue, and therefore of the asphaltenes, depends on the severity of the reaction (and therefore on the conversion): HFT can grow strongly even after a small increase in conversion.

In all thermal processes aimed at the conversion of residues and / or other heavy charges, a problem is linked to the poly condensation of high molecular weight molecules (resins and asphaltenes). These secondary reactions give low-value products (pitch and coke), affect the stability of the desired products, induce many difficulties in the design and operation of the plants and, consequently, must be prevented or at least controlled. Since all thermal activation reactions involve a free radical mechanism, one of the p3 ways to suppress polycondensation reactions is to use hydrogen-donors.

Another problem related to the use of cracked OCs is that of the compatibility of the luxant used to correct some characteristics of such OCs.

The compatibility of a cracked residue with a flux depends, among other things, on the degree of dilution. The more the residue is diluted, the more the concentration of the pepper initially present in its oily medium decreases. In any case, paraffinic luxants cannot be used, as these products destabilize asphaltenes. If an OC presents stability problems, it is possible to correct this parameter by mixing the cracking residue with products rich in aromatics and / or asphaltenes with high peplicability.

This would make it possible at least to reduce the value of OC ATZ (eg LCO, diesel, OC BTZ, aromatics) with considerable costs, given the quantities of "diluents" required (up to 80 - 90%) and the differences of price (for example the devaluation from OC BTZ to OC ATZ is currently worth about 35000 Lit / ton). It is essential that any corrective action is taken before other less suitable components of the mixture are added to the residue from cracking, since asphaltenes , once flocculated, they can hardly be re-peppered.

For the same reason, the sequence of operations for mixing the components is also very important.

The instability of OCs containing cracking residues may not result directly after mixing and may occur later. This is due to the fact that the asfallen / oil system is a viscous medium in which phase changes a '/ are relatively slow. The siudge content (HFT) of OCs after mixing can change after long periods of storage or during prolonged heating; it can increase or decrease in relation to the nature of the {luxants. If it were possible to correct 1HFT with a chemical compound to be dosed in Eccola percentage sul'OC without devaluing large quantities of fluxes, an improvement in the current state of the art would therefore be achieved.

If it were then possible to make the OC stable even when diluted with paraffinic bussanti, a further improvement of the state of the art would be achieved.In the current state of the art no additive is used to repeptize the already flocculated asphaltenes, especially for what concerns the correction dcifHFT of fuel oils.

There are compounds suitable for stabilizing the asphalts in solution, which are mainly used in the treatment of the raw material to its extraction to avoid clogging of the equipment due to the deposition of asphaltenes. Their range of application is therefore limited to milder problems since the destabilized asphaltenes in a crude are far lower than those destabilized by a thermal cracking residue. It is not excluded that these compounds may also have positive effects on tIFT, but their use in this sense, to our knowledge, has never been proven to date.

Another problem linked to the presence of asphaltenes is the formation of dirt on equipment of petroleum / petrochemical plants. Asphaltenes, together with other compounds, constitute the heavy part of the charges of said plants and cause the formation of agglomerates with a high C / H ratio which limit the heat exchange and / or Topcrativity of said equipment. Other compounds that cause fouling can be of the polymeric type (generated e.g. by the polymerization of ajcbenid compounds) and / or condensation products (e.g. phenanelone-indane)

The presence of heavy compounds in the fillers limits the conversion to light products in petroleum / petrochemical plants.

The presence of heavy compounds is also a source of particulate and / or soot emissions during combustion. Defects, these heavy compounds constitute the "core on which the drop of fuel (if liquid) is formed in the combustion chamber: the combustion of the drop will take place from the outside towards the inside and after vaporization of the volatile products an internal core will remain In this process both soot and particulate matter will be formed; it will be valid both for combustion through burners and in the combustion of fuels in engines

Heavy compounds and / or condensation products are also responsible for the formation of coke on the catalysts of petroleum / petrochemical plants, which, in turn, limits the conversion of said plants.

Currently all these problems are solved with formulations which are different from each other, for example of the type of dispersants to limit the formation of fouling or the darkness of asphaltenes, combustion catalysts to limit the particulate matter.

A dispersant consists of an anchoring polar group and a blocking alkylysus group; the palar group generally contains eternatoms of the type: oxygen, nitrogen, phosphorus. The dispersants adsorb on the surface of the asphaltic particles, the adsorbed molecule acts as a repulsive barrier between these particles, preventing agglomeration and therefore precipitation.

The various formulations of asphaltenes dispersants which have proved to be of industrial interest include the following classes of compounds: polymethacrylates. polyisobutylene succinimide, polyisobutylene succinate.

A polyisobutylene succinate is obtained by reaction between a succinic anhydride substituted with an oledine and an aliphatic polyhydric alcohol. A high molecular weight polyester is thus obtained.

the latest generation of asphaltenes dispersants is formulated with a laurylacrylate / hydroxyethylmethacrylate copolymer and a substituted phenol / formaldehyde resin (with a molecular weight of about 3000). It is supposed that they work by replacing the natural resins necessary for the stabilization of asphaltenes; also for this class of compounds there is no evidence that they can repeptize the asfahenes after precipitation and in any case there is no evidence of their effect on HFT. the dosage then necessary to 'replace * the natural resins would be of the order of 1%

Another type of dispersant formulation for asphaltenes consists of a mixture of alkylaryl-sulfonals, alkanolamin-alkylaryl-sulfonates and alkylaryl-sulphonic acids, which acts as a surfatlant and increases the surface tension of the raw material above the level at which the precipitation.

Other dispersants known in the current state of the art consist of: substituted amines, in which the substituent is a hydrocarbon containing at least 8 carbon atoms; b) acylated compounds containing nitrogen and having a substituent with at least 10 aliphatic carbon atoms, said substituent being obtained by reaction of a selling carboxylic acid with at least one arnine compound containing at least one -NH- group, said acylating agent being bonded to said compound aramine through an imido, starch, amidine or acyloxammonium bridge; c) nitrogen-containing condensed compounds of a phenol, an aldehyde and an arnine compound, having at least one -NH- group; d) esters of a substituted carboxylic acid '); e) phenols substituted with hydrocarbons; f) alkoxylated derivatives of an alcohol, a phenol or an amine. There is no evidence that compound data have been used in connection with the present invention.

In one of its preferential applications, the present invention provides compositions of additives and hydrocarbons which allow the stabilization of asphaltenes and / or their repeplization.

Unlike the current state of the art, it has been surprisingly seen that glycols and hydrocarbons (HC) aiogenated, alone or possibly in mixture with commonly used dispersants, have a positive effect, even at small concentrations, on the repeptization of asphaltenes. flocculated, and therefore on the HFT. All the more reason these compounds have an effect in preventing the destabilization of asphaltenes.

Unlike the current state of the art, classes of compounds that are completely different from those currently in use are used to stabilize asphaltenes. It is also possible to repeptize the flocculated asphaltenes.

To our knowledge, the use of an additive according to the present invention as a stabilizer and / or repeptizer of asphaltenes has never been proposed nor in connection with the treatment of fuel oils (containing or not cracking residues) to obtain their stabilization, neither their repeptization, nor a control on the HFT, nor in connection with the treatment of raw materials during the extraction phases and subsequent processing.

The usefulness of this additive in such connections must therefore be considered as surprising and out of the current state of the art.

According to this invention, the present invention provides an additive capable of repeating the flocculated asphaltenes and / or preventing their destabilization.

The additive claimed herein has been tested in the laboratory to verify its efficacy. The tests carried out were carried out according to the SMS 2696-83 method aimed at determining the current and potential content of dry sludge (the asfaheni) in ur. petroleum product.

The following examples are illustrative and should not be construed as a limitation of the present invention.

EXAMPLE N ° 2

In other tests it has also been seen that OC with additives also obtains an established flow rate.

To an OC destabilized with HFT · 0.51% 10% of JP8 or 10% of kerosene was added: the resulting IHFT was not evaluable since the mixture did not filter in the maximum analysis time. The same OC added with 2000 ppm of the additive 11203 was not only stable to flushing, but gave an HFT of 0.02% (without kero IHFT it was 0.15%).

EXAMPLE N 3

In another test it was also possible to mix a BTZ paraffin oil with an ATZ asphahenic oil. It is well known that this type of mixing is impossible without causing the destabilization of the asphaltenes: in fact, mixing from 10% to 80% of BTZ with the resulting ΑΤΖ HFT was indeterminable because the sample did not filter within the maximum analysis time. By treating ΙΆΤ2 with 2000 ppm of the additive 11203 it was possible to mix 30% of BT2 in the ATZ, obtaining an average HFT of 0.12%. The characteristics of the starting OCs are as follows:

It follows therefore that glycols and halogenal HCs are more effective than common dispersants in decreasing 1HFT or in stabilizing and / or repeptizing asphalts. Among the glycols, those with a low molecular weight (preferably up to 250) are to be preferred. among the halogenal HCs, halogenated aromatics are preferred. There seems to be a sort of synergy between the halogenated aromatics and the glycols.

