The method of dehydration of the emulsion of heavy pyrolysis resin

 

(57) Abstract:

The invention relates to the oil and gas industry and can be used for emulsion breaking the heavy pyrolysis resin. For dehydration of the emulsion of heavy pyrolysis resin conduct mixing water emulsion with a demulsifying agent, defending the working mixture before formation of the two-phase system and the phase separation was obtained. After mixing the aqueous emulsion and demulsifier the mixture was added an aqueous solution of mineral salts with a concentration of salts corresponding to at least 50% increase saturation of the aqueous solution. The mass ratio of the mixture:salt solution 1:0.5 to 1:10. The technical result - the deep dehydration of the original emulsion with residual water content less than 1 wt.%. table 1.

The invention relates to the oil and gas industry and can be used for the destruction of aqueous emulsions of heavy tar, a byproduct of the pyrolysis production.

As is known, the process of pyrolysis of any hydrocarbons produced pyrolysis gas, a liquid product - tar and coke. Pyrolysis tar is a complex mixture of aromatic, Vysokomolekulyarnye and unsaturated hydrocarbons in the liquid products of pyrolysis increases, what makes the resin valuable raw material for chemical industry.

In industrial practice often distinguish between light and heavy resin. Light pyrolysis resin has a density 0,9-0,98 g/cm2heavy pyrolysis resin (SCC) - 1,00-1,05 g/cm2. The output of the resin ranges from 3 to 40% on raw materials and mainly depends on the contact time and the molecular weight of the feedstock, increasing their growth. From TPS can be allocated to individual aromatic bi - and polycyclic hydrocarbons (naphthalene and its homologues, biphenyl, and others ). On the basis of SCC can be obtained peck for the production of electrode coke, polymer resin, widely used in construction materials and electrical products (see[1] - Stepanov A. C. Production of lower olefins. Kiev: Naukova Dumka, 1978, S. 216-217). Also, the SCC can be used as a component of boiler fuel.

However, the existing some pyrolysis production technology, providing water rinse the pyrogas in the column apparatus, leads to the formation of highly stable water emulsion of the TPS with a water content of up to 60 wt. %. This makes it virtually impossible the further processing of heavy pyrolysis resin, quoting.

In order to perform further processing TPS need a process that will ensure maximum removal of water from the aqueous emulsion TPS.

At the present time to prepare for the processing of heavy oils, which is also vodoprovodnoye (oil) emulsion, traditional technology is used - thermochemical dehydration and desalting using reagents demulsifiers (see[2] - Batueva I. Y., Gail A. A., Pokonova Y. C. and other petroleum Chemistry. - L.: Chemistry, 1984, S. 159). This process is carried out at a temperature in the range of 20-80oWith the reagent consumption is 50-600 g/t of raw material depending on the type of demulsifier and oil composition.

Features of chemical composition of the TPN associated with the presence of a large number of natural emulsifiers - resins, impedes the dehydration process according to the traditional scheme, suitable for petroleum hydrocarbons. The components of emulsion stabilizers, as well as high density, almost equal to the density of the aqueous phase, require the development of methods of dehydration TPS, taking into account the specifics of its physico-chemical properties. As our investigations have shown, even a significant increase in consumption Deema residual water in the IB below 30 wt.% (see table).

Known effective method of dehydration of high vodoprovodstroy emulsion (emulsion natural bitumen) mixing the partially dehydrated (due to the removal of free water released by heating the emulsion to 40-50oC) bitumen with demulsifier (nonionic surfactant) in an amount of 400 g/t of raw hydrocarbon diluent (solvent) - distillate fraction of PB in the ratio of 1:0.5 to 1:2, which in this case is injected to reduce the viscosity, the density of raw materials and increase effectiveness of demulsifier. Then there is the assertion of the mixture of emulsion and distillate at a temperature of 70-80oWith over 8-12 hours and removal of the liberated water, the residual water content in the dehydrated bitumen does not exceed 0.5% (see [3] - Ismagilov, I. H., Thrones Century. P. and other Experimental research and development of technologies for the dehydration of natural bitumen deposits Tataria // Series "Petroleum engineering"- M: VNIIEM, 1992, S. 47-48).

