HU219191B - Method for reducing of melting point of gasoline product - Google Patents

Abstract

The subject of the invention is a process for disposal of liquid hydrocarbons at room temperature using paraffin and/or wax. The method can be characterized by heating 95-99.5 parts by weight of paraffin or paraffin mixtures with a melting point of at least 40 °C, or wax or wax mixtures, or their mixture to a temperature at least corresponding to their melting point, and mixing 0.5-5 parts by weight of natural asphalt to the mixture, preferably gilsonite, and possibly 0.1–10 parts by weight of fly ash and/or 0.1–10 parts by weight of ground rubber and/or 0.1–5 parts by weight of talc and/or 0.5–1 parts by weight of chlorinated lime, and then the homogenized mixture is brought into contact with liquid hydrocarbon contamination, relative to its weight in an amount of at least 50% by volume, then the solidified homogeneous mixture is removed mechanically, and then, if desired, the paraffin and/or wax from the mixture is recovered and reused in a known manner. ŕ

Description

The present invention relates to a process for the disposal of hydrocarbons which are liquid at room temperature.

SUMMARY OF THE INVENTION The present invention relates to a process for the rapid and environmentally-friendly removal of pollutants caused by hydrocarbon products at room temperature, which can be used to eliminate hydrocarbon contamination on freshwater and seawater surfaces, and in the case of land spills or solid surfaces.

As used herein, liquid hydrocarbons are understood to mean any petroleum derivative or distillate having carbon numbers in the range of C5 through C15 and mixtures thereof which, under natural conditions such as atmospheric pressure and under normal ambient temperature conditions, do not release into the though intensely evaporated) retain their fluid nature.

In the process of the present invention, high-freezing paraffin (or a mixture of paraffins) heated above their melting point is added to the spilled liquid hydrocarbons in sufficient proportions to form a co-crystallizing solid, environmentally friendly mixture which is practically non-volatile and and finally recovering the paraffin component (s) in a known manner, which is then reused.

It is well known that the significant problem of our age is the increase of the environmental impact, the increase of the environmental load, which in many cases causes irreversible conditions, which endanger the wildlife itself. The reason for all this is basically the explosive growth of industrial production, coupled with significantly increased energy production and energy consumption.

Even today, about 30-30% of the energy sources are liquid and gaseous hydrocarbons, and in addition, oil and petroleum derivatives are the raw materials of many chemical technologies.

Increased production also poses a potential disaster risk, which must be taken into account at the extraction (mining) site, during transportation, and at the processing (eg refineries) and user (plant, storage, mining) requirements, despite.

The most hazardous properties of liquid hydrocarbons (petroleum derivatives or synthetically produced products) are precisely their natural fluidity. These

- increased evaporation and risk of explosion,

- flammability (low flash point),

- dispersal in water,

- infiltration into soil.

Due to their intensive evaporation, a large amount of air is released into the air in a short period of time, which can easily create a gas cloud which, either locally or over other areas, is a potential explosion center.

Practical experience has shown that the time between spillage and explosion or inflammation is extremely short, so time plays a crucial role in the effectiveness of damage prevention.

Another determining factor is the environment in which the spill occurs, as the effective remediation method can be selected depending on this.

In the case of out-of-date, corroded, submerged tanks, significant contamination of the surrounding soil is common, aggravated by the fact that the phenomenon is often only detected over a long period of time. Such problems can be found, for example, in abandoned military facilities, barracks, airports, out-of-date industrial sites and gas stations, but also due to accidental contamination of oil wells and accidental damage to the pipelines.

Liquid hydrocarbon that enters or into the soil penetrates its pores and is moved by gravity or capillary forces and, when it reaches the groundwater level, contaminates it and spreads along with any groundwater flow.

In the presence of oxygen, the degradation of liquid hydrocarbons into the soil by oil-degrading bacteria begins, but this natural process is extremely slow, contributing to the fact that anaerobic conditions become predominant in flooded soils and become the most potent bio-oxidative backbone.

There are many solutions for hydrocarbon decontamination of contaminated soils, including the use of drainage to reclaim large areas. In this known method, groundwater contaminated with liquid hydrocarbons (such as oil) is diverted and collected into monitor wells and, for example, special hydrocarbon sensors are used to pump the hydrocarbon layer to accumulate on the surface of the groundwater, as described in guideline HU 775.