For the purposes of the present invention, therefore, all the glycols or their derivatives can be used, these glycols and their derivatives being characterized by not being organized in polymeric form, in the sense that they are molecules of single compounds, even in adduct form, and not molecules. consisting of a chain in which a monomer is repeated; for the purposes of the present invention the following are considered as single glycols, for example: tetraethylene glycol, ethers (mono and di-), esters (mono and di-), ether-esters and ioethers of the single glycols.

Without wishing to be tied to any theory, the probable mechanism of action of halogenated HCs and glycols, both individually and synergistically, seems to be that by which halogenal HCs significantly increase the solubility of asphalts compared to non-halogenated ones; then the glycols, especially if they have a low molecular weight, "insinuate themselves * into the asphaltenic structure, helping to keep it in suspension (having polar groups, they can cause repulsion between the individual asphahenic particles).

Unlike the current state of the art, therefore, there seems to be no compound adsorbed on the asphaltenic particle, but rather a compound that causes an increase in stability or an increase in established values.

Likewise, any low molecular weight polar compound could be used in addition to any halogenated aromatic compound. Another possible mechanism of action (probably complementary to the previous one) is that, since glycols and / or halogenated HCs are excellent solvents of resins (both synthetic and natural), the resins are suitably dissolved and made available to a greater number of asphaltenes following their "delocalization"; it is also possible that in this mechanism of dissolution-delocalization of the resins the glycols and the other compounds claimed herein, in addition to without being linked to any specific theory, the action of the additive could also be that in which the solubitization of the asphalteru leads to a lower concentration of asphalts in the "solution * fuel oil and this, subsequently, leads to a" dissociation "(delamination) of the clusters rather than to their association ((dynamic model of asphaltenic molecules) - Chem Eng. Se Vol. 47 , 9-11, 1992)

In addition, since the asphalts are held together by hydrogen bonds and Yan der Waais forces, the -OH and / or polar groups insinuate between the clusters and cause their dissociation, hence the minor HFT.

In particular, the mechanisms hypothesized in the literature to explain the interaction between resins and asphalts are substantially two: cosolvency and / or specific interactions. The first type of interaction (coexistence) would be attributed to the greater polarity conferred by the resins on the oily medium in which the asphaltenes are immersed; in the second, the specific resin-asphaltenes interactions occur through hydrogen bonds. This last mechanism is considered to be of primary importance in the peptizing fiction that resins play.

This may also result in the action of glycols and / or other compounds with -OH groups, because they can form stronger hydrogen bonds with asphaltenes than asphalten-asphaltenene molecules and / or interact on the n-π layers between polyconjugal aromatic systems of adjacent molecules: in both cases the association of the single asphalt molecules will not be favored, but their dispersion.

The same effect can manifest the basic groups (e.g. amin :, carbazoles, benzopyroles, benzothiazoles, cyclic amides, quinolines, benzoquinolines, benzocarbazoles, thioquinolines, indoles, indolothiaphenes, carbazolothiophenes, imidazoles, etc.) and / or acid groups (e.g. e.g. carboxylic acids, naphthenic acids, esters, etc.) both for the reasons mentioned above (interaction with hydrogen bonds and / or with the forces of Vari der Waais), and because it is already known that asphalts have acid-base balances "internal" that favor the aggregation.

In general, according to the present invention, organic compounds can be used which contain eternatoms with at least one free doublet available, such that they can preferentially form hydrogen bonds with the asphaltenes and / or the heavy compounds present in the system to be treated.

The heteroalomas which are preferred according to the present invention are: N, O, Cl, Br, I, F, S.

Among the compounds described above, those characterized by hydroaromatic rings are to be preferred, since they favor the transfer and / or donation of hydrogen with the coke and / or petroleum radicals formed following the thermal degradation of a fluid according to the present invention. .

Furthermore, since it is already reported in the literature how changes in the dielectric constant can lead to changes in the dispersion of asphalt colloids in petroleum residues, solvents with different dielectric constant can increase the dispersion of asphalts: their effect will therefore probably depend on the nature of the asphaltenes molecules, as the different molecules will have different "response" to the change of dielectric constant of the medium.

A list of the dielectric constants of some solvents that can be used according to the present invention can be found in the Handhook of Chemistry and

For the purposes of the present invention, the heterocyclic compounds can be the most varied, since they contain atoms with free electron doublets which, as seen, contribute to solubilize the coke and keep the asphalts dispersed.

The heterocyclic compounds of the present invention include those selected from the following group: furans, thiophene, pine nuts, pyrazoles, imidazoles, triazoles, diliols, oxatiol, oxazoles thiazoles, oxadiazoles, oxalriazoles, dioxazoles, oxatiazole, pyrones, pyrones, pyrones, pyridazine, pyrimidine , pira zi na, piperazine, piperidine, triazines, osaazine, azine ossuaries, oxadiazines, morpholine, azepine, oxepine, liepine, diazepine, indane, induced, benzofurans, benzoliophenes, indoles, pyran-pyrrole, mdazole, indole, anthraxanyl, benzopyrane, annerine, quinolines, benzopyrones, cinnolire, quinazoline, naflaridine, pyrido-pyridines, benzoxazines, carbazole, xanthene, acridine, punita, benzopimrii, benzoriazoles, cyclic amides, benzoquinolines, benzocarbazoles, thioquinriazol, indidothiophols.

In the description of the previous group the plural is to be understood as including all the possible conformations of the compound, including the iso- forms: for example, the term "diliol" includes 1, 2 diliol and 1, 3 dithiol, "quinoline * includes quinoline and isoquinoline, ccc ..

As used in the present invention the term "hydrocarbon substituent" refers to a group having a carbon atom directly attached to the rest of the molecule and having a hydrocarbon or predominantly hydrocarbon character. Among these can be mentioned the hydrocarbon groups, including the abiatic one (eg alkyl or alkyl), alicyclic (eg cycloalkyl or cycloalkyl), aromatic, aromatic substituted with abiatic and / or alicyclic groups, condensal aromatics; the aliphalic groups are preferably saturated. Examples of these include: methyl, ethyl, proprio, botyl, isoburyl, perityl, slender, octyl, decyl, octadecyl, cyclohexyl, phenyl. Such groups may contain non-hydrocarbon substituents, provided they do not alter the predominant hydrocarbon layer of the group. Examples of these include the keto groups.

aio, hydroxy, nitro, cyano, alkoxy, scyl, sulphonium, sulphosaid, sulphide, amino. The groups can also and / or alternatively contain atoms other than carbon, such atoms being placed in a hydrocarbon chain or ring otherwise consisting of carbon atoms. Some of these types include, for example, oxygen, nitrogen and sulfur

Among the compounds described above, those selected in the following group are preferred: trichloroethylene, tetrachlorethylene, methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, melylglycol monomethyl ether, butylglycol monobutuether, toluene, heavy animins (e.g. the Soiaria RS41, marketed by BP Chemicals), ari! sulfur nati (eg Atlas MC 2343 marketed by Alias Europol (ICI)), glycerin, thioglycolic acid. itaphthalic acid, o - dichlorobcnzene, benzene, anthracene, carbon tetrachloride, carbon disulfide, pyridine, aniline, chloroform, tetralin, 1-methyl [naphthalene, diphenyl, phenanthrene, ocresol, phenol, nonylphenol, l-methyl2-ethrolide, diethyl, dimelylformamide (DMF), tetrehydroluran (THF), ethylndiamine, diethylamine, tnttylamine, propylamine, l- (3-araminopropit) -2-pyrrolidone, l- (3-aminopropes)) imidazola, N'ihydroxyjectylimidimidazones 2- (2-amnunoelylamino) ethanol, furfunlamine, isopropylamine, cumene, 1,3,5 trìmethylbenzene, 1,2,4 trìmethylbenzene, indane, tetrahydroquinone, 4-hydroxyindane, octaoal (famonium, maleic anhydride, tetrabutylammonium hydroxide, li p-tohndine, o-toluidine, thiophene, dipropylaramma, quinoline, isoquinoline, tetrahydroquinolbia, diphenylether, hexamethylbcnzene, propylbenzene, cyclohexylamine, 1-isopropyl-4-methyl-benzene, l, 2,3,5 tetramethylbenzene, carbohydrate dihydrogen , hydroquinone, die thihydroxylamate (DEHA), eayl alcohol, tetrahydrothiophene, morpholine, nitrobenzene, o-xylene, m-xylene, p-xylene, 2 mercaptohenzothiazole, butylamine, roctylamine, p ^ chlorolyphenol, 5.6 diiylrc> -4-R) ethylpyran, 2-methylfuran, benzothiophene, benzophenone, piperazine, piperidine, raesitilenc, examine, succinic anhydrous, decahedron naphthalene, ethylbenzene, 1/2 dimethylnaphthalene, 1.6 dimethylnaphthalene, p-c hymene, ethyl ether, isopropene ether, ethoxylethen2 -chlorotoluene, m-dichlorobenzene, monoethanolamine (MEA), diethanolamine (DEA), trìethanolamine (TEA), cis-de calm, trans-decalin, diethylene glycol, triethylene glycol, tetractylenglycolc, dodecylberucnc, laurel alcohol! ko, myrisiic alcohol, salicylic acid, 8-idkoxyquinoline, benzotrìazole, tolyltrìazole, liodighcole, salicylic aldehyde, p> toluenesulfonic acid. dibutylftaUto, dinomlfUiato. meli I helium ketone (MEK), meilisobutyl ketone (MIBK), methyl-tcrbinyl ketone (MTBE), sulfolane, cyclohexane, 3,6-dioxphthalimide, 3,6-tetramethyldiatnminoxanthone, a. naphthylamine, β naphthylamine, acridine, fluorescein, quininic acid, coumaric acid, l-naphthol-4-sulfonic acid, 2-naphthol-3,6-disulfonic acid, naphthotic acid, β naphthol, α-naphtholsulfonic acid, 1,4 -naflolsulfonic, coumarin, mctanol / KOH mixtures. To these compounds it is necessary to add the following compounds, hereinafter better defined: BDM, GCAG, GSAG.