This method has several disadvantages: the content of residual water in dehydrated TPS is more than 4 wt.% (see table); add thinners changes the composition of raw materials and reduces technical and economic parameters of the process.

The task image is Denmark residual water less than 1 wt.%

The problem is solved by the method of dehydration of the emulsion of heavy pyrolysis resin comprising mixing a water emulsion TPS with demulsifier, defending the working mixture before formation of the two-phase system and the phase separation was obtained. After mixing the aqueous emulsion and demulsifier the mixture was added an aqueous solution of mineral salts with a concentration of salts corresponding to not less than 50% saturation, when the mass ratio of the mixture: salt solution 1:0.5 to 1:10.

The invention is illustrated by the following examples.

Example 1. Take 100 g of raw material (water emulsion TPS with a water content of 50 wt. %), add the demulsifier Reapon-4B in an amount corresponding to its consumption of 300 g/t of raw materials, and conduct dehydration using a pre-prepared aqueous solution of sodium chloride NaCl (concentration CNaCl= 350 g/l, the mass ratio of the solution to a capacity of 0.5). Mixing the emulsion with a solution of salt was carried out in a thermostatted at 80oWith a separating funnel using electronically to the full distribution of water in the emulsion phase. After settling in for 1-1 .5 hours at the same temperature produces a two-phase system: bottom - water phase, asteady. This system has a clear interface and easy to split. We obtained after separation dehydrated TPS determine the content of residual water by the method of Dean and stark (see[4] - GOST 2477-65. Determination of water content.).

Example 2. Take 100 g of raw material (water emulsion TPS with a water content of 50 wt.%), add the demulsifier analogously to example 1 and conducting dehydration using a pre-prepared aqueous solution of sodium chloride NaCl (CNaCl= 350 g/l, the mass ratio of the solution to the raw material to 1.0). Mixing the emulsion with a solution of salt was carried out in a thermostatted at 70oWith a separating funnel using electronically to the full distribution of water in the emulsion phase. Next, the process carried out analogously to example 1.

Example 3. Take 100 g of the raw material, add the demulsifier analogously to example 1 and conducting dehydration using a pre-prepared aqueous solution of sodium chloride NaCl (CNaCl=250 g/l, the mass ratio of the solution to a capacity of 2.0). Next, the process carried out analogously to example 1.

Example 4. Take 100 g of the raw material, add the demulsifier of Deproxin-157 (D-157) in an amount corresponding to its consumption of 400 g/t of raw materials, and conduct obezvozhivani the multiplicity of a solution to the raw material - 2,0). Next, the process carried out analogously to example 1.

Example 5 (the prototype). Take 100 g of raw material (water emulsion TPS with a water content of 50 wt.%), add the demulsifier Reapon-4B in an amount corresponding to its consumption of 400 g/t of raw materials, and conducting thermochemical dehydration adding hydrocarbon diluents are easy pyrolysis tar (LPS) and polyalkylbenzenes resin (ABS) when the mass ratio of the emulsion TPS: ABS: FSC=to 1.0:0.5 to 1.0 second. Mixing the emulsion with the solvent were carried out in a thermostatted at 80oWith a separating funnel using electronically to a uniform distribution of the solvent in the emulsion phase. After settling in for 8 hours at the same temperature produces a two-phase system: bottom - aqueous phase consisting of a mixture of spin-off of water and a solution of wax components in the diluent, the top hydrocarbon phase consisting of TPS dissolved in the diluent, and unremoved water. This system has no clear boundaries, but can be separated, but with the loss of a significant amount of hydrocarbons. We obtained after separation of the upper phase (solution dehydrated TPS in diluent) determine the residual water content is different TPS watering, other mineral salts and without salts listed in the table.