A relatively slow but environmentally friendly solution is provided by biotechnological methods that use microorganisms to break down the petroleum components.

This can be done by extracting contaminated soil and remediation in so-called regeneration prisms, or even without extracting the soil.

Examples include patents HU 174 531, HU 181 817 and HU 181 558, which combine organic matter (e.g. peat) with loosened soil and inoculate with microorganisms.

According to U.S. Patent No. 4,871,673, microorganisms are adsorbed on a porous support to enter the soil.

In addition, patent application HU 212 826 accelerates the degradation process by the addition of enzymes and biohumus from Eisenia foetida, which is still several months long.

HU 219 191 Β

An even more serious environmental problem is the contamination of living waters (lakes, rivers, seas) with oil and other liquid hydrocarbon products. Environmental pollution is particularly high in the case of sea-going oil tanker disasters - so there is extensive research into the production of materials that can remove pollution easily, quickly, and wherever possible.

The liquid hydrocarbon that is released into the water quickly spreads over its surface, forming a cohesive film-like layer, which prevents oxygen uptake and, where appropriate, can cause complete oxygen deficiency.

Dispersants can disperse oil contamination, but these agents (such as surfactants) are often more toxic than the oil itself. Therefore, it is essential for their selection that they are non-toxic and do not damage aquatic life (eggs, larvae, plankton).

In this known method, suitable surfactants are used to alter the oil-water interface tension with minimal chemical addition, to form dispersed droplets, and to prevent the droplets from sticking to or adhering to the solid surface and sediment. The advantage of this method is that it removes blocking from oxygen, thereby accelerating microbiological degradation, but has the disadvantage that it does not solve the removal of contamination and is not applicable to larger contaminants (very high chemical demand).

Also, the use of various sinking agents, such as sand, brick, cement, ash, chalk, or glass beads, whose mechanism of action is to adsorb it on a dispersed hydrocarbon (oil) spot and then sink more difficult than water, does not provide a definitive solution.

They are only recommended for use in seas and possibly deep ponds, since the sinking material permanently pollutes living water.

Another solution may be to stitch and then skim off the larger spills. This may be the case, for example, with the use of oil-deflecting chemicals or by mechanical means such as floating trees or so-called submersibles.

The use of oil deflecting chemicals is hampered by the fact that they cannot be used in ice water, strong ripples, and the skidding must be done quickly because they are stable for only a few hours (6-8 hours).

An example of a submersible wall is the solution proposed in patent application HU 205 327, in which rubber ground is placed in bags (jute) compartments fixed with tensioning ropes. The specialty of the solution is that it not only absorbs the oil contamination but also adsorbs on the rubber surface, and then a relatively long-term absorption process, which results in a heavily swollen (oil-saturated) mass with a specific gravity below water.

The most widespread, and perhaps most effective, hydrocarbon deprotection method is the use of various hydrophobic oil-binding adsorbents which are dispersed or even sprayed with a stream of water. These materials may be of organic origin such as wood shavings, sawdust, peat, straw, minerals such as perlite, expanded perlite, zeolite or synthetic origin such as polyurethane foam, cellulose, beads.

In the process of patent application HU 183 410, the hydrophobic character, and thus the efficacy of the agent, is enhanced by forming a polymeric coating which can be applied to any organic or inorganic particulate material which is capable of adhering to the outer and / or inner surface.

The key to selecting the right adsorbent (sorbent material) is that it has a high specific surface area, a low specific gravity, a high adsorption capacity and a sufficient pore size, and has good oil binding efficiency (contain absorbed oil) and, where possible, regenerated.

(The relatively inexpensive and significant amounts of peril used do not recover the bound oil and are therefore generally burned - a major disadvantage.)