Some of these compounds are known in the literature as stabilizers of asphyllenes, e.g. alkylphenols, but have never been used to reduce ΙΉΗΓ and / or in the other connections of the present invention.

EXAMPLE K ° 4

10% FOC (Cracking Fuel Oil - from Ethylene plant) was added to an OC, making the mixture non-filterable; following the addition of 4000 ppm of 1303) (85% solvent naphtha 15% commercial mixture of naphthenic acids): ΙΉΡΤ was found to be 0.11%

The additives described here, as characterized by the claims, therefore differ from the state of the art in that: a) they do not consist of polymeric, copolymer and / or long-chain compounds, but of single "non-nomcric" molecules, b) most probably not they adsorb on the surface of the particles, but they creep into them; c) contribute to increasing the solubility of asphaltenes in the ichphrocarbon phase; d) they preferably consist of low molecular weight compounds; e) they do not act exclusively by repulsive action between asphaltenic particles; f) can "delocalize" the resins.

For example, nitrobenzene has a strong effect on the molecular weight of asphaltenes, while pyridine removes most of the occluded resins.

The above evidences are a further confirmation that the additive described and claimed here acts as a repeptizer of the precipitating asphaltenes and prevents their destabilization, even under drastic conditions.

If such an additive acts in this sense, all the more reason it will work in "milder" situations, such as for example the removal of asphaltenes in the rough. In another preferential application, the present invention provides formulations which allow to reduce the fouling of asphaltenes during the production of crude oil.

During the normal production of the crude, the flocculation of asphaltenes and their subsequent precipitation originates from the soft chemical, electrical and mechanical processes that take place, including: a) addition of liquids with low surface tension; b) oxidation of asphaltenes particles; c) release of low molecular weight gas; d) acid washings; e) electrical neutralization of the charge during the flow of the liquid.

the various thermal, mechanical and solvent-based methods normally employed for the control of paraffins are only partially effective for the control of asphaltenes. This reduces the effectiveness of the hot oil method and mechanical cleaning. The solvent removal of the deposits is limited to the aromatic fractions; in addition, pure aromatic solvents such as xylene and toluene have little or no effect on the removal of asphaltic deposits from the formations.

The additives claimed herein can therefore find application in the processes of extraction of the crude (as well as in the processes of its refining) in order, for example, to be used for. a) assisting the de-emulsifiers; b) control the raw / water interphase (the asphaltenes are placed at the interphase, stabilizing the emulsion); c) clean the bottoms of the tanks; d) to clean the wells (both for production and for injection; e) to assist the water injection and clarification systems; f) clean the jet pumps and orifices

The decrease in asphalts (even in their size) also causes less foaming.

EXAMPLE N "5

Dispersion tests of asphaltenes were carried out as follows: a known quantity of sample (about 1 g) was introduced into 100 cc of n-heptane and it was stirred for 1 min; it was allowed to settle (asphaltenes precipitated) and the solvent was pipatalized to add new: finally the quantity of asphaltenes precipitated was noted.

On the same OC (HFT “0.56%) mentioned above, such a test was carried out: TOC Ul which allowed to precipitate 33% of asphalt per gram of sample; TOC added with 2000 ppm of 11203, let precipitate 4% of asphaltenes per gram of empiane. The dispersant based on phosphoric esters of Example 1 did not obtain any result.

EXAMPLE N 6

In a dispersion test, as per Example 5, a crude oil as such gave a deposit of 7% The same crude product added with 1000 ppm of a commercial product based on alkylaryl sulphonates gave a deposit of 6%, while the same crude product added with 1000 ppm of 13197 (83% GCAG 15% MTBE) gave a deposit of 2%; with 1000 ppm of 13005 (85% methanol 15% tetrahedroxy-p-benzoquinone) the deposit was 3%.

In another preferential application thereof, the present invention provides compositions of additives to be used as antifoulmg in petroleum and / or petrochemical plants.

In fact, in petroleum processes, the precipitation of asphaltenes is one of the main causes of soiling of the equipment used. For example, the preheating trains and the furnaces of the plants are subject to dirt from asphalt, as well as the lamellar packs do ì demistar of the columns, including the nozzles of the pumparounds. In all these as in other cases, the use of the additives claimed here solves the problems of dirty.

In another preferential application, the present invention provides formulations of additives which allow to reduce the fouling of process equipment and / or catalysts in the petroleum / petrochemical industry.

The term "coke" used in the present invention refers to the set of heavy non-distillable compounds which are formed following, but not limited to, the thermal action on a fluid.

The term "extractable substances" used in the present invention refers to coke and / or to the heavier fractions of a hydrocarbon and / or fuel composition, generated as a result, but not limited to, the thermal action on a fluid in chemical plants and / or petrochemical and / or petroleum refining and / or metallurgical and / or petroleum extraction and / or engines and / or boilers and / or burners of all types of furnaces.

Fouling and coke deposition generally occurs when hydrocarbons contact a heated metal surface; then changes take place in them, through chemical reactions that decompose their unstable components. Undesirable products of said changes include coke, polymerised products and the like. The same phenomenon of deposition of coke do fouling also occurs in us catalysts. The fouling of the catalysts causes a decrease in activators or an increase in the pressure drop of the reactor, which results in the discharge of the dirty catalyst from the reactor.

The deposition of coke and / or fouling occurs in process equipment (ovens, heat exchangers) which come into contact with the fluids object of the present invention. When the concentration of coke and / or fouling becomes unbearable due to the continuation of the process (e.g. the skin temperatures of the oven are high, the ΔΡ on the exchangers is high), the equipment is cleaned (e.g. deco'cing with steam for the oven, extraction of the bundle and cleaning with pressurized water for the exchangers).

It has now been found, surprisingly, that some compounds can significantly decrease the formation of coke and / or fouling. If the lower coke / fouling formation is pushed to high levels, a higher distillation yield in light products will be obtained in petroleum / petrochemical plants,

Some processes are now known for solubilizing coal from mines. In these processes, among Pewter, some chemical compounds are used that have the ability to extract the hydrocarbons contained in the hard coal. Such compounds are used at a 2-3: l ratio with coal.

Non-specific solvents are believed to be extracted, at temperatures <100 ° C. the resins and waxes present in coal, although the yields are low. Solvents of this type are eg. ethanol, benzene, acetone. Specific solvents dissolve 20-40% of carbonaceous substances at temperatures <200 ° C. Oxygen and nitrogen compounds are generally good solvents because of the free electron doublet, which makes them polar solvents (Fud, 1951, 30, 145-158)! nitrogenous compounds are typically better than oxygenated ones. Extraction yields of 35-40% can be obtained by extraction with pyridine, certain heterocyclic bases and primary aliphatic amines. The secondary and tertiary aliphatic amines are less effective due to the spherical impediment of the akhilic group which affects the interaction between solvent and carbon. Degrading solvents are effective at temperatures in the range of 200-400 ° C. Their action depends on the thermal degnization of the coal to form smaller and more soluble segments. Phenanthrene, diphenyl and heavy oil fractions are examples of such solvents. Reactive solvents dissolve the carbon by reacting with it at temperatures of about 400 ° C. Examples of such solvents are compounds containing hydroaromatic rings: e.g. lelralin gives a higher conversion than its aromatic counterpart and the hydroaromatic member of heterocyclic compounds, e.g. indolìna, is more effective than the aromatic member, eg. indole. Such solvents act as hydrogen donors or as hydrogen transfer agents. Cycloalkyls also act in this sense, alone or in mixture with other solvents. Using as solvents, for example, polyaromatic compounds with 3 or more rings, the chlorhexanes donate hydrogen in the presence of radicals derived from coal, giving rise to high extraction yields. Even isopropyl and methyl alcohols can act as hydrogen donors, in which case the transfer of hydrogen is favored by the presence of KOH or potassium isopropoxide (Fud, 1979, 58 (6), 433-437). Other solvents useful for solubilizing: carbon aone can be, for example: phenol in mixture with p-Loluenesulfonic acid (the latter used as a catalyst), erosol, formamide, acetonitrile, nitromethane, acetic acid, dioxane, letraidrofuran, diethyl ether, dimethylsulfoxide, dimethylformamide, ethylenedhemraine, N-methyl-2-pyirolidone, methylethyletone, 1,2 dimethoxyethane.