Provided in this invention a method of emulgirovanija combines both thermochemical and physical effects on the emulsion. Introduction of a solution of inorganic salts in the system contributes to a more complete distribution of the demulsifier in the hydrocarbon phase of the emulsion, which leads to an increase in its demulsifying action. On the other hand, the presence in the system of saline water with high concentration of salt increases the density of the aqueous phase in the emulsion system and increases thereby the difference of the densities of the phases, which positively affects the results of the sedimentation and separation of the water and TPS.

The dehydration process was carried out at a temperature that does not permit boiling of the aqueous phase in the system; at high multiplicities of the salt solution to a mixture of the emulsion and demulsifier possible the implementation process at a lower temperature.

The method of dehydration of the emulsion of heavy pyrolysis resin (SCC), including mixing water emulsion TPS with demulsifier, defending the working mixture before formation of the two-phase system and the phase separation was obtained, characterized in that after serenely, corresponding at least 50% increase saturation, when the mass ratio of the mixture: salt solution 1: 0.5 to 1: 10.

 

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SUBSTANCE: to oil emulsion is added surface-active demulsifying additive containing (i) aqueous solution of surfactant based on sodium salt of oxyethylated isononylphenol carboxymethylate expressed by general formula C9H19-C6H4-O-(-CH2-CH2O)nCOONa, where n=10-12, (ii) self-emulsifying organosilicon compound, and (iii) sodium or calcium chloride salt.

EFFECT: increased demulsifying power.

1 tbl, 13 ex

FIELD: composition for crude oil treatment in oil producing and oil refinery industry.

SUBSTANCE: claimed composition is obtained by mixing of four components. Oxyethylated isononylphenone sodium carboxymethylate of formula C9H19-C6H4-O-(-CH2-CH2O)nCOONa, where n = 12 is used as an active ingredient. Silicone is introduced in composition as self-emulsifying addition, and aqueous or aqueous-salt solution is used as solvent. Composition contains (mass %) oxyethylated isononylphenone sodium carboxymethylate 25-35; self-emulsifying silicone addition 0.01-1.0; calcium chloride 0-25; and as balance: water.

EFFECT: composition with high demulsifying action and reduced foaming formation in crude oil emulsion.

2 ex, 1 tbl

FIELD: crude oil treatment.

SUBSTANCE: invention is directed to treatment of crude oil before processing by destroying persistent oil-water emulsions, dehydration thereof, and desalting with various-purpose demulsifier. Preparation of the latter involves preliminary oxypropylenation of nitrogen-containing compound (etylenediamine, tetramethylenediamine, hexametylenediamine, or polyethylene-polyamine) on heating. Resulting mixture is subjected to further oxypropylenation and then oxyethylenation in presence of alkali catalyst on heating. Thus obtained demulsifier is finally dissolved in solvent at weight ratio (45-55):(55-45).

EFFECT: increased efficiency in destruction of oil-water emulsion and in removal of petroleum products from waste waters accompanied by good corrosion protection and anti-deposits effect.

2 cl, 3 tbl, 20 ex

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EFFECT: increased efficiency in protection of oil-field equipment against corrosion and asphaltene-tar-paraffin deposits and enabled and enabled simultaneous treatment of waste water to remove oil derivatives.

2 tbl, 16 ex

FIELD: oil and gas production.

SUBSTANCE: invention relates to pre-processing treatment of crude oil, in particular to dehydration and desalting of oil with the aid of surfactant additives. Composition of invention contains 15-17% glycerol-based ethylene oxide/propylene oxide block copolymer, 5-15% oxyethylated glycerol/toluene diisocyanate reaction product, additionally oxyethylated fatty acid-based amine ("Oksamin-15") or product of reaction thereof with phosphorus-containing compound ("Oksamin-F 15"), and solvent to 100%.

EFFECT: increased efficiency in protection of oil-field equipment against corrosion and asphaltene-tar-paraffin deposits and enabled and enabled simultaneous treatment of waste water.

2 tbl, 16 ex

FIELD: crude oil treatment.