Because of its importance, we would like to mention the Swedish-developed product Bregoil Sponge (manufactured by Breg. Sp. Int. Inc. New York), which is made of specially prepared waste fibers and is biodegradable. This material can absorb four to seven times its weight of oil while swelling several times its volume, without the particles becoming sticky or sticky. A large part of the absorbed oil can be recovered by pressing and the remaining droplets can be used as fuel. The product is recommended for decontamination of harbors, lakes, beaches, motorways, industrial sites. (Source: Chemical Eng., Vol. 90, No. 7, p. 49)

Sorbent materials have the advantage of being able to remove impurities on the water surface or solid surfaces (such as driveways), but have the disadvantage that they do not reduce the flammability of the hydrocarbons they bind, so they require the same high safety standards as the impregnated material itself.

Finally, it should be noted that biotechnological methods can be used to eliminate hydrocarbon contamination of waters, provided that their relatively slow mechanism of action is permissible. An example would be the process according to patent application HU 178 724, which helps to accelerate the decomposition process by adding to the water the nitrogen and phosphorus salts made lipophilic and suspended. The advantage of these solutions is that they are non-toxic and do not disturb the ecological balance.

Comparing the hydrocarbon deprotection methods outlined above, it can be concluded that there is no method that would be effective in all circumstances under different circumstances. The solution to be used in the given case must be chosen according to the actual situation, even in combination with known solutions. The remediation method

EN 219 191 Β the economic aspect must always prevail over the ecological and environmental aspects, of which we should emphasize

- speed (to minimize the presence of volatile constituents in the air and to prevent the risk of explosion or inflammation),

- the substance used is non-toxic and / or environmentally friendly,

- do not drain absorbed material,

- and, where possible, recoverable, reusable (do not burden the environment unnecessarily).

The present invention is directed to the development of a novel process which is capable of satisfying the above requirements to the fullest extent possible, but which is also capable of removing liquid hydrocarbons which are found on land or on the surface of waters.

It is known that heavy distillates, distillation residues, such as gas oils (diesel oils), fuel oils and fuel oils obtained during the atmospheric distillation of crude oils, have high paraffin content and thus have high paraffin content.

In order to ensure that the oils are sufficiently fluid even during cold (winter) periods and that the lubricants are sufficiently viscous, a variety of paraffin removal processes have been developed to remove these high-freezing hydrocarbon components. (Paraffin removal may be accomplished by filter presses, molecular sieves, solvent dilution and cooling of the dilute solution, and catalytically, depending on the structure of the paraffin content (microcrystalline, amorphous paraffins).

The present invention is based on the discovery that when liquid hydrocarbons are normally mixed with liquid paraffins, the pour point of the resulting mixture (solution) is significantly increased, resulting in a homogeneous structure at room temperature or at ambient, e.g.

It should be noted here that paraffins are understood to mean a mixture of high molecular weight, open-chain, saturated hydrocarbons having carbon numbers predominantly in the range of C24-C25 (ErdeiGrúz T .: Chemical Science, K.. K. 1963). Within this, the macroparaffins are in the range of 18-30 ° C. Semi-microcrystalline intermediates have carbon numbers in the range of about 30-40 per molecule, but also contain components other than normal hydrocarbons and have a melting point. Microcrystalline paraffins have a carbon number of 40-50 and a melting point of 60-104 ° C.

It has further been found that if the paraffins, paraffin blends, waxes or wax blends are not used alone, 0.5 to 5% by weight of natural asphalt, preferably gilsonite, is added to the blend, thereby improving its disposal.

A preferred process variant is that 0.1 to 10% by weight of fly ash, preferably power plant fly ash and / or 0.1 to 10% by weight of fine gum and / or 0.1 to 5% by weight of talc and / or 0.5 to 2% by weight of chlorine is mixed.

The fly ash, gum powder, talc and chlorine additives are used in a very finely divided manner and these additives are used only where appropriate.

The surface of the mixture containing the paraffin and / or wax and natural asphalt is increased by the mixed fly ash, gum powder and talc, thereby improving the disposal effect.

The role of chlor-lime is to disinfect, since the contaminated material often contains organic contamination that needs to be disinfected.

The power plant fly ash is preferably used in a particle size of 0.005-0.009 mm, the rubber powder is used in a particle size of 0.001-1.0 mm, talc is used in a particle size of 0.01-0.001 mm and a chlorine pulp is used in a particle size of 0.1-0.001 mm.

The present invention relates to a process for the disposal of hydrocarbons which are liquid at room temperature using paraffin and / or wax.