A particular application of these compounds consists in the extraction of coal in superoritic conditions; in fact it is known that fluids under supercritical conditions increase the solubility of solids.

The use of these compounds, nor the use of fluids in supercritical conditions, has never been proposed in connection with the petroleum / petrochemical industry, (apart from tetralin and / or dimethyl sulfoxide at dosages of 3-5 % on the charge) especially in the connection of decreasing the formation of coke and / or fouting in the process equipment or, still less, to increase the distillation anger in light products.

Their use in these connections must therefore be considered as an advancement of the state of the art.

In fact, if they succeed in soiubilizing the coal, even more solubilize the heavy components of the crude and / or the coke that forms on the equipment, this translating to ea. in lower coke / foulmg and / or higher yields in light products and / or undermine HFT. In particular, the amount of additive injected will be higher than the coke deposited on the equipment, thus succeeding in obtaining its solubilization.

Without this being interpreted as a limitation of the present invention, some of these compounds, useful in the solubilization of coal, have already been mentioned above.

The performance will be increased if the chosen compound is in supercritical conditions under the 'normal' process conditions for the plant it is injected into. The compounds which therefore appear particularly interesting for the purpose are those which have a low critical pressure and a high critical temperature, so that they are more efficient at the reaction conditions of the plants (for the tiratic cracking, e.g. 480 - 500 ° C and 1.4 - 3 MPa); these compounds are preferentially chosen from those mentioned above or between compounds which contribute to improving the stability of asfallenes (and therefore alkanes will be discarded).

This constitutes an important difference with the state of the art of the application of supercritical fluids since, in the coke exhaustion or in the combustion, the compounds are artificially parted under supercritical conditions, in specifically designed plants: in the process claimed here the compounds are chosen specifically in so that, preferentially, they are in "hypercritical, or dense supacrylic conditions, under the normal process conditions of already existing plants." In particular, there is no petraliferous / ptrolchemical plant that uses an "external" fluid which becomes supercritical when it enters the process, in order to influence coke / fouling / yields.

Supercritical extraction is similar to both solvent extraction and distillation While the leaching of a solid with a liquid stream is a form of liquid extraction, the vaporization of a substance in a gas carrier stream is a form of distillation . All, below its critical temperature, the solvent will be liquid, while above its critical temperature it will be gassed at any pressure. In this way both processes can be carried out with the same solvent. In supercritical extraction the carrier gas is a supercritical gas, and under the conditions in which it is carried out it is difficult to physically distinguish between the two processes. Small changes in temperature and pressure in the critical region cause extremely large changes in the solvent's high density and dissolving power. The density, viscosity and diffusivity for a typical supercritical fluid are intermediate between those of a liquid and a gas.Although a supercritical fluid has a density approaching that of a liquid for high solvent capacity, the diffusivity is greater than several magnitude thus achieving better mass transfer rates

In the supercritical extraction according to the present invention, an organic solvent under supercritical conditions is used for the extraction of extractable substances. The process involves selective extraction of hydrogen-rich compounds for extractable substances and is based on the ability of heavy substances to vaporize in the presence of a compressed supercritical gas. For example, the products obtained by heating the coke to 400 ° C cannot be separated from the coke itself by distillation, due to the low temperature, while at higher temperatures an undesirable polymerization of the products takes place; however, when solvent vapors compressed near their critical temperature are used, the heavy organic compounds of coke acquire a high volatility. Under favorable conditions, a 1000-fold increase in volatility can be obtained, which allows the extraction of low volatile compounds at considerably lower temperatures than their own boiling points. in fact, as shown in the following description, a series of compounds and / or formulations have been found, according to the present invention, which allow it to reduce the quantity of coke formed to atmospheric pressure. It is obvious that such formulations will be more effective if they will contain compounds active in themselves in the reduction of coke which are in supercritical conditions under normal operating conditions of the plant.

Examples of other preferable compounds can be those of the group described from page. 32 line 14 on p. 33 line 20.

To better evict the supercritical efect it is good to select those compounds that have the highest Tc and the lowest Pc compared to the process ones.

In petroleum processes, for example, operating pressures vary from 0.1 to 8 MPa depending on the plant considered. Generally the highest pressures occur in catalytic reactors. Inside the process furnaces the pressure varies, eg. generally between 0.4 - 3.5 MPa, within the exchangers between 1 - 5 MPa.

For example, hexamethylbenzene has a Tc = 494 ° C and a Pc = 2.35 MPa: under the reaction conditions of a Coking plant it will be in a supercritical state and will solubilize the coke formed in the furnace, as well as contribute to the volatile reaction. of the heavy compounds present in the coke and / or in the heavy fractions of the feedstock. Visbreaking conditions (VBK) vary between 420 and 500 ° C and between 0.3 and 2 MPa at the exit of the furnace. Liquid phase cracking occurs under the process conditions. Generally, the severity of VBK is referred to as the yield in light products, ie gas and petrol, absolute or isoviscosity. The maximum permissible severity is determined by the stability of the residue and differs for the various feeds. Following the reactions that take place during VBK, a slow kinetic flocculation of asphaltenes can occur with consequent instability of the residue and of the products derived from it (fuel oils, bitumens). In practice, a formation of sludge and sediment is observed in the VBK residue.

Still referring to the present invention, to decrease HFT or CCR or increase distillation yields, all those solvents which are used in industry and in literature for the solubilization of fossil cardboard can also be used. Without being intended as a limitation of the present invention, some of these compounds have already been repaired in the present disclosure.

To evaluate the effectiveness of the formulations used, the ASTM D-4530 was used, in which the sample under examination is brought, at a programmed temperature, until the solvent used in the formulations deserves a particular mention.

Normally the chemical additives used in the hydrocarbon industry are conveyed in a solvent whose main characteristic must be that of economy, as well as non-toxicity. To this end, it is common practice to use aromatic naphtha as solvents, in particular heavy aromatic naphtha (from coal or petroleum).

In another preferred application, the present invention provides new types of solvent for the formulation of chemical products for industry.

The transextrication reaction between vegetable oil and alcohol (eg methyl, ethyl) which leads to the formation of mixtures of esters to be used as vegetable diesel (biodiesel) is now known. In this reaction, glycerin is formed as a sulproduct. This glycerin is not pure, but contains unreacted fatty acids, unreacted alcohol and water. A typical composition of this by-product can be, for example, the following: 60-70% glycerin, 15-30% fatty acids, 10-20% alcohol, 5-10% water.

For its subsequent industrial use, this by-product must therefore be subtracted from fatty acids, alcohol and water, as well as being bleached, with a consequent increase in costs.

On the other hand, surprisingly, both the mixture of esters (biodiesel) and glycerin with or without fatty acids can be used as a solvent in the formulations of chemical products for industry.

In particular, in the hydrocarbon industry, for example, corrosion inhibitors, antifouling, defoamers and de-emulsifiers can be formulated with these solvents. Compounds with supercritical * properties and / or other compounds according to the present invention.

In this specification, "GCAG" denotes fatty acid glycerin resulting from the above transesterification reaction, "GSAG" denotes fatty acid-free glycerin and "BDM" denotes the mixture of methyl esters.

These solvents are also particularly active in the reduction of coke formation and in the stabilization of the asfalLems, according to the present invention, and must therefore be included in the above lists. Their activity derives from the fact that they contain compounds according to the present invention (cs. esters, acids, alcohols) EXAMPLE N ° 7

Compounds can also be included in the formulations according to the present invention, also selected from those claimed herein, which possess particular properties.

Eg. salicylic acid chelates iron and prevents e-asphaltenes from forming aggregates, hence its usefulness as «nltfouling. Thiol-amroins break the poly and poly sulfide bridges that are present in heavy molecules, thus making it possible to have less sulfur in coking coke and / or OC. 1-metibiaphylene is reported to increase the colloidal stability of highly paraffinic residues.