SUBSTANCE: objective of invention is treatment of crude oil before processing, in particular dehydration, desalting of oil, destruction of water-oil emulsions, and improvement of rheological properties to facilitate transportation of oil through crude oil lines. Composition contains 25.0-55.0% of nonionic demulsifier, notably ethylene oxide/propylene oxide block copolymer based on monoethylene glycol with average molecular mass 4300, 5.0-75.0% of diethylene glycol production distillate (including 20.0-40.0% ethylene glycol methyl ether, 30.0-60.0% diethylene glycol methyl ether, 2.0-5.0% methanol, and 15.0-18.0% water), and solvent, preferably methanol (to 100%).

EFFECT: enhanced oil dehydration and desalting efficiency and improved rheological properties of oil.

1 dwg, 2 tbl

FIELD: crude oil treatment.

SUBSTANCE: polymer-containing trapped emulsion is pumped from earthen container into settler containing fresh industrial water to obtain emulsion-to-water volume ratio 1:2. Resulting mix is heated via circulation through heat-exchange to 70-80°C while simultaneously receiving demulsifier in amount 20-50% of its estimated amount and aqueous solution of active chlorine-releasing compound in amount corresponding to 0.2-0.4 kg active chlorine per 1 m3 trapped emulsion. Hot trapped emulsion is then pulped to section of dispersers disposed in tubes supplying fresh industrial water preheated to 40-50°C while simultaneously feeding the rest of demulsifier to pump pumping trapped emulsion observing emulsion-to-water volume ratio (1-2):9. Dispersing cycle is repeated at least twice while draining after each cycle separated water. Finally, inverted emulsion is settled to residual water content 1%.

EFFECT: increased emulsion destruction efficiency due to increased degree of oil dehydration and lowered concentration of suspended impurities.

2 ex

FIELD: chemical technology.

SUBSTANCE: invention relates to agents used in destruction of aqueous-petroleum emulsions and can be used in dehydrating petroleum in industrial units in petroleum preparing. The composition for destruction of aqueous-petroleum emulsions and treatment of sewage waters comprises dimethyl phosphite, nitrogen-containing compound, non-ionogenic surface-active substance, Phosphenox H-12, solvent and alkylbenzene sulfoacid in the following ratio of components, wt.-%: dimethyl phosphite, 0.01-2.0; nitrogen-containing compound, 0.2-2.0; non-ionogenic surface-active substance, 25.0-70.0; Phosphenox H-12, 1.0-15.0; alkylbenzene sulfoacid, 0.1-15.0, and solvent, the balance. Invention provides the development of effective de-emulsifying agent of aqueous-petroleum emulsion showing the complex effect for high-viscous oils.

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3 tbl, 20 ex

FIELD: crude oil treatment.

SUBSTANCE: oil emulsion is preliminarily separated from drainage water and, after addition of demulsifier, oil desalting process is carried out by washing moving emulsion under dispersing conditions with a washing fluid in at least two steps. Volume of washing fluid added in the first desalting step is larger than that in the second step by a factor of 2.0-2.5. Washing fluid is notably 3-10% aqueous sodium nitrate solution, which is preheated before addition to at least 45°C in both desalting steps. In the first step, oil is subjected to hot settling preferably for 2 h and, in the second step, 3 h. Demulsifier utilized is based on oil-soluble surfactants added in amounts 25 to 55 g/t.

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7 cl, 2 ex

FIELD: petroleum extracting and petroleum processing industry.

SUBSTANCE: invention relates to preparing petroleum-soluble composite possessing high demulsifying effect. The composite is prepared by simple components mixing. As an active base the composite comprises sodium salt of oxyethylated isononylphenol carboxymethylate with the oxyethylation degree value 10-12. As a low-temperature solvent the composition comprises methanol-aldehyde fraction (waste in production of butyl alcohols) and water in the following ratio of components, wt.-%: oxyethylated isononylphenol carboxymethylate sodium salt, 45.0-55.0; methanol-aldehyde fraction, 43.5-50.0, and water, the balance, up to 100. Invention provides high demulsified capacity of the composition with low solidification point.

EFFECT: improved and valuable properties of composite.

2 ex

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