The process is characterized in that 95 to 99.5 parts by weight of paraffin or paraffin mixtures having a pour point of at least 40 ° C, or a wax or wax mixture, or a mixture thereof, is heated to at least their melting point and 0.5 to 5 parts by weight of natural asphalt are added. , preferably gilsonite and optionally 0.1 to 10 parts by weight of fly ash and / or 0.1 to 10 parts by weight of gum flour and / or 0.1 to 5 parts by weight of talc and / or 0.5 to 1 part by weight of chlorine and then the homogenized mixture is liquid contact with a hydrocarbon impurity in an amount of at least 50% by weight, and the solidified homogeneous mixture is mechanically removed.

In the process according to the invention, the paraffin or the paraffin mixture is recovered from the mixture after the mechanical removal in a known manner and reused.

Optionally, the liquid hydrocarbon impurity itself is preferably heated to at least the melting point of the paraffin or paraffin mixture used.

It is also desirable to carry out the process of heating both the hydrocarbon impurity and the paraffin or paraffin mixture to a total temperature at least such that the paraffin or paraffin mixture melts.

It is further preferred that the mixture containing the paraffin or the mixture containing paraffin is applied to the surface of the liquid hydrocarbon contamination by means of a pressurized heating device.

Preferably, effective contacting is achieved by stirring.

The process of the present invention preferably utilizes commercially available intermediate paraffins.

Where appropriate, a mixture of two or more commercial products may be employed.

It is also advantageous to mix the liquid paraffin or the paraffin mixture in a 1: 1 by volume ratio to the liquid hydrocarbon.

HU 219 191 Β

The following examples illustrate the process of the present invention, but are not to be construed as limiting the scope thereof.

Example 1

Curing kerosene

(a) Pour 50 parts by weight of kerosene into a vessel fitted with a stirrer and heat the vessel to 50 ° C. To the heated hydrocarbon is added 50 parts by weight of a melting point of 90 ° C of intermediate paraffin containing 95 parts by weight of paraffin and 5 parts by weight of gilsonite. After complete mixing, the liquid mixture is poured into cooling water at 20 [deg.] C., at which time the mixture solidifies.

The solidified material is removed from the surface of the water by mechanical filtration.

b) The experiment is repeated using the same conditions, but the liquid mixture is poured into a mold and solidified at room temperature.

Example 2

Hexan's conclusion

As described above, 50 parts by weight of hexane were poured into a vessel, the temperature of which was raised to 50 ° C, and 30 parts by weight of 90 ° C intermediate paraffin melt containing 90 parts by weight of paraffin, 0.1 parts by weight of gilsonite and 9.9 parts by weight of 0.005 mm. and particle size talc.

After thorough mixing, the mixture is poured into a mold and allowed to cool to room temperature. At this temperature, the cooled mixture became solid.

From the solidified mixture, paraffin and hexane are separated by distillation.

Example 3

Engine oil binding

We pour tap water into a basin and add 100 parts by weight of motor oil, which spreads over the surface of the water.

200 parts by weight of a liquid intermediate paraffin mixture heated to 100 ° C containing 84 parts by weight of a mixture of paraffins of various freezing points, 3 parts by weight of gilsonite, 0.5 parts by weight of 0.01 mm talc, 5 parts by weight 0.1 mm powder containing 5.5 parts by weight of 0.009 mm power plant fly ash and 2 parts by weight of 0.01 mm chlorine resin.

The melt mixture is prepared by weighing the paraffin mixture into a vessel with a heating jacket, melting it and adding the additives with constant stirring.

This homogenized mixture is applied to the oil spot.

The mass is then stirred and allowed to solidify.

After solidification, the solid oil-paraffin mixture is removed by mechanical filtration.

The remaining water remained completely clear, leaving only a trace of oil on the color of the water.

The experiment was repeated using water mixed with sea salt. The result was the same.

Example 4

The conclusion of Pakura

100 parts by weight of the pakurah were heated to 80 ° C and then 60 parts by weight of a paraffin mixture containing 95.4 parts by weight of a 1: 1 mixture of paraffin and wax, 5 parts by weight of gilsonite and 0.1 part by weight of a 0.01 mm granular gum were added. contain.