Tetrahydroquinoline (THQ) is a potent H'donor (of tetralin) and can be used according to the present invention, e.g. to decrease fouling. THQ-ethanol and THQ-t etralin blends (preferably with 2-10% THQ) can also be used. 4-hydroxyindane has a combined solvoit index "greater than THQ.

EXAMPLE N ° 9

]] Vacuum residue (80% Es-Sìder 20% Brega) was added with 1000 ppm of 13155 (85% GCAO, 10% Toluene, 5% DMF). Simulated distillation (ASTM D-2887) was carried out to evaluate what the CCR gain means in terms of yields. The results are shown in figure I, where they are compared with respect to the blank (not added).

production of ethylene for sterni cracking).

In the formation of coke during the pyrolysis of hydrocabides, indices, especially raetylindenes, and naphthalenes, especially aceles and naphthalenes are important intermediates as precursors of coke. From other literature data other coke precursors are indicated, especially by reaction with fenalem. The coking speed increases with the conversion.

Since all known antifouling additives are formulated with heavy aromatic solvents, and these contain indoles and naphthalenes, it can be said that the antifouling itself contributes, even if minimally, to the formation of coke.

In fact, naphtha derived from coal contains a good part of alkylbenzenes, indines, tetralin, cyclopentane, ckloesane, t-decalin and naphthalene.

As will also be seen for the reduction of particulate emissions in fuels, the choice of the solvent is therefore particularly important.

The solvent chosen will therefore have the fundamental characteristic of not containing indanes and / or indeni and / σ fcnolenes and / or naphthalenes.

In the formulation of additives, for the purposes of the present invention, other types of solvent selected, but not limited to, from the following group can therefore be chosen; hexane, cyclohexane, benzene, toluene, xylene, cumene, MTBE, diethyl ether, mettl-isobutylketone, melylethetone, GCAG, GSAG, biodiescl.

EXAMPLE N ° 10

The feed from an ethylene plant (virgin naphtha and gas oil) was distilled; 10% of distillation residue was added with 1000 ppm of various formulations. Of

The coke deposits adhering to the metal surface are polar in nature.

The type of coke formed (porous or compact (graphite)) depends on the rheology of the tars and the type and concentration of the asphaltenes. Coke is more porous if the asphaltenes have a non-aromatic polycyclic structure, and more compact for aromatic asphaltenes. In this sense, the presence of non-aromatic polycyclic HCs in the formulation of Chemicals and / or the effect of the Chemicals resulting in a lower aggregation of asphaltenes helps in the formation of a better coke.

Among the compounds of the present invention the nitrogenous compounds in general, preferably the amines, even more preferably the cyclic amines, contribute to varying the morphology of the coke. Other compounds useful in such a connection are, for example, toluene which gives a fibrous and needle coke. As another example, tetrabutylammonium hydrosaid is an excellent swelling agent and can be included in the formulation as it will help to change the morphology of the formed coke, which will be more easily removable.

The swelling agents are well known in the tolubilization / extraction techniques of the fossil cartoon, but have never been used in the petroleum / petrochemical industry. In their known uses, the swelling agents in contact with the coal penetrate it and cause it to swell. The factors which control the amount of carbon that swells in a solvent are: a) the degree of solvent-carbon interactions, b) the degree of carbon branching (cross-link density). The swelling ratio is the ratio of the volume of! swollen coal, in equilibrium with the solvent, with respect to the volume of the original coal

In general, the solvents used for this purpose also have excellent properties of solubilization de coal.

Using swelling agcnts also the dccocking of equipment, eg. of the process ends, will be facilitated precisely because of the change in the morphology of the coke formed (from "needle-likc" to ’fluffy" or ’cloud-like")

In such connections, the swelling agents can therefore be used both in the metered formulations of continuous in the process (as forming part of hydrocarbon compositions or of fuels) according to the present invention, and during the decoking of equipment, e.g. in the decoking steam to the ovens and / or in the pressurized water used to clean heat exchangers, especially for those solvents which are also soluble in water.

Solvents mythologized as swelling agents fall into two classes: hydrogen bonding and non-hydrogen bonding. In general, and this confirms what has been seen in the present invention, the former are reported to be 25-50% more effective than the latter; the effectiveness of the latter can be increased following a first extraction of the coal with a solvent that forms hydrogen bond with it

The high efficacy in swelling, and therefore in the penetration of the solvent into the carbon, is attributed to the replacement of carbon-carbon hydrogen bonds with carbon-solvent hydrogen bonds: the same principle is also used, among others, in the present invention.

Among the swelling agents that do not form hydrogen bonds are preferred: gasolines, toluene, methyl clonir, cyclohexane, nitromethane, nitro benzene, acetooitrile, CCl ^, naphthalene, diphenyl, xylene, tetraline and methylyclohexane. Among the swelling agents forming hydrogen bonds are preferred: pyridine, methanol, ethanol, ethylenediamine, propanol, 1,4-dioxane, acetone, methylene chloride, chloroform, formamide, aniline, chloro benzene, o-dichlorobenzene, carbon disulfide, tetai drofuran, N, N-dimethylaniline, diethyl ether, drmethyl sulfoxide, acetophenone, dimethylformamide, ethyl acetate, methyl acetate, methylethyketone. 1-methyl-2-pyrrolidone, quinoline. A particular application of the present invention, as already mentioned above, therefore consists in adding a solvent soluble in water to favor the decoking and / or cleaning of equipment and / or the cleaning of materials contaminated with hydrocarbon products or petroleum fuels. Other compounds according to the present invention can be used in this connection, characterized by their solubility in water, which also have the ability to dissolve the hydrocarbon products of petroleum or coking fuels present.

Composite sheets will be injected eg. in the decoking steam to the ovens and / or in the pressurized water used to clean heat exchangers and / or in the cleaning of beaches / soils / sludge etc. contaminated eg. from oil.

In a particular application, the present invention allows the cleaning of apparatuses without them being disassembled. For and and for the heat exchangers it will not be necessary to extract the bundle, but the cleaning will be carried out "in situ" by circulating a solution (aqueous or hydrocarbon) containing the additives according to the present invention in a still further particular application, the the present invention also provides compositions for degassing the equipment (making the equipment "gas free" before inspection). These compositions, by solubilizing the hydrocarbons present, will make the atmosphere of the equipment non-explosive and allow for faster entry of maintenance personnel , avoiding long degassing (reclamation) through the use of steam (which is currently common practice).

a method for applying such compounds consists, for example, in adding the water with them and recirculating the water with the additives until it has an approximately constant content of dissolved compounds, or injecting them into the steam. A further advantage of this method is that the sohibited compounds can be recovered, even the heaviest ones, without their release into the atmosphere (as is the case with steam reclamation).

The equipment that can be cleaned according to the present invention includes, but is not limited to, refinery plants, floaters, API tanks, desalters, heat exchangers, columns, lines, storage tanks, etc.

Still in this connection, a further particular application of the present invention consists in limiting the soiling from HC on equipment in which SCOTTA water containing HC. For example, sour Water Stripper (SWS) plant often contains appreciable quantities of HC in charge (even> 500 ppm). These HCs cause dirt problems in the SWS system (columns, head condensers) which in the downstream systems (if, for example, the SWS column bottom acts as desalter washing water, the preheating exchangers of all water will result in oil dirty).

pi col ina, piperozine, pipcridine, propylamine, propylene glycol, propanol, propionamide, pyrazine, pyridazine, pyridine, pirogue, 2-pyrrolidoDe, N-methyl-2-pyrrolidone, quinazoline, quinoxaline, tetraethylene glycol, tetanusulfamine, tetanus sulfate GCAG, GSAG.

Some compounds described above also have additional advantages: for cs formaldehyde binds H2S and mercaptans.

EXAMPLE N ° 11

A beaker contained 10 g of a vacuum distillation residue.After 5 washes with 10 g of hot water containing 1% of methylglycol the weight of the residue was reduced to 4g

As already mentioned, in another preferential application, the present invention provides formulations which reduce fouling in process equipment.

An application that has been tested in the laboratory has been that of anti-fouling for the column bottom circuits (sluny) of FCC systems. The ability of the additives to maintain dispersion of the asphahenes and heavy substances present in the slumy has been evaluated. HDS implant loads were also evaluated

EXAMPLE N ° 12

10 cc of shery were placed in a centrifuge tube containing 90 cc of n-heptane, stirred and then left to settle for 15 min. 70 cc of mixture were then pipetted and 70 cc of n-heptane were added, stirring and letting sit for 15 min: finally, the amount of sediment was determined. Less sediment at the end of the test means a greater dispersion of the same (which will be eliminated during pipetting). A more successful technology for the fouling treatment of slurry circuits (Product 1) was evaluated on a sample of sluny treated with a commercial additive (Product 2); below are the results obtained.

EXAMPLE N ° 13

In another preferential application, the present invention provides formulations which reduce the coke content on the catalysts, also increasing the light yields.

During the feed processing process, a small part of the oil will decompose through secondary reactions and by polymerization and condensation it will form solid substances which will deposit on the surface of the catalyst forming coke. Coke causes a loss of catalytic activity, through chemical interaction with catalytic materials and blocking access to active sites. This deactivation reduces the life of the catalyst and causes economic losses.

EXAMPLE N 15

To test the coke reduction capacity we tested a formulation with the Micro Activity Test (MAT) according to ASTM D 5154-92. Here are the values

There is therefore a decrease in coke and an increase in the yields of distillates.

This application is particularly useful in hydrodesulphurization and / or hydrogenation and / or reforming plants, where the process pressure is such (generally> 5 MPa) to allow a wide choice of compounds that are supercritical under normal operating conditions, according to the present invention.

In another preferred application, the present invention provides novel formulations of discmulsifying products.

due to "micro spiosions" (Fuel, vol70, 1991,917-923). The peculiarity of GOAG is that the glycerin contained in it will favor the phenomenon of micro-explosions at a temperature higher than that of water: in fact, the limitation of water is that it "explodes" at low T; glycerin, "exploding * at high T, favors even more the fragmentation of the "core" of the drop just when the particulate core is about to form and not before, thus making it much more effective.

Among the formulations used for the CCR, those containing DMF are almost "ideal" for this application: DMF, in addition to solubilizing the coke, decomposes at high T forms formic acid, a compound well known for the abatement of ΝΟχ: this will result in also a significant reduction of this pollutant, and this is an added value.

In general, according to the present invention, compounds can be used which are insoluble in the oil phase (preferably HC), but which are dispersible therein; their boiling temperature will preferably be> 100 ° C. In this connection, the compounds selected from the following group can preferably be used:

These compounds can be injected directly into the oil phase and / or dispersed in the oil phase by means of a suitable emulsifier or injected in a suitable solvent and then dispersed in the oil phase with a suitable emulsifier.

Still on the subject of 'micro-explosions', organic nitro-compounds, especially high-boiling substances (eg nitro-alkylbenzcni), can also be used for compounds which explode at boiling temperature or other compounds according to the present invention; particularly useful are the triazoles and the substituted tetrazoles. In this connection, the compounds selected from the following group can preferably be used: 2,3,4 LrinitroanisolD, 1,3, S "trimethyl <2a4 ^ iinLtrobenzenel 1,3,5-trimethyl-2,4,6-thnitrobenzene, benzordroxamic acid , 2,4,6-trìnitro-m-cresol, n troglycerin, 1,3,6,8-tetrahydronflalene,, 1,3, S-trìnilronai \ alene, 2,5-didroxy-3.6> dinitro «p · benzoquinone , 2,4,6 trimitrufenol (picric acid), trinitrotoluene, trinitroacclonitrile 23,5-trinitro-p-xylene, triazoles or tetrazoles substituted with 0-2 C1-C20 hydrocarbon substituents

EXAMPLE N "17

On an OC without additive and one with additives with 1000 ppm of 13147 (80% CICAG 5% Pyridine 15% DMF) tests were carried out in burners, making smoke number and CO measurements on the flue gases. of the smoke number is made on a scale from 0 to 10; the evaluations are made on a filter in which the gases pass during the measurement. An evaluation of 10 means black, so the lower the number the better the performance; CO are expressed in

In another preferred application, the present invention provides additives and hydrocarbon compositions exhibiting less aggregation. This is particularly useful in cleaning plant equipment.

For example, when it is necessary to maintain a tank of petroleum products, it must be cleaned and reclaimed. Cleaning generally involves expensive mechanical interventions that involve disposal of the tank debris removed in the operation. Such foundations are generally made up of hydrocarbons, water and sediments, all well amalgamated and / or emulsified.

There is already a procedure (see Hydrocarbon Processing of January 1980) which provides for the use of chemical dispersants to facilitate the cleaning of the tanks. In this connection, the additives according to the present invention have proved to be much more active than other existing formulations.

EXAMPLE N ° 18

A tank base of crude oil (about 200 g) was added with 2000 ppm of 11200 (70% Naphtha 15% Methylglycol 15% o-Dìchlorobenzene) in a beaker, adding about 400 g of crude diluent. The mixture was kept under stirring for 3 days (T-SO ° CX after adding 500 ppm of a commercial pyridine-modified desemulsifier according to the present invention. It was stirred for another 2 days and allowed to settle for 1 day; yes

In another preferential application, the present invention provides formulations of additives and compositions of hydrocarbons and fuels with lower gaseous and / or particulate and / or soot and / or PAR emissions.

The dynamic stability of jet fuels will also be improved. It is measured with ASTM D 3241-92, in which a heated steel rod is passed through by a fluid at a pressure of 3.45 MPa.

Metal compounds reduce smoke at the expense of increased grazing emissions, since the additive is emitted in the form of oxide or sulfate, which contributes high particle mass in the exhaust smoke. an additive that reduces the emissions of gas oils and jet fuels that is free of metals, that is combustible and that does not contribute to the weight of the particulate matter emitted.

A further preferential application of the present invention is the reduction of the "coke * formation of the biodieseL E1. It is known in the literature that during combustion the biodicsel leaves a" resinous * "carbonaceous residue which creates problems both on the burners of the boilers and in the engines. internal combustion (deposits on the heads and gaskets) The results obtained by the present invention are of great interest and confirm the characteristics of the technology. In fact, if for the Vacuum residue it can be thought that some products may "mask * their effect (eg. N -heptane precipitates asphalts and therefore, with a sample that is not well homogenized, a 'deasphalted' sample is evaluated X in the biodiesel, there are no asphaltenes of the petroleum type and therefore the effect of the technology is clearly that of avoiding the aggregation of heavy molecules that are formed at high temperatures.

Tests were carried out to evaluate the carbon residue on biosiesel as it is and on 10% of the distillation residue of biodtesel and diesel fuel for motor vehicles. These last two tests are particularly severe as the fraction used is the heaviest part of the fuel, that is, the one that contributes to the formation of the carbonaceous residue. Being able to reduce this parameter will therefore contribute to reducing emissions, unburnt hydrocarbons, particulates and soot generated during the combustion of fuels.

In the formulation of the additives in these connections "supercritical * compounds may be added.

The starting diesel fuel had the following characteristics:

In the reduction of! In addition to the active ingredients used in the various formulations, a further novelty is the solvent used on CCR on self-reducing diesel. In fact, the solvent normally used for all Chemicals is heavy aromatic naphtha. In this solvent, however, there is a considerable amount of iridane (even 30%). From literature data, indane is considered to be responsible for the instability of gas oils, as it combines with phenalenone to form sediments; moreover, it has long been known that some nitrogenous compounds cause instability in gas oils. The addition of a common solvent therefore introduces an instability factor in the diesel fuel, hence the need for its replacement. Preferred solvents are: a) biodiesel, because it helps to lower the CCR of the residue and has a high cetane number; b) cyclohexane, to avoid aromatics (which have low cetane), c) MTBE due to its low cost and CCR reduction activity; d) THF for the activity in reducing CCR and because hydrogen-donor, e) no solvent. In particular, cyclohexane was favored because it has a low cost, and because it reduces the CCR of the residue, others to have a good cetane.

In a further preferential application, the present invention therefore provides formulations of additives to be used without any solvent, by injecting only the active principle. This application also has the advantage of saving the transport costs of the solvent (which often constitutes 60-90% of the formulations), reducing the overall costs of the additives, as well as having the aforementioned technical advantages.

EXAMPLE N ° 20

An engine test was conducted using a Fiat Tipo D (1700 cc diesel engine) at full load and at variable speed; The tests were carried out on a

Exhaust emissions during the running of the aforementioned engine were also assessed. It was found that HC emissions were reduced from 0.652 g / CV-h of the diesel oil without additive to 0.498 g / CV-h of the diesel fuel with the additive. The rotational particulate matter emitted was reduced from 0.365 g / CV-h for diesel without additive to 0.297 g / CV-h for diesel with additive. These reductions were achieved without significant changes in ΝΟχ and CO emissions.

PAH emission was then evaluated. expressed in ng of PAH per mg of paniculate emissions. The average test results for the two fuels at two load levels

A qualitative evaluation was then made on some parts of the engine after a 60,000 km run with diesel fuel additives; glow plugs, injectors and the interior of the combustion chambers were all clean and in excellent condition.

And products according to the present invention therefore reduce exhaust smoke, improve combustion and reduce engine consumption and dirt and improve emissions levels.

In another preferred application, the present invention provides additives and fuel compositions with lower carbon residue.