The mixture of pakura with the paraffinic mixture is homogenized, the mixture solidifies at 60 ° C, and the solidified mixture is removed by filtration.

Example 5

Binding of tetrachlorobenzene

Tetrachlorobenzene was mixed in a melted paraffinic melt heated to 70 ° C using a closed vessel.

The paraffinic mixture contains 99.1 parts by weight of a paraffin mixture and 0.8 parts by weight of gilsonite.

The contents of the sealed vessel were heated to 90 ° C.

The melt is then poured through a fine heated filter and the mixture is allowed to solidify. The volume ratio of tetrachlorobenzene to the paraffinic mixture was 1: 1.

The quality parameters of the intermediate paraffin used in the examples are as follows:

viscosity 100 ° C, m ² / s 5.7 drop points 64 ° C penetration 25 ° C, 0.1 mm 19 oil content,% 0.95

Although in some examples intermediate paraffin was used, it will be appreciated that other high-freezing paraffins may be used in the same manner.

Optionally, it may be advantageous to use two or three different compositions or structures of paraffin, such as a defined volume blend of polymer-modified microcrystalline semi-refined wax and crude paraffin. (This facilitates post-process separation, for example.)

The actual volume percentages used depend on the particular materials used, i.e. the composition of the hydrocarbon to be bound and the paraffinic mixture used, but also the environmental impact. Optimal values can be determined by recording phase diagrams.

Due to the low heat capacity of the paraffins, the mixture hardens in a very short time, in an instant. This fact requires immediate intervention as soon as possible for effective remediation, especially for liquid hydrocarbons spilled on soil surfaces, since a paraffinic mixture cannot penetrate the pores, thus essentially eliminating surface runoff.

In summary, despite the limitations of use, the significance of the process of the present invention lies in the fact that the resulting solid

EN 219 191 Β environmentally friendly (non-toxic), harmless to the environment (practically low vaporization or very high flash point), and recoverable and reusable (does not burden the environment, so no deposit required), thus relatively expensive economical due to multiple use of paraffin.

A particular advantage of the solution is that the resulting malaria can be eliminated in a very short time (the freezing is almost instantaneous) and then the final product can be removed from the site without danger and stored anywhere for any length of time.

Claims (8)

PATENT CLAIMS A process for the disposal of hydrocarbons which are liquid at room temperature using paraffin and / or wax, characterized in that 95 to 99.5 parts by weight of paraffin or paraffin mixtures having a freezing point of at least 40 ° C or a mixture of waxes or waxes are heated to at least their melting points. and adding to the mixture 0.5 to 5 parts by weight of natural asphalt, preferably gilsonite, and optionally 0.1 to 10 parts by weight of fly ash and / or 0.1 to 10 parts by weight of gum flour and / or 0.1 to 5 parts by weight of talc and / or 0.5 to 1 part by weight of chlorine, followed by contacting the homogenized mixture with a liquid hydrocarbon impurity in an amount of at least 50% by weight, mechanically removing the solidified homogeneous mixture, and optionally recovering the paraffin and / or wax from the mixture; we use it again. Process according to claim 1, characterized in that after removal of the solidified mixture, the paraffin or the paraffin mixture and / or the wax or the wax mixture is recovered in a known manner and reused. 3. A process according to any one of claims 1 to 4, characterized in that the paraffin or the mixture containing the paraffin or the wax or the wax mixture is heated to a temperature corresponding to the melting point. The process according to claim 1 or 2, characterized in that the liquid hydrocarbon impurity is heated to a temperature corresponding to the melting point of the mixture containing the paraffin and / or wax used. 5. A process according to any one of claims 1 to 3, characterized in that the mixture containing the paraffin or the mixture of paraffin and / or wax or wax is applied by pressurization to the surface of the liquid hydrocarbon contamination. 6. The process of claim 1 wherein the intermediate paraffin is used. A process according to claim 1, wherein a mixture of two or more paraffins or waxes of different compositions is used. 8. A process according to any one of claims 1 to 4, characterized in that the liquid hydrocarbon contaminant is mixed in a 1: 1 ratio by volume with a liquid paraffin or a mixture of paraffin and / or wax or wax mixture.