It has already been seen that some formulations according to the present invention contribute to reducing particulate emissions and that they act on the heavy part of the fuel (10% of the distillation residue).

However, the case of compliance with the commercial specification of the carbonaceous residue of the fuel is different.

On gas oils this specification is evaluated by measuring the CCR of 10% of the distillation residue; the specification is therefore evaluated after having distilled the sample, on the residual part.

It has been surprisingly seen that the additives and fuel compositions according to the present invention manage to have a significantly lower CCR than the starting one.

This is particularly important for diesel fuels of vegetable origin (biodiesel), which have much higher CCRs than petroleum ones.

Compounds suitable for this purpose are preferably those at a boiling temperature (Teb)> 200 ° C, even more preferably those with Teb> 300 ° C.

An exemplary list of compound numbers, according to those claimed in accordance with the present invention, can be found in the Handbook of Chemistiy and Physics 74 Edition - CRC Press · pages 3-12 to 3-523. Among these compounds, those selected from the following group are preferable: β-anthraquinoline, anthraquinone, antipyrine,

EXAMPLE N ° 21

A petroleum diesel had a CCR of 0.09% on 10% of the distillation residue. The additive of 1000 ppm of 13198 (75% dclohexane, 5% DEHA, 10% THF.

10% Morpholine) brought the CCR to 0.02%

EXAMPLE N ° 22

A vegetable gas oil (rapeseed methyl ester) had a CCR on 10% of the still residue of 0.24%. The yield of 1000 ppm of 13113 (85% Nafta 15% Solane RS41) brought the CCR to 0.10%. The additive of 10000 ppm of 13037 (85% Naphtha 15% Trictylene glycol) brought the CCR to 0.12%.

In a particular application of the pre-invented invention, on the other hand, the process conditions can be used to make additives hypercritical which are not so under normal operating conditions.

For this, the pressure inside a Visbreaker oven can be raised to about 14 ale to 25 "t to make it possible to use p-toluidine, hexamethylbenzene, etc. These compounds can also be used in the combustion of HC by means of an apparatus that makes them supercritical, to allow a lower formation of particulate and / or soot and reduce SOx emissions. ΝΟχ, PAH.

In a further application of the present invention it is possible to treat the residue in charge, to make it better penetrate the catalyst, in a plant for the demetalization of the residues and / or their conversion into light (catalytie hydrocracking).

Another preferential application of the present invention is evident from the analysis of Example 3. The hydrocarbon compositions according to the present invention are in fact characterized by their own better flow elements.

It is now known that the paraffinic components of hydrocarbons worsen their sliding characteristics. In this sense, the addition of non-paraffinic components in the formulation, for example, of the fuel oil helps to naturally lower, for example, the pour point. This operation is well known in the refining of petroleum products, but is not normally used for the aforementioned problems of compatibility between paraffinic residues and asphaltenic residues.

Since the present invention solves the compatibility problems between residues of different nature, it will also be possible to carry out blending between them such as to satisfy the cold characteristics of the final products as well.

Example N ° 3 provides confirmation of what is described here, as can be seen from the analysis of the Pour Point and the viscosity: adding an asphalenic residue to a paraffinic one significantly lowers both the Pour Point and the viscosity of the paraffinic residue. The addition of a formulation according to the present invention allows to obtain this, without any compatibility problem.

The present invention is also useful for separating organic compounds from solid waste and / or harmful waste (e.g. petroleum waste, drilling mud, refinery mud, and the like). It is also suitable for extracting oil from contaminated materials, such as: catalyst fines, filters, filter aids, drilling waste, steel mill trimmings, leaching waste, etc. The present invention is also useful for cleaning filter beds, earth contaminated by organic waste, etc. and to extract bitumen from oil shale.

It is also useful in reducing the viscosity of liquid fuels and waste materials.

Without being bound to any specific ratio between the components, the typical additive formulations for the applications of the present invention can be in the following range: solvent 0 * 100%; active 100-0%. The typical dosage for the applications of the present invention can vary between 1-200 ppm by weight referred to the material to be treated, preferably from 50-11000 ppm, even more preferably from 100-4000 ppm.

From what has been seen in the description of the present invention, the application cases are manifold; likewise, its operating conditions of use may vary.

It is obvious to those skilled in the art that the quantities of additives used according to the present invention will depend on the constituents of the HC and / or the fuel and / or the residues and / or the operating conditions and / or the results to be achieved. The present invention will therefore not be limited by any specific amount of additive to be used, although it must be substantially within the ranges specified above. The same will apply to the operating conditions of use of the present invention.

In general it can be stated that the addition temperatures are comprised between 1-2000 ° C, preferably between 1-1300 ° C, more preferably between 1-900 ° C. and the pressures will vary from 0 to 15 MPa.

Since asphaltenic molecules are very complex and of a nature dependent on the fluid that originates them, therefore of highly variable and unpredictable structure, it is not possible to define a formulation according to the present invention which gives excellent results with all eg. residues, fuel oils, fuels, crude oils to which the present invention can be effectively used. It will therefore be necessary to determine on a case-by-case basis which is the best formulation, without deviating from the general principles and dosages described in the present invention.

Without further deviating from the purposes of the present invention, all the formulations of compounds described in the present invention can also incorporate suitable and high-purpose quantities of already known compounds which have the effects and characteristics described herein. Therefore, the inclusion of, for example, dispersants, stabilizers for asphaltenes, combustion catalysts, detergents, in the formulations of compounds claimed herein cannot therefore jeopardize the novelty of the present invention. Likewise, the additive formulations according to the present invention can be used alone, as the sole additive for oils, or in combination with other additives for oils. such as pour point lowerers or dewaxing aids, corrosion inhibitors, antioxidants, slime inhibitors, etc.

Although the present invention has been described in relation to its preferential and / or particular applications it is obvious that various modifications may become apparent to those skilled in the art once the present description has been read. It is understood that the invention described herein is intended to cover such modifications as included within the scope of the following claims.

Claims (1)

CLAIMS 1) Aqueous hydrocarbon compositions and / or fuel and / or additives, characterized by one or more of the following properties: a) stabilization and / or re-epilation of the asphalts contained therein; b) reduction of fouling or coke in equipment in which such compositions flow; c) reduction of the VHFT do of the CCR do of the sliding characteristics; d) increase in conversion yields; e) reduction of the formation of soot and / or SOx of ΝOχ and / or PAH particles generated during their combustion; f) reduction of the coke formed on catalysts; g) presence of low cost solvents giving high activity regarding properties from a) to f). 2) Compositions according to claim 1 characterized by a greater stabilization or repeptization of the asphaltenes or greater stability to the blending or lower HFT or lower carbon residue or lower Pour Po bit or viscosity. 3) Compositions according to claim 2 characterized by the presence of one or more additives. 4) Additive according to claim 3 in which the formulations may contain one or more of the following classes of compounds: glycols of general formula 6) Additive according to claims 4 and 5 characterized by the presence of selected solvents in the following group: hexane, benzene, methanol, ethanol, GCAG, GSAG, biodiesel, MTBE, cyclohexane, cumene, toluene, xylene, ethyl ether, MEK, MIBK; or characterized by the lack of solvent. 7) Compositions according to claims 1 -6 characterized by a lower dirtying power and / or by a lower formation of coke in the apparatuses in which they flow and / or are contained and / or by higher conversion yields and / or by lower form. of coke on catalysts and / or from lower gaseous and / or particulate emissions. 8) Compositions according to claim 7 characterized by the presence of an additive according to claims 4-6. 9) Compositions according to claim 8 characterized by the presence of an additive which is in supercritical conditions under the normal operating conditions of the apparatuses in which said compositions flow and / or are contained. 10) Additive according to claim 9 characterized by a critical pressure <8 MPa, preferably <5 MPa. even more preferably <3.5 MPa, and from a critical temperature> 200 ° C, preferably between 200 ° C and 500 ° C. 11) Additive according to claims 9-10 where active compounds are selected from the following group: letrachloromethane, dimethylamine, erylamine, di formate, 12) Compositions according to claim 7 consisting of a hydrocarbon feed which enters a distillation and / or thermal conversion and / or catalytic conversion plant present in an oil refinery and / or petrochemical plant, in which the relevant equipment is preferably selected from the group: heat exchangers, columns, reactors, lamellar packs, demisters, setlers, tanks, ovens, lines, burners, boilers. 13) Compositions according to claims 7-12 characterized by the presence of coke with a different morphology than the same compositions in which an additive according to the present invention is not present. 14. Compositions according to claim 13 characterized by the presence of sweliingagents. 15) Compositions according to claims 13-14 characterized by the presence of a compound preferably selected from the following group: benzene, toluene, methyl chloride, cycloxane. nitramethane, mtrobenzene, acetonitrile CCl4, naphthalene, diphenyl, xylene, tetraline, methylcyclohexane, pyridine, methanol, ethanol, ethylenediaramine, propanol, 1,4-dioxane, acetone, methylene chloride, chloroform, formamide. aniline, chlorobenzene, o-dichlorobenzene, carbon disulfide. 19) Compositions according to claim 1 characterized by the use of compounds in the aqueous phase and / or in the vapor phase to favor the decoking, cleaning and reclamation of equipment and / or the cleaning of materials contaminated with hydrocarbon products or petroleum fuels. 20) Compositions according to claim 19 wherein the apparatuses are preferably selected from the following group; refinery plants, fi olers, tanks quinoasaline, tetraethylene alcohol, p-tolueasulfonic acid, triethylamine, GCAG, GSAG. 22) Compositions according to claim 1 characterized by the use of compounds with hydrogenation catalyst functions, selecting the following elements from the metal-organic compounds: Mo, Co, Ni, Fe; such compounds being added in the formulations of the present invention so that their final concentration in the compositions is between 10 and 150 ppm by weight. 23) Compositions according to claim 22 wherein the metal-organic compounds are prepared by reaction of an inorganic compound of the metal with a congest according to the present invention, preferably of the acid type. 24) Hydrocarbon and / or fuel compositions according to claim 1 characterized by an increased combustion efficiency due to lower gaseous emissions and / or reduction of the formation of particulate and / or filigree and / or $ Οχ do ΝΟχ do PAH generated during their combustion causes less fouling of the burners and combustion equipment, including the interiors of ovens and boilers, such as to cause minor blowing. 25) Compositions according to claim 24 characterized by the use of the compounds according to claims 4-6. 26) Compositions according to claim 24 characterized by the uses) of compounds which are insoluble in the oil phase (preferably HC), but which are dispersible therein; the boiling temperature of these compounds being preferably> 100 ° C, and being the same preferably selected from the following group: glycerin, MEA, DEA, TEA, succinimide, GCAG, GSAG, 2,3-dimeth, sianiline, 2-entJ3quinonsulfonic acid , 2-aminobenzamide, benzenesulfonic acid, bcnzimidazole, benznfuran, bipyridyl, putrescine (1,4 diaram mobutnno), butantride, 2-caprolatlane, cyclodecanol, diethylene glycol dibenzithether, trìazoethanol, N-3 5,6 hexanesol, hydantoin, hydroquinone dibeiuoate, hexacarboxybenzenic acid, ethylmiri state, 2-ammonium-3-chlorophenol, 2-amino-3-nitrophend, diaminophenol, 4-methyl-o-femlendiamine, triethylphosphine sulfide, isobutylpiperidine (2-hydroxyethyl) piperidine, 3-methylpiperidine, 1,3-diamino-2-propandan, 5-chloro-3-methyl-pyrazole, 3-methyl-1-phenyl-5-pyrazolinone, 2,4- or 3 ^ -diaminopyridine, 4-hydroxypyridine, methylpyrimidine, 8-aminoquinoline, monobenzyl ether resorcinol, monomethyl ester succinic acid, aci do o-tolylacetic, 1, 2,3 or 1,2,4 trìazole, trìisopropanolamine. Such compounds being able to be injected directly into the oil phase, dissolve into the oil phase by means of a suitable emulsifier, or injected into a suitable solvent and then dispersed in the oil phase with a suitable emulsifier. 27) Compositions according to claim 24 characterized by the use of compounds which give rise to "micro-explosions", such compounds being selected from the group of organic nitro-derivatives, especially the high-boiling compounds which erode at the boiling temperature of other compounds according to the present invention. 28) Compositions according to claim 27 characterized by the use of compounds selected preferably from the following group: 2,3,4 trinitroanisdo, 1,3,5 "trimethyl -214-dinylrobenzene 1,3,5-trimethyl-214,6- binitrobenzcne, benzohydroxamic acid, 2,4,6-trìiutro-m-cresole, nitroglycerin, 1,3,6,8-tetrahydronfUlene, 1,3,5-trinitronafthalene, 2. didroxy-316-dinithio-p-benzoquinone, 2,4,6-trinitrophenol (picric acid), trinitrotoluene, trinitroacetonitrile, 2,3,5-trinitro-p-xylene, tnazole or tetrazoles substituted with 0-2 C1-C20 hydrocarbon substituents. 29) Combustible compositions according to claim I characterized by lower carbon residue and / or lower emissions of particulate or / or soot and / or gaseous SOx, NΟχ, PAH and / or lower deposits on the engine and / or higher thermal stability and / or higher oxidation stability. 30) Fuel compositions according to claim 29 characterized by the presence of an additive according to claims 4 -6. 31) Fuel compositions according to claims 29 and 30 selected from the following group: diesel oil, fuel oil, jet fuel, petrol, virgin naphtha. kerosene. 32) Additive according to claims 4-6 containing suitable quantities of dispersants, known in the state of the art and preferably select them from the following group: a) substituted amines, in which the substituent is a hydrocarbon containing at least 8 carbon atoms; b) saddled compounds containing nitrogen and events a substituent with at least 10 aliphatic carbon atoms, this substituent being obtained by reaction of an acylating caiboxylic acid with at least IBI amine compound containing at least one -NH- group, said acylating agent being bound to said compound amino across an imido, starch, amidine or acyloxiamonium bridge; c) nitrogen-containing condensed compounds of a phenol, an aldehyde and an amino compound, having at least one -NH- group; d) esters of a substituted carboxylic acid; e) phenols substituted with hydrocarbons; f) alkoxy derivatives of an alcohol, a phenol or an amine; g) polxmethacrylates, h) polyisobutylcene succinimide; i) polyisobutylene succinate; 1) alkylaryl-soiphonates; m) alkanolamin-alkylaryl-sulfonaU; n) .tlkylaryl- sulfonic acids. 33) Additive according to claim 1 characterized by an increased solvent power towards asphalts and / or by the penetration of polar compounds, preferentially alkylated, with low molecular weight (up to 400) into the interior of the asphaltenic molecule (up to 400) and / or by the stabilization of the resins and from their subsequent delocalization. 34) Additive according to claims 4-6 characterized by its use to avoid dirt from asphalting in the processes of extraction of the raw material (as well as in the processes of its refining) and / or in order, for example, to: a) assist the emulsifiers ; b) control the crude / water whole; c) clean the bottoms of the tanks; d) clean the wells (both for production and injection); e) assist the injection and water clarification systems; f) clean the jet pumps and orifices. 35) Compositions of blanks according to claims 1 and 34 characterized by having fewer foaming problems. 35) Solvent according to claim 6 suitable for formulating additives according to the present invention, or other additives, to be used preferentially in connection with the treatment of hydrocarbons, selected from the following group: corrosion inhibitors, antifouling, antifoamers, de-emulsifiers. 36) Solvent for compositions according to claim 1 characterized by the lack of compounds of the type: indenes, indanes, naflalenes, phenalenes and / or a lower content in nitrogenous compounds. 37) Additive according to any one of claims 1-36, characterized by the following composition: 0-100% solvent; active 100% - 0% 38) Additive according to claim 37 wherein: the dosage, referred to the composition to be treated, is comprised between 1 * 20,000 ppm, preferably between 50 * 8000 ppm, even more preferably between 100 -4000 ppm; the addition temperature is comprised between 1 * 2000 ° C, preferably between 1-1300 ° C, more preferably between 1-900 ° C; the addition pressures are between 0 and 15 MPa, preferably between 0 and 8 MPa, more preferably between 0 and 5 MPa. 39) Application of an additive according to claims 4, 5, 6, 11, 14, 15, 18, 21, 26 to separate organic compounds from solid waste and / or harmful waste (e.g. petroleum waste, drilling mud, mud refinery, and the like); to extract oil from contaminated materials, such as: catalyst fines, filters, filter aids, drilling waste, steel mill trimmings, leaching waste; to clean filter beds, earth contaminated by organic waste; to extract bitumen from oil shale. 40) Method for treating the compositions referred to in the present invention in order to reduce their dirtying power and / or to have less coke formation in the equipment in which they flow or are contained and / or to have greater yields in their conversion and / or lower coke formation on catalysts and / or lower gaseous and / or particulate emissions, characterized by the following steps: a) adding a compound according to the present invention to a fluid; b) injection of the additive fluid into an apparatus suitable for its use. 41) Method according to claim 38 characterized by the variation of the operating conditions of petroleum / petrochemical plants so as to make it possible to reach supercritical conditions for the use, in such conditions, of any compound according to the present invention. 42) Application of an additive according to claims 4-6 to modify the formulations of emulsifiers. 43) Application according to claim 42 in which the additive of the present invention is between and 20% of the final formulation. 44) Application of an additive according to claims 4-6 to treat the charge of a plant for the demetallization of residues and / or their conversion into light, such as for example a catalytic hydrocracking.